Renewable drops electrochemical sensor for sulfide ions detection

The design and characteristics of a novel electrochemical system, which uses a drop as a renewable electroanalytical sensor, are described. This article describes the performance of the electrochemical system, the coupling of the experimental arrangement with flow injection technique and a demonstration of its applicability for the measurement of sulfide. The method is based on renewable drops of ferricyanide ions, buffered by borate. The ferrocyanide ions, product of the reaction between ferricyanide and sulfide ions, are oxidized on a platinum microelectrode and the current measured is related to sulfide concentration. The measurements can be done in continuous or static flow mode. In continuous mode, the detection limit is 5.0 x 10(-5) mol L-1.

A disposaable electrochemical sensor for the rapid determination of levodopa

Levodopa (L-dopa), the biological precursor of catecholamines, is the most widely prescribed drug in the treatment of Parkinson's disease. The present work presents a proposal for the application of a gold screen-printed electrode an electrochemical sensor for monitoring L-dopa in stationary solution and a flow system. Using the electrooxidation of L-dopa at +0.63 V in acetate buffer pH 3.0 on a gold screen-printed electrode it is possible to obtain a linear calibration curve from 9.9 x 10(-5) to 1.2 x 10(-3) mol L-1 and a detection limit of 6.8 x 10(-5) mol L-1. Under amperometric conditions (E-app = 0.8 V; flow rate = 14.1 ml, min(-1); pH 3.0), an analytical calibration graph for L-dopa was obtained from 1.0 x 10(-6) mol L-1 6.6 x 10(-4) mol L-1 with a detection limit of 9.9 x 10(-7) mol L-1. The method was successfully applied to the determination of L-dopa in commercial dosage forms without any pre-treatment. (c) 2005 Elsevier B.V. All rights reserved.

Square-wave voltammetry applied to the analysis of the dye marker, solvent blue 14, in kerosene and fuel alcohol

The purpose of this paper is to develop an electroanalytical method based on square-wave voltammetry (SWV) for the determination of the solvent blue 14 (SB-14) in fuel samples. The electrochemical reduction of SB-14 at glassy carbon electrode in a mixture of Britton-Robinson buffer with N,N-dimethyiformamide (1:1, v/v) presented a well-defined peak at-0.40 V vs. Ag/AgCl. All parameters of the SWV technique were optimized and the electroanalytical method presented a linear response from 1.0 x 10(-6) to 6.0 x 10(-6) mol L-1 (r = 0.998) with a detection limit of 2.90 x 10(-7) mol L-1. The developed method was successfully utilized in the quantification of the dye SB-14 in kerosene and alcohol samples with average recovery from 93.00 to 98.10%.

Development of Ti-Mo alloys for biomedical applications: Microstructure and electrochemical characterization

Ti-Mo alloys from 4 to 20 Mo wt.% were arc-melted. Their compositions and surfaces were analyzed by EDX, XRF and SEM. The Mo mapping shows a homogeneous distribution for all alloys. The XRD analysis showed that the crystal structure of the alloys is sensitive to the Mo concentration; a mixture of the hexagonal alpha' and orthorhombic alpha '' phases was observed for the Ti-4Mo alloy, and the alpha '' phase is observed almost exclusively when the concentration of Mo added to the Ti reaches 6%. A significant retention of the beta phase is observed for the alloy containing 10% Mo, while at higher Mo concentrations (15% and 20%), retention of phase beta is only verified. Preliminary electrochemical studies have indicated a valve-metal behavior and good corrosion resistance in aerated Ringer solution for all alloys. (c) 2006 Published by Elsevier B.V.

Application of low-pressure gas chromatography-ion-trap mass spectrometry to the analysis of the essential oil of Turnera diffusa (Ward.) Urb.

Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 mum) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved. (C) 2003 Elsevier B.V. All rights reserved.

Determination of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography with electrochemical detection

A new methodology was developed for analysis of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography (HPLC) coupled to electrochemical detection. The electrochemical oxidation of 5-hydroxymetkylfurfural, 2-furfuraldehyde, butyraldehyde, acetone and methyl ethyl ketone derivatized with 2,4-dinitrophenylhydrazine (DNPH) at glassy carbon electrode present a well defined wave at +0.94 V; +0.99 V; +1.29 V; +1.15 V and +1.18 V, respectively which are the basis for its determination on electrochemical defector. The carbonyl compounds derivatized were separated by a reverse-phase column under isocratic conditions with a mobile phase containing a binary mixture of methanol /LiClO4(aq) at a concentration of 1.0 x 10(-3) mol L-1 (80:20 v/v) and a flow-rate of 1.1 mL min(-1). The optimum potential for the electrochemical detection of aldehydes-DNPH and ketones-DNPH was +1.0 V vs. Ag/AgCl. The analytical curve of aldehydes-DNPH and ketones-DNPH presented linearity over the range 5.0 to 400.0 ng mL(-1), with detection limits of 1.7 to 2.0 ng mL(-1) and quantification limits from 5.0 to 6.2 ng mL(-1), using injection volume of 20 mu L. The proposed methodology was simple, low time-consuming (15 min/analysis) and presented analytical recovery higher than 95%.

Electrochemical behavior of cobalt oxide coatings on cold-rolled steel in alkaline sodium sulfate

The electrochemical behavior of a coating of cobalt oxide on cold-rolled steel in alkaline sodium sulfate was Studied using the electrochemical techniques of open-circuit potential measurements and electrochemical impedance spectroscopy. The coating was prepared at different annealing temperatures ranging from 350 to 750 degreesC and characterized by SEM, EDX and XRD. Below 550 degreesC the composition of the coating was basically of Co3O4. At 750 degreesC CoO was formed and big cracks appeared on the film exposing an inner layer of iron oxides. Analysis of the EIS data is very difficult because of the complexity of the interface structure. It can be inferred that the charge transfer resistance of the coatings prepared at 350 and 450 C were higher than those for the coatings prepared at temperatures above 550 degreesC. (C) 2002 Published by Elsevier B.V. Ltd.

Sequential spectrophotometric determination of chromium(III) and chromium(VI) using flow injection analysis

A flow injection analysis (FIA) procedure for the speciation of Cr(III) and Cr(VI) using the 1,5-diphenylcarbazide (DPC) method is presented. As Cr(III) does not interfere in the Cr(VI) - DPC reaction, both Cr(VI) and total chromium [after the on-line oxidation of Cr(III) by Ce(IV)] are sequentially determined. Cr(III) is obtained by difference. Under the experimental conditions described, the calibration graphs are linear up to 2 μg mh1 of Cr(VI) and 4 μg ml-1 of Cr(III). The detection limits found were 18 ng ml -1 for Cr(VI) and 55 ng ml-1 for Cr(III), at a signal to noise ratio of 3. The common interfering elements in the Cr(VI) - DPC reaction were investigated under dynamic FIA conditions. The FIA method was also compared with the conventional spectrophotometric procedure.

NOISE GENERATED BY CAVITATION IN ORIFICE-PLATES WITH SOME GASEOUS EFFECTS.

An experimental investigation of the noise generated by cavitation in turbulent shear flows produced by confined sharp-edge orifice-plates is reported. The acoustic source strength of cavitation was determined by means of reciprocity type measurements. Experimentally determined scaling parameters are applied to a model to prototype scaling formula derived from dimensional analysis. The proposed formula is checked experimentally. Comparative photographic observations of the cavitation patterns for two different values of gas content are presented. The observed sound reduction, that occurs when supersaturated conditions exist downstream the orifice-plates, is explained by the effects of gas diffusion into the cavitation bubbles, and by simple acoustic attenuation.

Microstructural characteristics and electrochemical behavior of Co3O4 sintered electrodes

Co3O4 can be used as electrocatalyst for oxygen evolution reaction. The macro and microstructure of the oxide, obtained by compacting and sintering lithium-doped Co3O4 powder in atmosphere of dry air and in conditions of controlled temperature and time was analyzed by metallographic techniques. The porous material was characterized by XRD, SEM and EDS combined techniques. For working temperatures up to 1200°C, the pellet was consituted of particles with varying sizes over a wide range of particle size and, at higher temperatures CoO is formed and polymorphic transformation was observed. The materials were also characterized electrochemically in alkaline media by open circuit potential and potentiodynamic I/E measurements. The results were compared to those previously prepared by others by thermal deposition.

A method for the digital image analysis of ceramic grains based on shape factor segmentation

A very simple and robust method for ceramics grains quantitative image analysis is presented. Based on the use of optimal imaging conditions for reflective light microscopy of bulk samples, a digital image processing routine was developed for shading correction, noise suppressing and contours enhancement. Image analysis was done for grains selected according to their concavities, evaluated by perimeter ratio shape factor, to avoid consider the effects of breakouts and ghost boundaries due to ceramographic preparation limitations. As an example, the method was applied for two ceramics, to compare grain size and morphology distributions. In this case, most of artefacts introduced by ceramographic preparation could be discarded due to the use of perimeter ratio exclusion range.

Study of electrochemical oxidation and determination of albendazole using a glassy carbon-rotating disk electrode

In this work, electrochemical oxidation of albendazole (ABZ) was carried out using a glassy carbon-rotating disk electrode. Development of electroanalytical methodology for ABZ quantification in pharmaceutical formulations was also proposed by using linear sweep voltammetric technique. Electrochemical oxidation is observed for ABZ at E 1/2 = 0.99:V vs. Ag/AgCl sat, when an anodic wave is observed. Kinetic parameters obtained for ABZ oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51 ± 0.07) ± 10 -5:cm:s -1, with a αn a value equal to 0.76. Limiting current dependence against ABZ concentration exhibited linearity on 5.0 ± 10 -5 to 1.0 ± 10 -2:mol:l -1 range, being obtained a detection limit of 2.4 ± 10 -5:mol:l -1. Proposed methodology was applied to ABZ quantification in pharmaceutical formulations. © 2005 Elsevier SAS. All rights reserved.

Dynamic analysis of a new piezoelectric flextensional actuator using the J1-J4 optical interferometric method

Piezoelectric actuators are widely used in positioning systems which demand high resolution such as scanning microscopy, fast mirror scanners, vibration cancellation, cell manipulation, etc. In this work a piezoelectric flextensional actuator (PFA), designed with the topology optimization method, is experimentally characterized by the measurement of its nanometric displacements using a Michelson interferometer. Because this detection process is non-linear, adequate techniques must be applied to obtain a linear relationship between an output electrical signal and the induced optical phase shift. Ideally, the bias phase shift in the interferometer should remain constant, but in practice it suffers from fading. The J1-J4 spectral analysis method provides a linear and direct measurement of dynamic phase shift in a no-feedback and no-phase bias optical homodyne interferometer. PFA application such as micromanipulation in biotechnology demands fast and precise movements. So, in order to operate with arbitrary control signals the PFA must have frequency bandwidth of several kHz. However as the natural frequencies of the PFA are low, unwanted dynamics of the structure are often a problem, especially for scanning motion, but also if trajectories have to be followed with high velocities, because of the tracking error phenomenon. So the PFA must be designed in such a manner that the first mechanical resonance occurs far beyond this band. Thus it is important to know all the PFA resonance frequencies. In this work the linearity and frequency response of the PFA are evaluated up to 50 kHz using optical interferometry and the J1-J4 method.

CMOS-based active pixel for low-light-level detection: Analysis and measurements

An analysis of the active pixel sensor (APS), considering the doping profiles of the photodiode in an APS fabricated in a 0.18 μm standard CMOS technology, is presented. A simple and accurate model for the junction capacitance of the photodiode is proposed. An analytic expression for the output voltage of the APS obtained with this capacitance model is in good agreement with measurements and is more accurate than the models used previously. A different mode of operation for the APS based on the dc level of the output is suggested. This new mode has better low-light-level sensitivity than the conventional APS operating mode, and it has a slower temporal response to the change of the incident light power. At 1μW/cm2 and lower levels of light, the measured signal-to-noise ratio (SNR) of this new mode is more than 10 dB higher than the SNR of previously reported APS circuits. Also, with an output SNR of about 10 dB, the proposed dc level is capable of detecting light powers as low as 20 nW/cm2, which is about 30 times lower than the light power detected in recent reports by other groups. © 2007 IEEE.

The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium bis (trifluoromethanesulfonyl) imide [N6,2,2,2][N(Tf)2], 1-butyl-3-methylimidazolium hexafluorosphosphate [C4mim][PF6], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C4mpyrr][N(Tf)2], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][N(Tf)2], N-butyl-N-methyl-pyrrolidinium dicyanamide [C4mpyrr][N(NC)2] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][FAP] on a platinum microelectrode. In [N6,2,2,2][NTf2] and [P14,6,6,6][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion, which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P14,6,6,6][FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N6,2,2,2][NTf2] and [P14,6,6,6][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer is followed by a chemical reaction. © 2009 Elsevier B.V.