Cathodic stripping voltammetry and adsorptive stripping voltammetry of selenium(IV)

Cathodic stripping voltammetry of selenium(IV) in 0.1 M hydrochloric acid media yielded a nonlinear calibration graph for the concentration range 10^?9?10^?8 M. In this concentration range, adsorptive stripping voltammetry based on adsorption of the selenium/3,3′-diaminobenzidine complex on the surface of the hanging mercury drop electrode at the deposition potential of +0.05 V (vs. SCE) is more convenient. A linear calibration graph is obtained for selenium concentrations of 3×10^?9?3×10?8 M, with an accumulation time of 300 s.     

Adsorptive stripping voltammetry of chlordiazepoxide at the hanging mercury drop electrode

Controlled adsorptive accumulation at the hanging mercury drop electrode enables 0.8–11 × 10^?5 M chlordiazepoxide to be quantified by differential-pulse stripping voltammetry with accumulation times of 1–3 min. With 3-min accumulation, the peak current is enhanced 12-fold for 1.0 × 10^?7 M chlordiazepoxide compared to the current from differential pulse polarography. The detection limit is 0.9 × 10^?9 M for 4-min accumulation. The procedure is applied to spiked human serum after preseparation of the drug on a Sep-Pak C₁₈ cartridge.     

Determination of the Anticancer Drug Sorafenib in Serum by Adsorptive Stripping Differential Pulse Voltammetry Using a Chitosan/Multiwall Carbon Nanotube Modified Glassy Carbon Electrode

Adsorptive stripping differential pulse voltammetry (AdSDPV) was applied to the assay of sorafenib in human serum sample. Cyclic voltammetry at a carbon based screen printed electrode (SPE) permitted to detect the irreversible oxidation of SOR with formation of a new compound reversibly oxidized at a lower potential. Quantitative assays were realized using a chitosan/carboxylic acid functionalized multiwalled carbon nanotube modified glassy carbon electrode in 0.1 M phosphate buffer pH 7.0 in the presence of 50 % methanol. The AdSDPV method provided two linear responses within the concentration ranges 1×10^?8–8×10^?8 M and 1×10^?7–8×10^?7 M in serum with LOQ and LOD of 3.2×10^?9 and 9.6×10^?10 of lower linear range, respectively. The recovery of sorafenib in spiked serum was 97.5 %.     

Subnanomolar Determination of Indium by Adsorptive Stripping Differential Pulse Voltammetry Using Factorial Design for Optimization

Abstract

A highly sensitive method to determine of indium is proposed by adsorption stripping differential pulse cathodic voltammetry (AdSDPCV) method. The complex of indium ions with xylenol orange is analyzed based on the adsorption collection onto a hanging mercury drop electrode (HMDE). After accumulation of the complex at ?0.20 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from ?0.40 to ?0.75 V with the differential pulse method. Then, the reduction peak current of In(III)–XO complex is measured. The influence of chemical and instrumental variables was studied by factorial design analysis. Under optimum conditions and accumulation time of 60 s, linear dynamic range was 0.1–10 ng/ml (8.7 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.03 ng/ml (2.6 × 10^?10 M); at accumulation time of 5 min, linear dynamic range was 0.04–10 ng/ml (3.4 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.013 ng/ml (1.1 × 10^?10 M). The applicability of the method to analysis of real samples was assessed by the determination of indium in water, alloy, and jarosite (zinc ore) samples.     

Simultaneous Square‐Wave Voltammetric Determination of Paracetamol,Caffeine and Orphenadrine in Pharmaceutical Formulations Using a Cathodically Pretreated Boron‐Doped Diamond Electrode

An electroanalytical method for the simultaneous determination of paracetamol (PAR), caffeine (CAF), and orphenadrine (ORPH) using the square‐wave voltammetry (SWV) and a cathodically pretreated boron‐doped diamond electrode was developed. The method exhibits linear responses to PAR, CAF, and ORPH in the concentration ranges 5.4×10^?7–6.1×10^?5 M, 7.8×10^?7–3.5×10^?5 M, and 7.8×10^?7–3.5×10^?5 M, respectively, with detection limits of 2.3×10^?7 M, 9.6×10^?8 M, and 8.4×10^?8 M, respectively. The proposed method was successfully applied in the simultaneous determination of these analytes in pharmaceutical formulations.     

Determination of some quinoxaline-N-dioxide derivatives by adsorptive stripping voltammetry

Some derivatives of quinoxaline-N-dioxides, which are used as growth promoters in animals (Carbadox, Cyadox, Olaquindox), can be determined at nanomolar concentrations by stripping volatammetry from a static mercury drop electrode after adsorptive accumulation on the electrode surface. With differential pulse voltammetry, in 0.1 M sodium perchlorate with 5% (v/v) dimethylformamide, the detection limit for Cyadox is 3 × 10^?10 mol 1^?1 after accumulation for 300 s in stirred solution; detection limits are 2 × 10^?9 mol 1^?1 (180 s accumulation) for Carbadox and 7 × 10 mol 1^?1 (60 s accumulation) for Olaquindox. The relative standard deviations are 0.85% for Cyadox (4 × 10^?9 mol 1^?1), 0.54% for Carbadox (2 × 10^?8 mol 1^?1) and 0.95% for Olaquindox (2 × 10^?8 mol 1^?1). Surfactants interfere.     

Adsorptive stripping voltammetry of sex hormones at the static mercury drop electrode

Controlled adsorptive accumulation of testosterone, methyltestosterone and progesterone on the static mercury drop electrode provides the basis for direct stripping measurement of these compounds ar nanomolar concentrations. The adsorptive stripping behavior is evaluated with respect to preconcentration time and potential, stripping mode, concentration dependence, drop size and other variables. With 5-min accumulation, peak current enhancements of 45, 18 anal 12 are observed for 5 × 10^?8 M testosterone, progesterone and methyltestosterone, respectively, relative to direct pulse voltammetry. Detection limits are 1.6 × 10^?10 M for testosterone, 2 × 10^?10 M for progesterone and 3.3 × 10^?10 M for methyltestosterone with 15-min preconcentration. The relative standard deviation for 8 × 10^?8 M progesterone is 3.4% (n=8). Applicability to direct measurements of methyltestosterone in pharmaceutical formulations is assessed.     

Electrochemical studies of determination of C.I. Direct Red 80 based on a gold nanoparticles-modified carbon paste electrode

In this paper, a simple, convenient and sensitive electrochemical method has been developed for the determination of C.I. Direct Red 80. A gold nanoparticle modified carbon paste electrode was fabricated and used for study and sensitive determination of Direct Red 80 by cyclic voltammetry and differential pulse voltammetry. The overall analysis involved a two-step procedure: an accumulation step under open-circuit conditions, followed by voltammetric measurements of Direct Red 80 in a 0.1?M phosphate buffer solution at pH?=?3.0. The experimental conditions, such as the medium, pH and accumulation time, were optimised. The oxidation peak current was proportional to the concentration of Direct Red 80 from 5.0?×?10^?8 to 5.0?×?10^?7?M and 5.0?×?10^?7 to 3.0?×?10^?6?M, and the detection limit was 1.15?×?10^?8?M (S/N?=?3). The proposed method was used to detect Direct Red 80 in natural water and sewage with good accuracy.     

Enhanced electron transfer by bovine serum albumin covalently attached to glassy carbon electrode and its application to determination of hydroquinone

Bovine serum albumin (BSA) was covalently attached to glassy carbon electrode (GCE) surface by the electrochemical method. An enhancement for the redox of hydroquinone (HQ) on BSA/GCE was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy measurement. The electron transfer rate constant (k _s) on the BSA/GCE electrode is almost three orders of magnitude higher than that on bare GCE. The enhancing effect can be attributed to the electrostatic force between the positively charged HQ and negatively charged BSA. It is found that the enhanced redox process of HQ can be used to determine HQ sensitively. The oxidation current can reach 95% of its steady-state value within 30 s. The linear range for HQ determination is from 2.5 × 10^?8 M to 1.325 × 10^?6 M with a detection limit of 8.6 × 10^?9 M at a signal-to-noise ratio of 3. The study may provide a simple, rapid and sensitive method for determination of HQ which is present in the natural environment and in chemical industry effluent.     

Enantioselective recognition of penicillamine enantiomers on bovine serum albumin-modified glassy carbon electrode

As a natural chiral selector, bovine serum albumin (BSA) has been used to recognize penicillamine (Pen) enantiomers through electrochemical methods. The recognition and assay rely on the stereoselectivity of BSA embedded in ultrathin Al₂O₃ sol–gel film coated on the surface of glassy carbon electrode (BSA/GCE). The enantioselective interaction between Pen enantiomers and BSA was monitored by cyclic voltammetry and electrochemical impedance spectroscopy measurements, from which larger response signals were obtained from d-Pen. The factors influencing the performance of the modified biosensor were also investigated. The association constant (K) was calculated to be 1.93?×?10⁴?L?mol^?1 for d-Pen and 1.20?×?10³?L?mol^?1 for l-Pen. A good linear response was exhibited with the concentration of Pen enantiomers by BSA/GCE over the range of 1?×?10^?8–1?×?10^?1?mol?L^?1 with a detection limit of 3.31?×?10^?9?mol?L^?1.     

Electrochemical Investigations of the Anticancer Drug Idarubicin Using Multiwalled Carbon Nanotubes Modified Glassy Carbon and Pyrolytic Graphite Electrodes

The effect of surface modifications on the electrochemical behavior of the anticancer drug idarubicin was studied at multiwalled carbon nanotubes modified glassy carbon and edge plane pyrolytic graphite electrodes. The surface morphology of the modified electrodes was characterized by scanning electron microscopy. The modified electrodes were constructed for the determination of idarubicin using adsorptive stripping differential pulse voltammetry. The experimental parameters such as supporting electrolyte, pH, accumulation time and potential, amount of carbon nanotubes for the sensitive assay of idarubicin were studied as details. Under the optimized conditions, idarubicin gave a linear response in the range 9.36×10^?8–1.87×10^?6 M for modified glassy carbon and 9.36×10^?8–9.36×10^?7 M for modified edge plane pyrolytic graphite electrodes. The detection limits were found as 1.87×10^?8 M and 3.75×10^?8 M based on modified glassy carbon and edge plane pyrolytic graphite electrodes, respectively. Interfering species such as ascorbic acid, dopamine, and aspirin showed no interference with the selective determination of idarubicin. The analyzing method was fully validated and successfully applied for the determination of idarubicin in its pharmaceutical dosage form. The possible oxidation mechanism of idarubicin was also discussed. The results revealed that the modified electrodes showed an obvious electrocatalytic activity toward the oxidation of idarubicin by a remarkable enhancement in the current response compared with bare electrodes.     

The Convenient Determination of Palladium at a Solid Electrode via Adsorptive Stripping Voltammetry at a Glassy Carbon Electrode Modified with a Random Array of Mercury Nanodroplets

The detection of palladium using adsorptive stripping voltammetry reported by Wang et al. (J. Wang, K. Varughese Anal. Chim. Acta 1987, 199, 185 [3]) at a hanging mercury drop electrode is extended to a more convenient solid electrode. To this end a random array of 3.5×10⁸ mercury nanodroplets per cm² (65 nm average diameter) was electrodeposited on a glassy carbon substrate. Adsorptive stripping voltammetry was performed using 2×10^?4 M dimethylglyoxime as a chelating agent for the Pd(II) ion, with accumulation at ?0.20 V vs. SCE for 120 s and a linear detection range of 5–150 μM was determined with a limit of detection of 1.6 μM.     

Differential Pulse Voltammetric Determination of Montelukast in Tablets and Human Plasma by Using Chitosan Modified Carbon Paste Electrode

Electrochemical reduction and determination of montelukast (MKS) was studied in methanol – 0.1 M HCl solution (1 : 1, v/v) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at chitosan modified carbon paste electrode. The linear range was 1.70×10^?7–1.83×10^?5 M for DPV analysis. Limit of detection (LOD) and limit of quantification (LOQ) were 5.32×10^?8 M and 1.61×10^?7 M, respectively. The developed method was successfully applied to the determination of MKS in tablets and spiked human plasma. The results obtained were in good agreement with those obtained using a reported spectrofluorimetric technique.     

Determination of trace amounts of nickel by differential pulse adsorptive cathodic stripping voltammetry using calconcarboxylic acid as a chelating agent

A method for the determination of nickel(II) by stripping voltammetry is described. The method is based on the adsorptive accumulation of nickel(II) calconcarboxylic acid complex onto a hanging mercury drop electrode (HMDE), followed by the reduction of the adsorbed complex using differential pulse voltammetry. The optimum operating conditions and parameters were found to be 0.05 M NH₃/NH₄Cl buffer (pH = 9.5) as the supporting electrolyte, a ligand concentration of 1 × 10^?6 M, accumulation potential of ?0.5 V (vs. Ag/AgCl) and accumulation time of 60 s. At the optimized conditions, the peak current is proportional to the concentration of nickel in the range of 1.7 × 10^?9 to 4.7 × 10^?7 M (0.1–28 ng ml^?1) with a detection limit of 0.05 ng ml^?1. The relative standard deviation (n = 10) at nickel concentrations of 2, 10 and 15 ng ml^?1 varies in the range 0.76 to 2.1%. Possible interferences by metal ions, which are of great significance in real matrices, have been studied. The method was successfully applied to the determination of nickel content in a chocolate sample.     

Voltammetric studies on the interactions between camazepam metabolic series and human serum albumin. Determination of oxazepam using adsorptive stripping voltammetry

The behaviour of oxazepam in adsorptive stripping voltammetry was studied taking into account those conditions which have an influence on the accumulation step (electrolyte, pH, time, potential, drop size and stirring rate), rest time and stripping step (pulse amplitude and scan rate). Oxazepam can be determined at a hanging mercury drop electrode by differential-pulse voltammetry in 0.008 M Britton-Robinson buffer at pH 2.0 with a ?0.50 V accumulation potential. Its detection limit was found to be 3.6 × 10^?10 M (30-s accumulation) and the relative standard deviation for oxazepam concentrations in the range 2.8 × 10^?8?4.0 × 10^?7 M is lower than 2.8% (80-s accumulation). In addition, a procedure using adsorptive stripping voltammetry was developed to study the interactions occurring between human albumin and the camazepam metabolic series (camazepam, temazepam and oxazepam). The interactions decreased in the order temazepam ? oxazepam ? camazepam and the groups and structural modifications favouring interaction were determined.     

Voltammetric determination of selenosulfate ions at a mercury-film electrode

A procedure is proposed for the voltammetric determination of selenium as selenosulfate (SO₃Se^2?) ions at a mercury-film electrode (MFE). Selenosulfate ions are determined in the range from 2 × 10^?4 to 1.0 × 10^?3 M without analyte accumulation, using peak current at ?0.92 ± 0.02 V and in the range from 1 × 10^?7 to 2 × 10^?4 M after analyte accumulation with the open circuit, using peak current at ?1.18 ± 0.03 V as the analytical signal. The mechanisms of SO₃Se^2? reduction at an MFE under the conditions of direct voltammetry and stripping voltammetry with accumulation are proposed and discussed.     

Electrocatalytic Characteristics of Ferrocenecarboxylic Acid Modified Carbon Paste Electrode in the Oxidation and Determination of L‐Cysteine

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenecarboxylic acid modified carbon paste electrode (FCMCPE) in aqueous media using cyclic voltammetry and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00) in cyclic voltammetry, the oxidation of L ‐cysteine is occurs at a potential about 580 mV less positive than that an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α and catalytic reaction rate constant, K′_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear calibration curves were obtained in the ranges of 10^?5 M–10^?3 M and 4.1×10^?8 M–3.7×10^?5 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (2δ) were determined as 2.4×10^?6 M and 2.5×10^?8 M by CV and DPV methods. This method was also examined for determination of L ‐cysteine in some samples, such as Soya protein powder, serum of human blood by using recovery and standard addition methods.     

Adsorptive stripping voltammetry of electroactive organic compounds

Adsorptive stripping voltammetry at a hanging mercury drop electrode is described for various polarographically active compounds. Diazepam, nitrazepam, papaverine and aromatic nitro compounds can be determined at concentrations of 1 × 10^?9–1 × 10^?6 M with errors of 5–7%. The effects of changing accumulation potentials and times are considered. Interference by other surface-active agents may be removed by prior molecular exclusion chromatography.     

L‐Cysteine Voltammetry at a Carbon Paste Electrode Bulk‐Modified with Ferrocenedicarboxylic Acid

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, k_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10^?5 M–2.2×10^?3 M and 1.5×10^?5 M–3.2×10^?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10^?5 M and 1.4×10^?6 M by CV and DPV methods.     

Electrocatalytic Determination of Ascorbic Acid at the Surface of 2,7‐Bis(ferrocenyl ethyl)fluoren‐9‐one Modified Carbon Paste Electrode

A chemically modified carbon paste electrode with 2,7‐bis(ferrocenyl ethyl)fluoren‐9‐one (2,7‐BFEFMCPE) was employed to study the electrocatalytic oxidation of ascorbic acid in aqueous solution using cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The diffusion coefficient (D=1.89×10^?5 cm² s^?1), and the kinetic parameter such as the electron transfer coefficient, α (=0.42) of ascorbic acid oxidation at the surface of 2,7‐BFEFMCPE was determined using electrochemical approaches. It has been found that under an optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such an electrode occurs at a potential about 300 mV less positive than that of an unmodified carbon paste electrode. The catalytic oxidation peak currents show a linear dependence on the ascorbic acid concentration and linear analytical curves were obtained in the ranges of 8.0×10^?5 M–2.0×10^?3 M and 3.1×10^?5 M–3.3×10^?3 M of ascorbic acid with correlation coefficients of 0.9980 and 0.9976 in cyclic voltammetry and differential pulse voltammetry, respectively. The detection limits (2δ) were determined to be 2.9×10^?5 M and 9.0×10^?6 M with cyclic voltammetry and differential pulse voltammetry, respectively. This method was also examined for determination of ascorbic acid in pharmaceutical preparations.