Electrochemical determination of estradiol using a poly(l-serine) film-modified electrode

A thin film of poly(l-serine) was prepared via electropolymerization for the determination of trace levels of estradiol. In pH 5.0 phosphate buffer, l-serine was oxidized during the cyclic potential sweeps between −0.60 and 2.0 V, forming a thin film at the electrode surface. The electrochemical behavior of estradiol was investigated. The oxidation peak potential of estradiol shifts negatively at the poly(l-serine) film-coated glassy carbon electrode (GCE) compared with that at the bare GCE. Otherwise, the oxidation peak current greatly increases at the poly(l-serine) film-modified GCE. These phenomena suggest that the poly(l-serine) film exhibits catalytic activity towards the electrochemical oxidation of estradiol. Based on this, a sensitive, rapid and simple electrochemical method was proposed for the determination of estradiol. The limit of detection is evaluated to be 2.0 × 10⁻⁸ mol L⁻¹. Finally, this method was successfully used to determine estradiol in blood serum.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

Influence of electroosmotic treatment on the hydro-mechanical behaviour of clayey silts: preliminary experimental results

Preliminary results of an investigation focused on the influence of electrokinetic treatment on the mechanical and hydraulic behaviour of clayey soils are presented. The experimental programme aims at providing a contribution to the sustainability of contaminant extraction or containment via electroosmosis. Changes in the hydraulic and mechanical properties of two illitic clayey soils, subjected to a DC electric field, were investigated. Samples of the two soils were subjected to electrokinetic filtration, for different periods of time, and under different constant loads. Afterwards, they were tested under one-dimensional compression to detect changes in stiffness and hydraulic conductivity due to the electrical treatment. After the application of a DC field for a few hours, a small reversible increment in the average soil stiffness was observed, with respect to the untreated soil, while the hydraulic conductivity was not affected substantially. Dramatic changes of the mechanical and hydraulic soil properties, correlated to changes of the soil pH, were observed following non-conditioned electrokinetic treatment with duration of the order of days.     

A disposable sensor based on immobilization of acetylcholinesterase to multiwall carbon nanotube modified screen-printed electrode for determination of carbaryl

A simple method has been devised for immobilization of acetylcholinesterase (AChE) covalent bonding to a multiwall carbon nanotube (MWNT)-cross-linked cellulose acetate composite on a screen-printed carbon electrode (SPCE) and a sensitive and disposable amperometric sensor for rapid determination of carbaryl pesticide is proposed. The immobilized enzyme was preserved on this film because of the excellent biocompatibility and non-toxicity of cellulose acetate. Based on the inherent conductive properties of the MWNT, the immobilized AChE had greater affinity for ATCl and excellent catalytic effect in the hydrolysis of ATCl. MWNT improved the interface enzymatic hydrolysis reaction and increased the amperometric response of the sensor. Under optimum conditions, the inhibition of carbaryl on AChE increased linearly with the increasing concentration of carbaryl in two ranges, from 0.01 to 0.5 μg mL⁻¹ and from 2 to 20 μg mL⁻¹, with the correlation coefficients of 0.9985 and 0.9977, respectively. The detection limit was 0.004 μg mL⁻¹ taken as the concentration equivalent to 10% decrease in signal. The sensor showed acceptable stability, accuracy and could be fabricated in batches, thus it is economic and portable. This type of disposable enzyme-based amperometric sensor has extensive application potential in environmental monitoring of pesticides.     

Influence of pencil lead hardness on voltammetric response of graphite reinforcement carbon electrodes

This work studied the voltammetric response of graphite reinforcement electrodes made of different pencil lead hardness. The studies showed that harder graphite leads, regardless of their manufacturer, are more appropriate as electrode material for voltammetric purposes due to their higher peak currents, increasing sensitivity and reproducibility, with ΔEp closer to the theoretical value for a reversible system.     

FEM model of the ohmic resistance of IP-SOFCs

In the present work, the ohmic resistance of an integrated planar-SOFC (IP-SOFC) has been evaluated by developing a model whose equations have been solved numerically through an FEM method. The model allows to estimate the distribution of voltage and current density in the cell. A comparison between simulated and experimental data of area specific resistance is reported, which shows satisfactory agreement. The mathematical model has also been used to carry out some parametric studies for optimisation purposes. Indeed, a reduction in cell pitch length and an increase in electrode thickness are predicted to lead to a reduction in ohmic losses in IP-SOFCs.     

Synthesis and structural characterization of methacrylic acid/octadecyl acrylate‐graft‐poly(methylhydrosiloxane) by hydrosilylation

Methylmethacrylate (MMA) and octadecyl acrylate (OA) were grafted to poly(methylhydrosiloxane) (PMHS) by hydrosilylation, respectively, with hexachloroplatinic acid as catalyst, and the former was further hydrolyzed to prepare methacrylic acid (MAA)‐graft‐PMHS under the alkaline condition. Through orthogonal experiment, main factors affecting the graft reaction between OA and PMHS were discussed and arranged in a decreasing order according to their abilities of the effect on the hydrosilylation of OA with PMHS: catalyst dosage, reaction temperature, reaction time, material ratio, and solvent dosage. It was found that the hydrosilylation of OA with PMHS was easier to that of MMA with PMHS. Under optimal conditions, the grafting ratios of MMA with PMHS and OA with PMHS reached about 90 and 95%, respectively. FTIR and ¹H NMR spectra indicated that the hydrosilylation reactions followed the Markovnikov's rule and played a strong preference toward β‐1,2‐addition. The test of contact angle indicated that surface energy of a system was mainly dependent on the polar groups. The surface energy of OA‐graft‐PMHS (35.07 mN/m) was similar to those of PMHS (35.62 mN/m) and polyoctadecyl acrylate (36.57 mN/m), and lower than that of MAA‐graft‐PMHS (43.50 mN/m). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.