18 resultados para SECM


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In order to lower the excessive costs of metallic prosthesis materia Is alternatives to Ti and Ti alloys have been searched. in this study, the corrosion resistance of the DIN 1.4575 superferritic stainless steel, either solution annealed or solution annealed and aged at 475 degrees C for periods varying from 100 to 1080 h, was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods in Hanks` solution. The solution annealed and the aged for 1080 h samples were also tested using scanning electrochemical microscopy (SECM) in a 0.1 mol/L NaCl solution at 25 degrees C. The EIS results showed that the corrosion resistance of the DIN 1.4575 steel decreases with heat treatment time at 475 degrees C probably due to alpha prime formation. Besides the diminution of the overall impedance values, the low frequency limit of the Nyquist diagrams show a progressive change from an almost capacitive response to a resistive behavior as the heat treatment time increases. Pitting corrosion resistance also decreased with aging time at 475 degrees C.

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Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

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We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.

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Los requerimientos de métodos analíticos que permitan realizar determinaciones más eficientes en diversas ramas de la Química, así como el gran desarrollo logrado por la Nanobiotecnología, impulsaron la investigación de nuevas alternativas de análisis. Hoy, el campo de los Biosensores concita gran atención en el primer mundo, sin embargo, en nuestro país es todavía un área de vacancia, como lo es también la de la Nanotecnología. El objetivo de este proyecto es diseñar y caracterizar nuevos electrodos especialmente basados en el uso de nanoestructuras y estudiar aspectos básicos de la inmovilización de enzimas, ADN, aptámeros, polisacáridos y otros polímeros sobre dichos electrodos a fin de crear nuevas plataformas de biorreconocimiento para la construcción de (bio)sensores electroquímicos dirigidos a la cuantificación de analitos de interés clínico, farmaco-toxicológico y ambiental.Se estudiarán las propiedades de electrodos de C vítreo, Au, "screen printed" y compósitos de C modificados con nanotubos de C (CNT) y/o nanopartículas (NP) de oro y/o nanoalambres empleando diversas estrategias. Se investigarán nuevas alternativas de inmovilización de las biomoléculas antes mencionadas sobre dichos electrodos, se caracterizarán las plataformas resultantes y se evaluarán sus posibles aplicaciones analíticas al desarrollo de biosensores con enzimas y ADNs como elementos de biorreconocimiento. Se funcionalizarán CNT con polímeros comerciales y sintetizados en nuestro laboratorio modificados con moléculas bioactivas. Se diseñarán y caracterizarán nuevas arquitecturas supramoleculares basadas en el autoensamblado de policationes, enzimas y ADNs sobre Au. Se evaluarán las propiedades catalíticas de NP de magnetita y de perovskitas de Mn y su aplicación al desarrollo de biosensores enzimáticos. Se diseñarán biosensores que permitan la detección altamente sensible y selectiva de secuencias específicas de ADNs de interés clínico. Se estudiará la interacción de genotóxicos con ADN (en solución e inmovilizado) y se desarrollarán biosensores que permitan su cuantificación. Se construirán biosensores enzimáticos para la cuantificación de bioanalitos, especialmente glucosa, fenoles y catecoles, y sensores electroquímicos para la determinación de neurotransmisores, ácido úrico y ácido ascórbico. Se diseñarán nuevos aptasensores electroquímicos para la cuantificación de biomarcadores, comenzando por lisozima y trombina y continuando con otros de interés regional/nacional.Se emplearán las siguientes técnicas: voltamperometrías cíclica (CV), de pulso diferencial (DPV) y de onda cuadrada (SWV); "stripping" potenciométrico a corriente constante (PSA); elipsometría; microbalanza de cristal de cuarzo con cálculo de pérdida de energía por disipación (QCM-D); resonancia de plasmón superficial con detección dual (E-SPR); espectroscopía de impedancia electroquímica (EIE); microscopías de barrido electroquímico (SECM), de barrido electrónico (SEM), de transmisión (TEM) y de fuerzas atómicas (AFM); espectrofotometría UV-visible; espectroscopías IR, Raman, de masas, RMN.Se espera que la inclusión de los CNT y/o de las NP metálicas y/o de los nanoalambres en los diferentes electrodos permita una mejor transferencia de carga de diversos analitos y por ende una detección más sensible y selectiva de bioanalitos empleando enzimas, ADN y aptámeros como elementos de biorreconocimiento. Se espera una mayor eficiencia en los aptasensores respecto de los inmunosensores, lo que permitirá la determinacion selectiva de diversos biomarcadores. La modificación de electrodos con nanoestructuras posibilitará la detección altamente sensible y selectiva del evento de hibridación. La respuesta obtenida luego de la interacción de genotóxicos con ADN permitirá un mejor conocimiento de la asociación establecida, de la cinética y de las constantes termodinámicas. Los neurotransmisores podrán ser determinados a niveles nanomolares aún en muestras complejas.

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Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E-oc) and in the passive region (+0.30 V-ECS) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L-1 H3BO3 + 0.075 mol L-1 Na2B4O7 (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell. (c) 2007 Elsevier Ltd. All rights reserved.

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Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E-oc) and in the passive region (+0.30 V-ECS) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L-1 H3BO3 + 0.075 mol L-1 Na2B4O7 (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell. (c) 2007 Elsevier Ltd. All rights reserved.

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In this work, we present an investigation on the thickness of the eroded enamel layer in tooth samples after exposure to citric and hydrochloric acid by using Scanning Electrochemical Microscopy (SECM). Approaching curves with typical negative feedback behavior were obtained in enamel samples for evaluation of topographic changes. In a control experiment, SECM images showed no significant difference in the current monitored during the scan, implying that enamel demineralization did not occur in mineral water medium. Topographic SECM images obtained after contact with citric and hydrochloric acid for different periods of time showed a significant increase in the current relative to a previously protected surface, indicating the structural loss of enamel. The thickness of the enamel layer eroded after contact with hydrochloric acid was significantly higher when compared to the one obtained with citric acid. Hence, our results showed that the enamel acid erosion is a relatively fast process, which is strongly dependent on parameters such as pH, time, acid strength and acid concentration.

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Cancer is one of the principal causes of death in the world; almost 8.2 million of deaths were counted in 2012. Emerging evidences indicate that most of the tumors have an increased glycolytic rate and a detriment of oxidative phosphorylation to support abnormal cell proliferation; this phenomenon is known as aerobic glycolysis or Warburg effect. This switching toward glycolysis implies that cancer tissues metabolize approximately tenfold more glucose to lactate in a given time and the amount of lactate released from cancer tissues is much greater than from normal ones. In view of these fundamental discoveries alterations of the cellular metabolism should be considered a crucial hallmark of cancer. Therefore, the investigation of the metabolic differences between normal and transformed cells is important in cancer research and it might find clinical applications. The aim of the project was to investigate the cellular metabolic alterations at single cell level, by monitoring glucose and lactate, in order to provide a better insight in cancer research. For this purpose, electrochemical techniques have been applied. Enzyme-based electrode biosensors for lactate and glucose were –ad hoc- optimized within the project and used as probes for Scanning Electrochemical Microscopy (SECM). The UME biosensor manufacturing and optimization represented a consistent part of the work and a full description of the sensor preparation protocols and of the characterization methods employed is reported. This set-up (SECM used with microbiosensor probes) enabled the non-invasive study of cellular metabolism at single cell level. The knowledge of cancer cell metabolism is required to design more efficient treatment strategies.