A novel disposable electrochemical microcell: construction and characterization

An alternative technique for the fabrication of disposable electrochemical microcells containing working, reference and auxiliary electrodes on a single device is reported. The procedure is based on thermal-transfer of toner masks onto CD-R (recordable compact discs) gold surfaces to define the layout of the electrodes (contour). In a subsequent step, the layout is manually painted with a permanent marker pen. The unprotected gold surface is conveniently etched (chemical corrosion) and the ink is then easily removed with ethanol, generating gold surfaces without contamination. The final and reproducible area of the electrodes is defined by heat transference of a second toner mask. Silver epoxy is deposited on one of the gold bands which is the satisfactorily used as reference electrode. These microcells were electrochemically characterized by cyclic, linear, and square wave voltammetry, and several electroactive species were used as model systems. The area reproducibility of the electrodes for different microcells was studied and a relative standard deviation better than 1,0% (n = 10) was obtained. Disposable electrochemical microcells were successfully used in analysis of liquid samples with volumes lower than 200 µL and good stability and reproducibility (RSD less than 2.0%) were achieved. These microcells were also evaluated for quantification of paracetamol and dipyrone in pharmaceutical formulations.Este trabalho apresenta uma técnica alternativa de microfabricação para construção de microcélulas eletroquímicas descartáveis contendo os eletrodos de trabalho, auxiliar e de referência em um único dispositivo. Trata-se de um processo simples no qual a termo-transferência de máscaras de toner sobre superfícies de ouro obtidas a partir de discos compactos graváveis (CD-R) definem o formato dos eletrodos (contornos). Numa etapa seguinte, o formato é manualmente coberto com tinta usando uma caneta de retroprojetor. A superfície de ouro não protegida pela tinta é convenientemente removida (corrosão química) e a tinta, por sua vez, é facilmente removida com etanol gerando superfícies de ouro sem contaminação. A área final e reprodutível dos eletrodos é definida pela termo-transferência de uma segunda máscara de toner. O eletrodo de referência é obtido por meio de uma deposição manual de cola de prata sobre uma banda de ouro. As microcélulas foram eletroquimicamente caracterizadas usando as técnicas de voltametria cíclica, voltametria linear e voltametria de onda quadrada e várias espécies eletroativas como sistemas modelo. A reprodutibilidade de área dos eletrodos para diferentes microcélulas foi estudada e um desvio-padrão relativo melhor do que 1,0% foi obtido. As microcélulas descartáveis foram usadas com sucesso para a análise de amostras em volumes menores que 200 µL demonstrando boa estabilidade e reprodutibilidade (RSD menor que 2,0%). Essas microcélulas também foram avaliadas para a quantificação de paracetamol e dipirona em formulações farmacêuticas.(FAPEMIG) Fundação de Amparo à Pesquisa do Estado de Minas GeraisConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Fast batch injection analysis system for on-site determination of ethanol in gasohol and fuel ethanol

AbstractA simple, accurate and fast (180injectionsh−1) batch injection analysis (BIA) system with multiple-pulse amperometric detection has been developed for selective determination of ethanol in gasohol and fuel ethanol. A sample aliquot (100μL) was directly injected onto a gold electrode immersed in 0.5molL−1 NaOH solution (unique reagent). The proposed BIA method requires minimal sample manipulation and can be easily used for on-site analysis. The results obtained with the BIA method were compared to those obtained by gas-chromatography and similar results were obtained (at 95% of confidence level)

Simultaneous determination of ethanol and methanol in fuel ethanol using cyclic voltammetry

AbstractA new and simple strategy for the simultaneous determination of ethanol and methanol in fuel ethanol using cyclic voltammetry at a gold electrode is reported. A fuel ethanol aliquot was added into an electrochemical cell containing 0.5molL−1 NaOH and 0.1% (v/v) of methanol as the electrolyte and both analytes were determined using cyclic voltammetry. Ethanol was selectively detected at +0.19V and both compounds were detected at +1.20V. Current subtraction (using a correction factor) could be used for the selective determination of methanol. The limits of detection were estimated to be 0.028% and 0.045% (v/v) for ethanol and methanol, respectively. The proposed method presented similar results to those obtained by gas chromatography at a 95% confidence level

Behaviour of the antioxidant tert-butylhydroquinone on the storage stability and corrosive character of biodiesel

AbstractThe behaviour of the antioxidant tert-butylhydroquinone (TBHQ) on the storage stability of biodiesel was investigated. Storage conditions were simulated through static immersion corrosion tests in biodiesel (with and without TBHQ) using copper coupons. Measurements of oxidation stability (Rancimat induction period) and metal release at different stages of corrosion were performed. After 24h of the static immersion test, the neat and TBHQ-doped biodiesels presented induction times below the EN 14214 limit (6h). Copper release was more intense in the neat biodiesel which evidenced that TBHQ retarded the corrosion process as a corrosion inhibitor. Ion trap–time-of-flight mass spectrometry (IT–TOF-MS) revealed the presence of considerable amounts of tert-butylquinone (TBQ) in the TBHQ-doped biodiesel exposed to the corrosion process. As TBHQ molecules adsorb at the copper surface to inhibit corrosion, these molecules are catalytically oxidised to TBQ. IT–TOF-MS also indicated the formation of new molecules of high molecular weight only presented in the TBHQ-doped biodiesel deteriorated by the corrosion process. MS2 spectra gave clear evidence of the formation of new complexes between free radicals of long-chain molecules (fatty acid derivatives) and TBQ radicals during biodiesel deterioration

Signatures of Galaxy-Cluster Interactions: Spiral Galaxy Rotation Curve Asymmetry, Shape, and Extent

The environmental dependencies of the characteristics of spiral galaxy rotation curves are studied in this work. We use our large, homogeneously collected sample of 510 cluster spiral galaxy rotation curves to test the claim that the shape of a galaxy's rotation curve strongly depends on its location within the cluster, and thus presumably on the strength of the local intracluster medium and on the frequency and strength of tidal interactions with the cluster and cluster galaxies. Our data do not corroborate such a scenario, consistent with the fact that Tully-Fisher residuals are independent of galaxy location within the cluster; while the average late-type spiral galaxy shows more rise in the outer parts of its rotation curve than does the typical early-type spiral galaxy, there is no apparent trend for either subset with cluster environment. We also investigate as a function of cluster environment rotation curve asymmetry and the radial distribution of H II region tracers within galactic disks. Mild trends with projected cluster-centric distance are observed: (i) the (normalized) radial extent of optical line emission averaged over all spiral galaxy types shows a 4%+/-2% increase per Mpc of galaxy-cluster core separation, and (ii) rotation curve asymmetry falls by a factor of two between the inner and outer cluster for early-type spirals (a negligible decrease is found for late-type spirals). Such trends are consistent with spiral disk perturbations or even the stripping of the diffuse, outermost gaseous regions within the disks as galaxies pass through the dense cluster cores.Comment: 17 pages; to appear in the April 2001 Astronomical Journa

Towards a tidal loading model for the Argentine-German Geodetic Observatory (La Plata)

We present a regionalized model of ocean tidal loading effects for the Argentine-German Geodetic Observatory in La Plata. It provides the amplitudes and phases of gravity variations and vertical deformation for nine tidal constituents to be applied as corrections to the observatory’s future geodetic observation data. This model combines a global ocean tide model with a model of the tides in the Río de la Plata estuary. A comparison with conventional predictions based only on the global ocean tide model reveals the importance of the incorporation of the regional tide model. Tidal loading at the observatory is dominated by the tides in the Atlantic Ocean. An additional contribution of local tidal loading in channels and groundwater is examined. The magnitude of the tidal loading is also reviewed in the context of the effects of solid earth tides, atmospheric loading and non-tidal loadsFacultad de Ciencias Naturales y Muse

Towards a tidal loading model for the Argentine-German Geodetic Observatory (La Plata)

We present a regionalized model of ocean tidal loading effects for the Argentine-German Geodetic Observatory in La Plata. It provides the amplitudes and phases of gravity variations and vertical deformation for nine tidal constituents to be applied as corrections to the observatory’s future geodetic observation data. This model combines a global ocean tide model with a model of the tides in the Río de la Plata estuary. A comparison with conventional predictions based only on the global ocean tide model reveals the importance of the incorporation of the regional tide model. Tidal loading at the observatory is dominated by the tides in the Atlantic Ocean. An additional contribution of local tidal loading in channels and groundwater is examined. The magnitude of the tidal loading is also reviewed in the context of the effects of solid earth tides, atmospheric loading and non-tidal loadsFacultad de Ciencias Naturales y Muse

Dephasing time of composite fermions

We study the dephasing of fermions interacting with a fluctuating transverse gauge field. The divergence of the imaginary part of the fermion self energy at finite temperatures is shown to result from a breakdown of Fermi's golden rule due to a faster than exponential decay in time. The strong dephasing affects experiments where phase coherence is probed. This result is used to describe the suppression of Shubnikov-de Haas (SdH) oscillations of composite fermions (oscillations in the conductivity near the half-filled Landau level). We find that it is important to take into account both the effect of dephasing and the mass renormalization. We conclude that while it is possible to use the conventional theory to extract an effective mass from the temperature dependence of the SdH oscillations, the resulting effective mass differs from the $m^\ast$ of the quasiparticle in Fermi liquid theory.Comment: 14 pages, RevTeX 3.0, epsf, 1 EPS figur

Determinação simultânea de ácido ascórbico e ácido acetilsalicílico usando análise por injeção em fluxo com detecção amperométrica pulsada

A simple flow system with multiple pulse amperometric detection using a single working electrode is proposed for simultaneous determination of ascorbic (AA) and acetylsalicylic (AAS) acids in pharmaceutical formulations. The procedure is based on application of two potential pulses: 0.90 V/50 ms: oxidation and determination of AA without the interference of AAS; 1.35 V/50 ms: oxidation of both compounds and quantification of AAS by current subtraction using a correction factor. Sampling rate was estimated as 125 injections per hour and the limits of detection were 0.17 and 0.16 µmol L-1 for AA and AAS, respectively. Results for commercial samples agreed with those obtained using HPLC