Silsesquioxane as a New Building Block Material for Modified Electrodes Fabrication and Application as Neurotransmitters Sensors

Nanostructured films comprising a 3-n-propylpyridiniunn silsesquioxane polymer (designated as SiPy(+)Cl(-)) and copper (II) tetrasulfophthalocyanine (CuTsPc) were produced using the Layer-by-Layer technique (LbL). To our knowledge this is the first report on the use of silsesquioxane derivative polymers as building blocks for nanostructured thin films fabrication. Deposition of the multilayers were monitored by UV-Vis spectroscopy revealing the linear increment in the absorbance of the Q-band from CuTsPc at 617 nm with the number of SiPy(+)Cl(-)/CuTsPc or CuTsPc/SiPy(+)Cl(-) bilayers. FTIR analyses showed that specific interactions between SiPy+Cl- and CuTsPc occurred between SO(3)(-) groups of tetrasulfophthalocyanine and the pyridinium groups of the polycation. Morphological studies were carried out using the AFM technique, which showed that the roughness and thickness of the films increase with the number of bilayers. The films displayed electroactivity and were employed to detection of dopamine (DA) and ascorbic acid (AA) using cyclic voltammetry, at concentrations ranging from 1.96 x 10(-4) to 1.31 x 10(-3) molL(-1). The number and the sequence of bilayers deposition influenced the electrochemical response in presence of DA and AA. Using differential pulse technique, films comprising SiPy(+)/CuTsPc were able to distinguish between DA and ascorbic acid (AA), with a potential difference of approximately with 500 mV, in the concentration range of 9.0 x 10(-5) to 2.0 x 10(-4) molL(-1), in pH 3.0.

Development of impedimetric and optical calcium biosensor by using modified gold electrode with porcine S100A12 protein

We describe the development of a label free method to analyze the interactions between Ca(2+) and the porcine S100A12 protein immobilized on polyvinyl butyral (PVB). The modified gold electrodes were characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and surface plasmon resonance (SPR) techniques. SEM analyses of PVB and PVB-S100A12 showed a heterogeneous distribution of PVB spherules on gold surface. EIS and CV measurements have shown that redox probe reactions on the modified gold electrodes were partially blocked due the adsorption of PVB-S100A12, and confirm the existence of a positive response of the immobilized S100Al2 to the presence of calcium ions. The biosensor exhibited a wide linear response to Ca(2+) concentrations ranging from 12.5 to 200 mM. The PVB-S100A12 seems to be bound to the gold electrode surface by physical adsorption: we observed an increase of 1184.32 m degrees in the SPR angle after the adsorption of the protein on the PVB surface (in an indication that 9.84 ng of S100A12 are adsorbed per mm(2) of the Au-PVB electrode), followed by a further increase of 581.66 m degrees after attachment of the Ca(2+) ions. In addition, no SPR response is obtained for non-specific ions. These studies might be useful as a platform for the design of new reusable and sensitive biosensing devices that could find use in the clinical applications. (C) 2010 Elsevier B.V. All rights reserved.

Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Application of Microelectrode Voltammetry to Study the Properties of Surfactant Solutions: Alkyltrimethylammonium Bromides

Microelectrode cyclic voltammetry (MV) has been employed to investigate the micellar properties of solutions of homologous alkyltrimethylammonium bromides, RMe(3)ABr, R = C(10), C(12), and C(14), in water and in the presence of added NaBr. The micellar self-diffusion coefficient was calculated from the limiting current for the reversible electron transfer of micelle-bound ferrocene. From the values of this property, other parameters were calculated, including the micellar hydrodynamic radius, RH, and aggregation number, N(agg); the latter was also theoretically calculated. We determined the values of the diffusion coefficient as a function of various experimental variables and observed the following trends: The diffusion coefficient decreases as a function of increasing surfactant concentration (no additional electrolyte added); it decreases as a function of increasing surfactant concentration at fixed NaBr concentration; and it shows a complex dependence (increase then decrease) on the NaBr concentration at a fixed RMe(3)ABr concentration. The value of the intermicellar interaction parameter decreases and then increases as a function of increasing NaBr concentration. These results are discussed in terms of intermicellar,interactions and the effect of NaBr on the micellar surface charge density and sphere-to-rod geometry change. The NaBr concentration required to induce the latter change increases rapidly as a function of decreasing the length of R: no geometry change was detected for C(10)Me(3)ABr. Values of N(agg) increase as I function of increasing the length of R and are in good agreement with both literature values and values that were calculated theoretically. Thus, MV is a convenient and simple technique for obtaining fundamental properties of surfactant solutions, including additive-induced changes of micellar parameters (N(agg)) and morphology changes.

A New Insight on the Preparation of Stabilized Alpha-Nickel Hydroxide Nanoparticles

Nickel hydroxide can provide an outstanding cathode material in alkaline secondary batteries, however the progressive decrease of the charge capacity as a function of the number of oxidation/reduction cycles is a challenging problem to be solved. New improvements on the electrochemical properties of electrode materials can be achieved by exploiting the much better performance of alpha-nickel hydroxide. Such materials were obtained in a stable form by sol-gel method and characterized by thermogravimetric analyses, UV-Vis spectroscopy, X-ray diffractometry, scanning and transmission electron microscopy, cyclic voltammetry and electrochemical quartz crystal microbalance techniques. The results revealed not only the formation of the alpha-Ni(OH)(2) phase, but also a much better electrochemical reversibility and stability as compared with similar materials obtained by electrochemical precipitation method.

Electro-oxidation of ethanol on PtSn/CeO(2)-C electrocatalyst

PtSn/CeO(2)-C electrocatalyst was prepared in a single step by an alcohol-reduction process using ethylene glycol as solvent and reducing agent and CeO(2) (15 wt%) and Vulcan XC72 (85 wt%) as supports. The performance for ethanol oxidation was investigated by cyclic voltammetry and in situ FTIR spectroscopy. The electrocatalytic activity of the PtSn/CeO(2)-C electrocatalyst was higher than that of the PtSn/C electrocatalyst. FTIR studies for ethanol oxidation on PtSn/C electrocatalyst showed that acetaldehyde and acetic acid were the principal products formed, while on PtSn/CeO(2)-C electrocatalyst the principal products formed were CO(2) and acetic acid.

The influence of acetic acid on the ethanol electrooxidation on a platinum electrode

In the presented work, the evaluation of the influence of acetic acid in the electrochemical environment on the ethanol electro-oxidation reaction on a polycrystalline platinum electrode is presented for the first time. Using cyclic voltammetry. chronoamperometry and in situ Fourier Transformed IR spectroscopy (FTIR) it was demonstrated that an inhibition of the ethanol oxidation reaction occurs for bulk acetic acid concentrations of the order 0.1 mu mol L(-1) -5 mmol L(-1). This inhibition effect is related to the decrease of CO(2) and acetaldehyde production as confirmed by spectroscopic results. (C) 2011 Elsevier B.V. All rights reserved.

Nitrate reduction on Pt single crystals with Pd multilayer

Nitrate reduction on palladium multilayers deposited on platinum single crystal electrodes was studied by cyclic voltammetry and FTIR spectroscopy in acid and alkaline media. The results are compared with those obtained with bulk palladium single crystals. The reaction is sensitive to the electrode surface structure, the reactivity depending on the solution pH. In acid solution nitrate was reduced at potentials below the potential of zero total charge (pztc), when the electrode is negatively charged. Competition between nitrate, hydrogen and anion adsorption and NO formation and accumulation at the surface are proposed as the main reasons for the slow reaction rate. On the bulk palladium single crystal electrodes, NO formation leads to a fast blockage of the surface resulting in a very low activity for nitrate reduction. In alkaline solution, nitrate is reduced at more positive potentials with significantly higher current being measured on the Pd multilayer on Pt(100) electrode. (C) 2008 Elsevier Ltd. All rights reserved.

On-line mass spectrometry of the electro-oxidation of methanol in acidic media on tungsten carbide

The electro-oxidation of methanol at supported tungsten carbide (WC) nanoparticles in sulfuric acid solution was studied using cyclic voltammetry, potentiostatic measurements, and differential electrochemical mass spectroscopy (DEMS). The catalyst was prepared by a sonochemical method and characterized by X-ray diffraction. Over the WC catalyst, the oxidation of methanol (1 M in a sulfuric acid electrolyte) begins at a potential below 0.5 V/RHE during the anodic sweep. During potentiostatic measurements, a maximum current of 0.8 mA mg(-1) was obtained at 0.4 V. Measurements of DEMS showed that the methanol oxidation reaction over tungsten carbide produces CO2 (m/z=44); no methylformate (m/z=60) was detected. These results are discussed in the context of the continued search for alternative materials for the anode catalyst of direct methanol fuel cells.

Electroanalytical determination of promethazine hydrochloride in pharmaceutical formulations on highly boron-doped diamond electrodes using square-wave adsorptive voltammetry

The electrochemical oxidation of promethazine hydrochloride was made on highly boron-doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square-wave adsorptive voltammetry results obtained in BR buffer showed two well-defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s(-1), step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96 x 10(-7) to 4.76 x 10(-6) mol L-1, and calculated detection limits of 2.66 x 10(-8) mol L-1 (8.51 mu g L-1) for peak 1 and of 4.61 x 10(-8) mol L-1 (14.77 mu g L-1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. ne applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.

Electrodeposition and characterization of thin selenium films modified with lead ad-atoms

The deposition and characterization of Se films doped with Pb underpotentially deposited (UPD) ad-atoms was studied in this work. The employed experimental techniques were cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, UV-vis spectroscopy and atomic force microscopy. The initial deposition of Se film by chronoamperometry yielded a thin film composed of approximately 700 layers. The Pb UPD on Se was achieved by chronoamperometry in a potential value previously determined in voltammetric experiments. This deposition yielded a deposition charge of approximately 7.5% of the total one. The film resistance altered from 320 Omega cm(2) for Se to 65 Omega cm(2) for the Se/Pb one. Flat band potential values and number of acceptors and donors were also calculated for both films and the values obtained were + 0.95 and -0.51 V for Se and Se/Pb, respectively. The Se coating presented 1.2 x 10(17) cm(3) acceptors while the Se/Pb one presented 3.2 x 10(17) cm(3) donors. The band gap values for both films were 2.4 eV and 1.9 eV, correspondingly. (C) 2008 Elsevier B.V. All rights reserved.

Carbon-dispersed Pt-Rh nanoparticles for ethanol electro-oxidation. Effect of the crystallite size and of temperature

This work presents results of studies of carbon-dispersed Pt-Rh (1:1) nanoparticles as electrocatalysts for the ethanol electro-oxidation. The influences of the crystallite size and the cell temperature on the yields of CO2, acetaldehyde and acetic acid are investigated. Metal nanoparticles were prepared by two different routes: (1) impregnation on carbon powder followed by thermal reduction on hydrogen atmosphere and (2) chemical reduction of the precursor salts. The surface active area and the electrochemical activity of the electrocatalysts were estimated by CO stripping and cyclic voltammetry in the absence and in the presence of ethanol, respectively. Reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR) and Differential Electrochemical Mass Spectrometry (DEMS). The electrochemical stripping of CO and the electrochemical ethanol oxidation were slightly faster on the Pt-Rh electrocatalysts compared to Pt/C. Also, in situ FTIR spectra and DEMS measurements evidenced that the CO2/acetaldehyde and the CO2/acetic acid ratios are higher for the Pt-Rh/C materials in relation to Pt/C. This was ascribed to the activation of the C-C bond breaking by Rh, this being more prominent for the materials with smaller crystallite sizes. (C) 2008 Elsevier B.V. All rights reserved.

Electrocatalytic behavior of glassy carbon electrodes modified with multiwalled carbon nanotubes and cobalt phthalocyanine for selective analysis of dopamine in presence of ascorbic acid

This work describes the development, electrochemical characterization and utilization of a cobalt phthalocyanine modified carbon nanotube electrode for the quantitative determination of dopamine in 0.2 mol L-1 phosphate buffer contaminated with high concentration of ascorbic acid. The electrode surface was analyzed by cyclic voltammetry and electrochemical impedance spectroscopy which showed a modified surface presenting a charge transfer resistance of 500 Omega, against the 16.46 k Omega value found for the bare glassy carbon surface. A pseudo rate constant value of 5.4 x 10(-4) cm s(-1) for dopamine oxidation was calculated. Voltammetric experiments showed a shift of the peak potential of DA oxidation to less positive value at 390 mV as compared with that of a bare GC electrode at 570 mV. The electrochemical determination of dopamine, in presence of ascorbic acid in concentrations up to 0.1 mol L-1 by differential pulse voltarnmetry, yielded a detection limit as low as 2.56 x 10(-7) mol L-1.

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film-modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at -50 mV vs. SCE by electrochemical oxidation using differential pulse voltamtnetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly-copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83-9.90 mu mol L(-1), with detection limit 12.2 nmol L(-1) (2.02 mu g L(-1))

A Graphite-Polyurethane Composite Electrode for the Analysis of Furosemide

A graphite-polyurethane composite electrode has been used for the determination of furosemide, a antihypertensive drug, in pharmaceutical samples by anodic oxidation. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrooxidation process at +1.0 V vs. SCE over a wide pH range, with the result that no adsorption of analyte or products occurs, unlike at other carbon-based electrode materials. Quantification was carried out using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry. Linear ranges were determined (up to 21 mu mol L-1 with cyclic voltammetry) as well as limits of detection (0.15 mu mol L-1 by differential pulse voltammetry). Four different types of commercial samples were successfully analyzed. Recovery tests were performed which agreed with those obtained by spectrophotometric evaluation. The advantages of this electrode material for repetitive analyzes, due to the fact that no electrode surface renewal is needed owing to the lack of adsorption, are highlighted.