Sławomira Skrzypek

Square wave adsorptive stripping voltammetric determination of famotidine in urine

Electrochemical studies of famotidine were carried out using voltammetric techniques: cyclic voltammetry, linear sweep and square wave adsorptive stripping voltammetry. The dependence of the current on pH, buffer concentration, nature of the buffer, and scan rate was investigated. The best results for the determination of famotidine were obtained in MOPS buffer solution at pH 6.7. This electroanalytical procedure enabled to determine famotidine in the concentration range 1x10(-9)-4x10(-8)molL(-1) by linear sweep adsorptive stripping voltammetry (LS AdSV) and 5x10(-10)-6x10(-8)molL(-1) by square wave adsorptive stripping voltammetry (SW AdSV). Repeatability, precision and accuracy of the developed methods were checked. The detection and quantification limits were found to be 1.8x10(-10) and 6.2x10(-10)molL(-1) for LS AdSV and 4.9x10(-11) and 1.6x10(-10)molL(-1) for SW AdSV, respectively. The method was applied for the determination of famotidine in urine.

Conditioning of renewable silver amalgam film electrode for the characterization of clothianidin and its determination in selected samples by adsorptive square-wave voltammetry.

A new square-wave adsorptive stripping voltammetric (SWAdSV) method was developed for the determination of the neonicotinoid insecticide clothianidin (Clo), based on its reduction at a renewable silver amalgam film electrode (Hg(Ag)FE). The key point of the procedure is the pretreatment of the Hg(Ag)FE by applying the appropriate conditioning potential (-1.70 V vs. Ag/AgCl reference electrode). Under the optimized voltammetric conditions, such pretreatment resulted in the peak for the Clo reduction in Britton-Robinson buffer pH 9.0 at about -0.60 V, which was used for the analytical purpose. The developed SWAdSV procedure made it possible to determine Clo in the concentration range of 6.0×10(-7)-7.0×10(-6) mol L(-1) (LOD=1.8×10(-7) mol L(-1), LOQ=6.0×10(-7) mol L(-1)) and 7.0×10(-6)-4.0×10(-5) mol L(-1) (LOD=1.3×10(-6) mol L(-1), LOQ=4.2×10(-6) mol L(-1)). The repeatability, precision, and the recovery of the method were determined. The effect of common interfering pesticides was also investigated. Standard addition method was successfully applied and validated for the determination of Clo in spiked Warta River water, corn seeds samples, and in corn seeds samples treated with the commercial formulation PONCHO 600 FS.

The Influence of Protonation on the Electroreduction of Bi (III) Ions in Chlorates (VII) Solutions of Different Water Activity

We examined the electroreduction of Bi (III) ions in chlorate (VII) solutions under varied protonation conditions of the depolariser using voltammetric and impedance methods. The results of the kinetic parameter correlation lead to the statement that the changes in the amount of chloric (VII) acid against the amount of its sodium salt in the supporting electrolytes of the low water activity have a significant influence on the rate of Bi (III) ion electroreduction. The increase of the concentration of chloric acid sodium salt, as well as the chloric (VII) acid alone within the particular concentration of the supporting electrolyte, inhibits the process of Bi (III) ion electroreduction. It should be associated with the reorganisation of the structure of the double layer connected with the slow dehydration inhibited by ClO 4− ions. The standard rate constants ks values with the increase of the chlorate (VII) concentrations for all the solutions examined of chlorates (VII) confirms the catalytic influence of the decrease of water activity on the process of Bi (III) ion electroreduction. The multistage process is confirmed by the non-rectilinear 1nkf = f(E) dependences.

β–Cyclodextrins incorporated multi-walled carbon nanotubes modified electrode for the voltammetric determination of the pesticide dichlorophen

In this work, a glassy carbon electrode modified with β-cyclodextrins and multi-walled carbon nanotubes (β-CDs/MWCNTs/GCE) was constructed and applied for the square-wave adsorptive stripping voltammetric (SWAdSV) determination of the pesticide dichlorophen (Dcp). For the first time, this compound was electrochemically investigated. The voltammetric measurements were conducted in phosphate buffer (PBS) at pH 6.5 as a supporting electrolyte, and SWAdSV technique parameters were optimized. A linear calibration curve in the wide concentration range from 5.0 × 10-8molL-1 to 2.9 × 10-6molL-1 was obtained. Excellent analytical performance in terms of limit of detection (LOD) of 1.4 × 10-8molL-1 was achieved. The utility of the proposed method was verified by the quantitative analysis of Dcp in Pilica River water samples with satisfactory results. The characterization of modified electrodes was conducted by means of atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). Moreover, in this work, the dissociation constants (pKa) of Dcp using potentiometric pH titration were estimated. The stoichiometry of the Dcp-β-CDs inclusion complex formed in solution was determined by proton nuclear magnetic resonance (1H NMR) spectroscopy, and a binding constant (β2) was estimated from NMR titration studies.

Voltammetric behaviour and quantitative determination of pesticide iminoctadine

Iminoctadine (IOD) was determined in spiked river water samples by square wave voltammetry (SWV) using a cyclic renewable silver amalgam film electrode (Hg(Ag)FE). It was found that the compound can act as an electrocatalyst. In Britton–Robinson buffer at pH 6.5 a signal connected with the catalytic hydrogen evolution reaction was detected at −1.8 V versus Ag/AgCl. Validation of the method was carried out. The LOD and LOQ have been estimated to be 2.6 × 10−9 mol L−1 and 8.5 × 10−9 mol L−1, respectively.

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at −0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10−8 to 6.0 × 10−8 mol L−1 with detection and quantification limit 3.0 × 10−9 and 1.0 × 10−8 mol L−1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.

Voltammetric behavior and quantitative determination of ambazone concentrations in urine and in a pharmaceutical formulation

The use of square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode (Hg(Ag)FE) for the analytical determination of ambazone in urine samples and pharmaceutical formulations is described. A single reduction peak in Britton-Robinson buffer at pH 4.0 was detected at about −1.4 V versus Ag/AgCl. Mechanistic studies have shown that the compound can act as an electrocatalyst. The method was validated. The analytical curve was linear in the concentration range from 1.0×10−9 to 1.0×10−7 mol L−1. The detection and quantification limits were found to be 3.0×10−10 mol L−1 and 1.0×10−9 mol L−1, respectively. The proposed method was successfully applied to ambazone determination in real samples.

Application of the catalytic properties of methionine to the determination of Bi(III) as well in the presence of Cu(II) ions at low levels by square wave voltammetry

ABSTRACT A simple and fast method for the determination of Bi(III) in the presence Cu(II) in non-complexing solution was proposed. The catalytic activity of L-methionine on Bi(III) ions electroreduction as well as lack of this amino acid influence on Cu(II) ions electroreduction process were utilised. The calibration graph of Bi(III) in 4 mol dm−3 chlorate (VII) in the presence of 5 × 10−2 mol dm−3 methionine is linear in the range of concentrations of Bi(III) from 3 × 10−7 to 1 × 10−4 mol dm−3. The detection and quantification limits were found to be 1.53 × 10−7 and 5.12 × 10−7 mol dm−3, respectively. Precision and recovery of the method were investigated by determination of Bi(III).

Electrode mechanism and voltammetric determination of selected guanidino compounds

AbstractThe present review describes the recent results on the electrochemical activity of bio-guanidino compounds, such as famotidine, metformin, acyclovir, ganciclovir, zanamivir, moroxydine as well as guanidino compounds, such as S-[(2-guanidino-thiazol-4-yl)methyl]isothiourea hydrochloride, 2-guanidino-1,3-thiazole, 2-guanidinobenzimidazole. The focus is on analyzing the electrode mechanism of the guanidino compounds at the hanging mercury drop electrode and at the silver amalgam film electrode, as well as on the character of the square wave (SW) voltammetric signals. It has been stated, that the compounds can act as electrocatalysts — they are protonated and adsorbed at the surface of the electrode, after which the protonated forms of the compounds are irreversibly reduced, yielding their initial form and hydrogen. The experimental adsorption data obtained by measuring the differential capacity of the double layer, the zero charge potential, and the surface tension at the zero charge potential have established the adsorption processes underlying their electrochemical activity. The analytical application of the obtained voltammetric signals in the determination of these compounds in biological samples is also presented. This review concentrates on our own results in the context of general developments in the field.

The mechanism of electropolymerization of nickel( ii ) salen type complexes

Ni(II) complexes with (±)-trans-N,N′-bis(salicylidene)-1,2-cyclohexanediamine ([Ni(salcn)]), and its methyl ([Ni(salcn(Me))]) and tert-butyl ([Ni(salcn(Bu))]) derivatives have been synthesized. Anodic electropolymerization has been used to form electrodes modified by polymer films. FTIR and FTIR ATR methods showed that the obtained films consist of polymers of phenyl–phenyl type. The structure of poly[Ni(salcn)] is built with 1,2,4- and 1,2,3,5-substituted chains. A three-step process of the oxidation of the complexes and their films has been ascertained on the basis of cyclic voltammetry measurements. Furthermore we have also detected the oxidized species which probably serve as intermediates for polymer formation. The influence of the substituent in the phenolate moiety on the type of reaction after which the dimerization and polymerization reaction occurs has been evidenced. Furthermore the substituent dependence on the stability of the phenoxyl radical complex and the Ni(II)-phenoxonium cation has been noticed. For the [Ni(salcn(Bu))] complex, an additional electropolymerization step – the adsorption of the reagent on the electrode surface – has been observed.