Simulation of Alternative Differential Multi-pulse Voltammetry. Evaluation of the Electrochemical Reversibility by the Voltammogram Symmetry

A theoretical analysis of reversible and kinetically controlled electrode reactions in conditions of alternative differential multi-pulse voltammetry (ADMPV) is presented. The degree of reversibility, as well as symmetry of the electron transfer reaction, can be estimated by visual inspection of the ADMP voltammogram. The values of electron transfer coefficient and the standard rate constant of a simple electrode reaction Ox + ne− ⇄ Red, can be determined from the slope of linear dependence of the peak currents ratio on the logarithm of pulse duration. The criteria for recognition of reversible and kinetically controlled electrode reactions by alternative differential multi-pulse voltammetry are given.

Electrochemical oxidation of atorvastatin and its adsorptive stripping determination in pharmaceutical dosage forms and biological fluids

Electrochemical behavior of atorvastatin (AT) and optimum conditions to its quantitative determination were investigated using voltammetric methods. Some electrochemical parameters such as diffusion coefficient, surface coverage of adsorbed molecules, electron transfer coefficient, standard rate constant and number of electrons were calculated using the results of cyclic voltammetry. A tentative mechanism for the oxidation for AT has been suggested. The oxidation signal of AT molecule was used to develop fully validated, new, rapid, selective and simple square-wave anodic adsorptive stripping voltammetric (AdsSWV) and differential pulse anodic stripping voltammetric (AdsDPV) methods to direct determination of AT in pharmaceutical dosage forms and biological samples. For the AdsDPV and AdsSWV techniques, linear working ranges were found to be 1.0 × 10–7–5.0 × 10–6and 3.0 × 10–7–5.0 × 10–6mol l–1, respectively. The detection limits obtained from AdsDPV and AdsSWV were calculated to be 6.55 × 10–8and 1.53 × 10–7mol l–1, respectively. The methods were successfully applied to assay the drug in tablets, human blood serum and human urine.

Electrochemical and Spectroscopic Dynamics of Nanostructured Polynuclear Sulphonic Acid-Doped Poly(2, 5-dimethoxyaniline)

Conducting and electroactive nanostructured poly(2, 5-dimethoxyaniline), PDMA, doped with anthracene sulphonic acid, ASA, and phenanthrene sulphonic acid, PSA, respectively, were prepared by oxidative polymerisation of 2, 5-dimethoxyaniline, DMA, with ammonium persulphate as oxidant. Scanning electron microscope, SEM, images of the polymers showed well defined nanotubes and fibrils with diameters of between 50 to 100 nm and 200 to 300 nm for PDMA-ASA and PDMA-PSA, respectively. Evidence of the incorporation of ASA and PSA into the PDMA backbone was provided by UV-Vis and FTIR analyses. Electrochemical interrogation of the sulphonic acid-doped polymers by cyclic voltammetry showed that both PDMA-ASA and PDMA-PSA exhibit quazi-reversible electrochemistry. The standard rate constant, ko, for the charge transfer reactions of PDMA-ASA and PDMA-PSA were 3.81 x 10-4 cm s-1 and 3.27 x 10-5 cm s-1, respectively. There was a relationship between the ko value and the formal potential, E0ʹ, of the polymeric nanomaterial. PDMA-ASA that had larger ko value gave an E0ʹ value of 134 mV which was lower than that of PDMA-PSA by 19 mV, indicating that PDMA-ASA has lower activation energy than PDMA-PSA for the electron transfer process Electrochemical impedance spectroscopy over a range of potentials showed that the polymeric nanotubues exhibited high conductivities, though the SA-doped polymer was more conducting.

Unusual Influence of the Temperature on the Standard Rate Constants of Charge Transfer for the Eu(III)/Eu(II) Redox Couple in Chloride-Bromide Melts

The influence of bromide ions and temperature on the standard rate constants of the Eu(III)/Eu(II) redox reaction was determined. Cyclic voltammetry was used for the calculation of the kinetic parameters. It was shown that in NaCl-KCl (equimolar mixture)-NaBr (15 wt%)-EuCl3 melts increase of the temperature from 973 K up to 1023 K leads to a drastical decrease of the standard rate constant ks for the Eu(III)/Eu(II) redox reaction. This unusual influence of the temperature on the ks value was explained by a change of the electron transfer mechanism. It is suggested that at 1023 K another mechanism becomes dominant - the transfer of electrons through dissolved bromine in the melt. Bromine appeared in the melt due to the decomposition of chloride-bromide or bromide complexes of Eu(III), and the concentration of bromine in the melt increased with the growth of temperature.

Electroreduction of Cr(VI) from solutions of bifunctional alcohols

The effect of bifunctional alcohols ethylene glycol (EG) and 1,2-propylene glycol (1,2 PG) on the kinetic parameters for the irreversible chromate ion reduction were investigated by polarographic and coulometric methods of analysis. The electroreduction of chromate ion in neutral bifunctional alcohol solutions proceeds according to the scheme: Cr(VI)–Cr(III)–Cr(II) and the values of the standard rate constant k*0 decrease in the order H2O > EG > 1,2 PG. The values of real activation energy, Q, activation energy of diffusion, QD, and frequency factor log A° have been calculated. The obtained values of QD as well as Q proved the diffusion nature of limiting current. The values of the frequency factor log A° decrease in the order H2O > EG > 1,2 PG, which points to a less favourable orientation of the electroactive ions at the electrode surface in glycols.

The electrochemical behavior of flavin adenine dinucleotide in neutral solutions

A detailed investigation of the electrochemical behavior of flavin adenine dinucleotide (FAD) in neutral solutions has been carried out at Hg and glassy carbon electrodes. At FAD concentrations of about 10−4 M, cyclic voltammetry (CV) shows a pair of anodic and cathodic peaks having a peak separation at low sweep rates indicative of a two-electron transfer process and yielding a formal redox potential for FAD of −0.206 ± 0.003 V vs. NHE at pH 7. Evidence for FAD adsorption was obtained in experiments at high sweep rates, from the effect of time of exposure of the electrode surface to FAD in solution and from the effect of the potential limits on the cyclic voltammetric response. The process of FAD adsorption was studied in detail in dilute FAD solutions (ca 10−6 M) using a hanging mercury drop electrode and the techniques of CV and ac voltammetry. Three distinct stages of FAD adsorption were observed and a model of the orientation of FAD on the electrode surface as a function of time and potential is presented. In addition, the kinetics of oxidation and reduction of adsorbed FAD was studied for each of the stages of FAD deposition, and a surface standard rate constant of ca. 40 s−1 was obtained for Stages II and III of FAD adsorption.