Electrochemical modified electrodes based on metal-salen complexes

A general view of the electroanalytical applications of metal-salen complexes is discussed in this review. The family of Schiff bases derived from ethylenediamine and ortho-phenolic aldehydes (N,N'-ethylenebis(salicylideneiminato) - salen) and their complexes of various transition metals, such as Al, Ce, Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo, Ni, and V have been used in many fields of chemical research for a wide range of applications such as catalysts for the oxygenation of organic molecules, epoxidation of alkenes, oxidation of hydrocarbons and many other catalyzed reactions; as electrocatalyst for novel sensors development; and mimicking the catalytic functions of enzymes. A brief history of the synthesis and reactivity of metal-salen complexes will be presented. The potentialities and possibilities of metal-Salen complexes modified electrodes in the development of electrochemical sensors as well as other types of sensors, their construction and methods of fabrication, and the potential application of these modified electrodes will be illustrated and discussed.

Thermoplastic starch/natural rubber blends

Thermoplastic starch/natural rubber polymer blends were prepared using directly natural latex and cornstarch. The blends were prepared in an intensive batch mixer at 150 degreesC, with natural rubber content varying from 2.5 to 20%. The blends were characterised by mechanical analysis (stress-strain) and by scanning electron microscopy. The results revealed a reduction in the modulus and in tensile strength, becoming the blends less brittle than thermoplastic starch alone. Phase separation was observed in some compositions and was dependent on rubber and on plasticiser content (glycerol). Increasing plasticiser content made possible the addition of higher amounts of rubber. The addition of rubber was, however, limited by phase separation the appearance of which depended on the glycerol content. Scanning electron microscopy showed a good dispersion of the natural rubber in the continuos phase of thermoplastic starch matrix. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Electrochemical sensor for sulfite determination based on a nanostructured copper-salen film modified electrode

The electrochemical preparation described herein involved the electrocatalytic oxidation of sulfite on a platinum electrode modified with nanostructured copper salen (salen=N,N'-ethylenebis(salicylideneiminato)) polymer films. The complex was prepared and electropolymerized at a platinum electrode in a 0.1 mol L-1 solution of tetrabutylammonium perchlorate in acetonitrile by cyclic voltammetry between 0 and 1.4V vs. SCE. After cycling the modified electrode in a 0.50 mol L-1 KCI solution, the estimated surface concentration was found to be equal to 2.2 x 10(-9) Mol cm(-2). This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the copper(II)/copper(III) couple. The potential peaks of the modified electrode in the electrolyte solution (aqueous) containing the different anions increase with the decrease of the ionic radius, demonstrating that the counter-ions influence the voltammetric behavior of the sensor. The potential peak was found to be linearly dependent upon the ratio [ionic charge]/[ionic radius]. The oxidation of the sulfite anion was performed at the platinum electrode at +0.9V vs. SCE. However, a significant decrease in the overpotential (+0.45V) was obtained while using the sensor, which minimized the effect of oxidizable interferences. A plot of the anodic current vs. the sulfite concentration for chronoamperometry (potential fixed = +0.45V) at the sensor was linear in the 4.0 x 10(-6) to 6.9 x 10(-5) mol L-1 concentration range and the concentration limit was 1.2 x 10(-6) mol L-1. The reaction order with respect to sulfite was determined by the slope of the logarithm of the current vs. the logarithm of the sulfite concentration. (C) 2009 Elsevier Ltd. All rights reserved.

Application of the Potentiometric Stripping Analysis with Constant Current for the Determination of Lithium Ions Using a Spinel-Type Manganese (IV) Oxide-Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Development of an electrochemical sensor for determination of dissolved oxygen by nickel-salen polymeric film modified electrode

An amperometric oxygen sensor based on a polymeric nickel-salen (salen = N,N'-ethylene bis(salicylideneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at platinum electrode in acetonitrile/tetrabutylammonium perchlorate by cyclic voltammetry. The voltammetric behavior of the sensor was investigated in 0.5 mol L-1 KCl solution in the absence and presence of molecular oxygen. Thus, with the addition of oxygen to the solution, the increase of cathodic peak current (at -0.25 V vs. saturated calomel electrode (SCE)) of the modified electrode was observed. This result shows that the nickel-salen film on electrode surface promotes the reduction of oxygen. The reaction can be brought about electrochemically, where the nickel(II) complex is first reduced to a nickel(I) complex at the electrode surface. The nickel(I) complex then undergoes a catalytic oxidation by the molecular oxygen in solution back to the nickel(II) complex, which can then be electrochemically re-reduced to produce an enhancement of the cathodic current. The Tafel plot analyses have been used to elucidate the kinetics and mechanism of the oxygen reduction. A plot of the cathodic current vs. the dissolved oxygen concentration for chronoamperometry (fixed potential = -0.25 V vs. SCE) at the sensor was linear in the 3.95-9.20 mg L-1 concentration range and the concentration limit was 0.17 mg L-1 O-2. The proposed electrode is useful for the quality control and routine analysis of dissolved oxygen in commercial samples and environmental water. The results obtained for the levels of dissolved oxygen are in agreement with the results obtained with a commercial O-2 sensor. (C) 2012 Elsevier B.V. All rights reserved.

Determination of Analgesics (Dipyrone and Acetaminophen) in Pharmaceutical Preparations by Cyclic Voltammetry at a Copper(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Phytase immobilization on modified electrodes for amperometric biosensing

Phytase (myo-inositol hexaphosphate phosphohydrolase) and phytic acid (myo-inositol hexaphosphate) play an important environmental role, in addition to being a health issue in food industry. Phytic acid is antinutritional due to its ability to chelate metal ions and may also react with proteins decreasing their bioavailability. In this work, we produced biosensors with phytase immobilized in Layer-by-Layer (LbL) films, which could detect phytic acid with a detection limit of 0.19 mmol L-1, which is sufficient to detect phytic acid in seeds of grains and vegetables. The biosensosrs consisted of LbL films containing up to eight bilayers of phytase alternated with poly(allylamine) hydrochloride (PAH) deposited onto an indium-tin oxide (ITO) substrate modified with Prussian Blue. Amperometric detection was conducted in an acetate buffer solution (at pH 5.5) at room temperature, with the biosensor response attributed to the formation of phosphate ions. In subsidiary experiments with the currents measured at 0.0 V (vs. SCE), we demonstrated the absence of effects from some interferents, pointing to a good selectivity of the biosensor. (c) 2007 Elsevier B.V. All rights reserved.

Electrochemical characterization of the paste carbon modified electrode with KSr2Ni0.75Nb4.25O15-delta solid in catalytic oxidation of the dipyrone

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

Structure and Physical Properties of EVA/Starch Precursor Materials for Foaming Applications

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

Thermomechanical characterization of PVDF and P(VDF-TrFE) blends containing corn starch and natural rubber

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

Development of an electrochemical sensor for potassium ions based on KSr(2)Nb(5)O(15) modified electrode

In the work described by this paper, we studied the development of a selective potassium ion sensor constituted of a carbon paste electrode modified (CPEM) with a novel KSr(2)Nb(2)O(15). The material KSr(2)Nb(2)O(15) is an oxide with the tetragonal tungsten bronze structure (TTB) type are in forefront both in the area of research as well as in industrial applications. The sensor response to potassium ions was linear in the concentration range 1.26 x 10(-5) at 1.62 x 10(-3) mol L(-1) (E (mV) = 32.7 + 51.1 log [K(+)]). The sensor based KSr(2)Nb(2)O(15), of the TTB-type presented very good potentiometric response, with a slope of 51.1 mV/dec (at 25 degrees C) and detection limit for the potassium ions of 7.27 x 10(-5) mol.L(-1)

An electrochemical sensor for dipyrone determination based on nickel-salen film modified electrode

An amperometric dipyrone sensor based on a polymeric nickel-salen (salen = N,N'-ethylenebis(salicydeneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at a platinum electrode in acetonitrile/tetrabuthylamonium perchlorate by cyclic voltammetry. After cycling the modified electrode in a 0.50 mol L-1 KCl solution, the estimated surface concentration was found to be equal to 1.29 x 10(-9) mol cm(-2). This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the nickel(II)/nickel(III) couple. A plot of the anodic current versus the dipyrone concentration for chronoamperometry (potential fixed = +0.50 V) at the sensor was linear in the 4.7 x 10(-6) to 1.1 x 10(-4) mol L-1 concentration range and the concentration limit was 1.2 x 10(-6) mol L-1. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

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

Efeito da concentração do amido de milho na liberação de paracetamol de comprimidos

Este trabalho avaliou a influência da concentração de amido de milho nas características físicas e na liberação in vitro de paracetamol a partir de comprimidos. Os granulados foram analisados quanto à granulometria e densidades aparentes bruta e compactada e os comprimidos quanto ao peso médio, espessura, dureza, friabilidade, tempo de desintegração. Os comprimidos foram preparados a partir de granulados obtidos por granulação a úmido, utilizando cozimento de amido a 10% como agente granulante, segundo três formulações. Embora os comprimidos obtidos tenham apresentado características dentro dos limites farmacopéicos, os resultados indicam que variações da concentração de amido provocam diferenças nos diversos parâmetros físicos estudados. Concentração mais alta de amido em pó dá origem, provavelmente, à interação entre os componentes da fórmula, interferindo na liberação in vitro do fármaco. Isto demonstra a importância de se otimizar a concentração dos adjuvantes numa formulação de comprimidos, pois, embora uma pequena variação nesta concentração não exerça efeito significativo no tempo de desintegração, a quantidade de fármaco liberado pode ser substancialmente alterada.

Physical properties of pectin-high amylose starch mixtures cross-linked with sodium trimetaphosphate

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)