Use of adsorptive square-wave anodic stripping voltammetry at carbon paste electrode for the determination of amlodipine besylate in pharmaceutical preparations

The antihypertensive drug amlodipine has been characterized voltammetrically in a carbon paste electrode by means of anodic stripping voltammetry. An adsorptive stripping method in a carbon paste electrode for trace determination of amlodipine has been described. Cyclic voltammetric studies indicated the oxidation of amlodipine besylate at the electrode surface through a single two-electron irreversible step fundamentally controlled by adsorption. A study of the variation in the peak current with solution variables such as pH, ionic strength, concentration of amlodipine, possible interference, and instrumental variables, such as preconcentration time and accumulation potential, has resulted in the optimization of the oxidation signal for analytical purposes. By anodic adsorptive anodic stripping voltammetry, the calibration plot was linear in the range 9.9 × 10^?9 ? 1.4 × 10^?7 M with a detection limit of 2 × 10^?10 M in a carbon paste electrode at pH 11.0. The procedure was successfully applied to the assay of amlodipine besylate in some commercial products in the market (Amlopres®, Amlodipine, and Norvasc®). The percentage recoveries were in agreement with those obtained by the reference method.     

Electrochemical determination of 5-hydroxytryptamine using mesoporous SiO<Subscript>2</Subscript> modified carbon paste electrode

A mesoporous SiO₂ was synthesized according to the published work, and then used to modify the carbon paste electrode (CPE). The electrochemical behaviors of 5-hydroxytryptamine (5-HT) at the bare CPE and the mesoporous SiO₂ modified CPE were compared. Owing to the huge surface area, unique mesopores and strong adsorptive ability, the oxidation signal of 5-HT at the mesoporous SiO₂ modified CPE greatly increased, compared with that at the bare CPE. This clearly suggests that the mesoporous SiO₂ modified electrode shows efficient and remarkable enhancement effect towards 5-HT. Based on this, a sensitive, rapid and convenient electrochemical method was developed for the determination of 5-HT after optimizing the experimental parameters such as supporting electrolyte, content of mesoporous SiO₂ as well as accumulation time. The linear range is from 2.0 × 10⁻⁷ to 1.5 × 10⁻⁵ mol/l, and the limit of detection is as low as 8.0 × 10⁻⁸ mol/l after 2-min accumulation. The relative standard deviation (RSD) for 10 mesoporous SiO₂ modified CPEs is evaluated to be 6.7%. Finally, this novel method was successfully used to determine 5-HT in human blood serums.     

Voltammetric determination of azithromycin at the carbon paste electrode

Azithromycin (AZ) is the first member of a class of macrolide azalides antibiotics called azolides. A simple and selective square-wave voltammetric (SWV) method has been developed for the determination of azithromycin in pure form, in pharmaceutical preparation and in biological samples. Determination of azithromycin was accomplished with hand-make carbon paste electrode (CPE) in oxidative screen mode. The counter and reference electrodes were a Pt wire and a Ag/AgCl, respectively. Various parameters that can influence the peak signal (effect of buffer, ionic strength, accumulation time, pH and the composition of the paste) have been scrutinized. The best results were obtained in acetonitrile—aqueous 1 M sodium acetate-acetic acid buffer (pH 4.6) containing 0.1 M KCl (1:9; v/v) using a 15% paraffin oil CPE. The limits of detection and quantification of the pure drug are 0.463 and 1.544 ppb (with the correlation coefficient, r=0.9785and the standard deviation, S.D.=0.1 (n=5), for the accumulation time of 60 s), respectively. The method was successfully applied to the determination of the drug in urine and two forms of pharmaceutical formulations. Recoveries were 99.2—100.5% with S.D.=0.1—and 0.8% (n=5).     

Voltammetric study of nifuroxazide at unmodified and Sephadex-modified carbon paste electrodes

The electrooxidation of nifuroxazide was investigated by cyclic and differential-pulse voltammetry at carbon paste and Sephadex-modified carbon paste electrodes. Nifuroxazide is irreversibly oxidized at all pH values and gives rise to a well-defined oxidation peak. The modification of the carbon paste surface with Sephadex allowed a preconcentration process to take place for nifuroxazide such that higher sensitivity was achieved compared with the bare surface. The influence of the scan rate, time of accumulation, modifier loading, solution conditions and pH on the adsorptive step at the modified carbon paste electrodes was investigated. The direct determination of the drug in urine is also discussed. Received: 2 June 1998 / Revised: 29 January 1999 / Accepted: 2 February 1999     

Simultaneous determination of catechol and hydroquinone by carbon paste electrode modified with hydrophobic ionic liquid-functionalized SBA-15

Hydrophobic ionic liquid-functionalized SBA-15 modified carbon paste electrode (CPSPE) was fabricated, and its electrochemical performance was investigated by cyclic voltammetry, electrochemical impedance spectra, and chronocoulometry in K₃Fe(CN)₆/K₄Fe(CN)₆ solution. Compared with carbon paste electrode (CPE) and SBA-15 modified carbon paste electrode (CSPE), the electron transfer ability was in the sequence as: CPSPE>CSPE>CPE. Meanwhile, the electrocatalytic activity of CPSPE to catechol and hydroquinone was evaluated by cyclic voltammetry, and then, the linear concentration ranges were obtained by the amperometric detection from 2.0?×?10^-5 to 3.2?×?10^-4 M for catechol and 5.0?×?10^-5 to 5.5?×?10^-4 M for hydroquinone, with the detection limits of 5.0?×?10^-7 and 6.0?×?10^-7 M, respectively. The advantages of both ionic liquids and heterogeneous supports made CPSPE exhibit high electrocatalytic activity towards the redox of catechol and hydroquinone by significantly improving their reversibility and enhancing their peak currents. In addition, the present method was applied to the determination of catechol and hydroquinone in artificial wastewater sample, and the results were satisfactory.     

Voltammetric studies of indigo adsorbed on pre-treated carbon paste electrodes

The adsorptive behaviour of indigo on the surface of pre-treated carbon paste electrodes (CPE) has been studied in various aqueous media at different pH, by cyclic (CV) and alternating current voltammetry (ACV). Cyclic voltammograms of this molecule are characterised by two main electrodic processes in the potential range from −0.7 V to +0.9 V (vs. Ag/AgCl/sat. KCl), which are reversible in the pH range of 3–11, these being irreversible when both are recorded at pH 1. The first one at pH 1 becomes purely reversible when the applied potential range is from −0.2 V to +0.2 V and constitutes the best analytical signal. Due to these electrodic features a significant increase in sensitivity was achieved when the signal was recorded by alternating current voltammetry. Indigo was quantified by CV and ACV, in 0.1 M HClO₄ pH 1 and 0.1 M Tris-HCl pH 7.2 solutions. Limits of detection in the sub-nanomolar range were achieved for a 5-min accumulation time by ACV. These data provides useful information about the suitability of this electrodic process as a detection scheme in the development of alkaline phosphatase (AP) based voltammetric affinity devices, in which indigo is generated by the enzymatic hydrolysis of the 3-indoxyl phosphate substrate.     

Electrochemical determination of lead(II) using a montmorillonite calcium-modified carbon paste electrode

Utilizing the fascinating properties of montmorillonite calcium (MMT-Ca), such as huge cationic exchange capacity, strong adsorptive ability, high chemical and mechanical stability, an MMT-Ca modified carbon paste electrode (CPE) was constructed for the sensitive determination of Pb²⁺. In 0.01 mol·L⁻¹ HCl, Pb²⁺ was firstly exchanged and accumulated on an MMT-Ca modified CPE surface and secondly reduced to Pb at −0.90 V. In the following potential sweep from −0.90 to −0.50 V, reduced Pb was oxidized, resulting in an obvious stripping peak at −0.58 V. After optimizing the parameters, such as determining medium, content of MMT-Ca, accumulation potential and time, an electrochemical method was developed for the analysis of Pb²⁺. Compared with bare CPE, the MMT-Ca modified CPE significantly enhances the sensitivity of Pb²⁺ analysis. The limit of detection is evaluated to be 6.0 × 10⁻⁹ mol L⁻¹ Pb²⁺. Finally, this method was successfully employed to determine trace levels of Pb²⁺ in water samples. The first two authors contribute equally do this work     

Voltammetric sensor for buzepide methiodide determination based on TiO2 nanoparticle-modified carbon paste electrode

In this work, we have prepared nano-material modified carbon paste electrode (CPE) for the sensing of an antidepressant, buzepide methiodide (BZP) by incorporating TiO₂ nanoparticles in carbon paste matrix. Electrochemical studies indicated that the TiO₂ nanoparticles efficiently increased the electron transfer kinetics between drug and the electrode. Compared with the nonmodified CPE, the TiO₂-modified CPE greatly enhances the oxidation signal of BZP with negative shift in peak potential. Based on this, we have proposed a sensitive, rapid and convenient electrochemical method for the determination of BZP. Under the optimized conditions, the oxidation peak current of BZP is found to be proportional to its concentration in the range of 5 × 10⁻⁸ to 5 × 10⁻⁵ M with a detection limit of 8.2 × 10⁻⁹ M. Finally, this sensing method was successfully applied for the determination of BZP in human blood serum and urine samples with good recoveries.     

An electrochemical sensor for p-aminophenol based on the mesoporous silica modified carbon paste electrode

A mesoporous silica was synthesised and used to modify the surface of carbon paste electrode (CPE). The electrochemical behaviours of p-aminophenol were investigated. Compared to the unmodified CPE, the mesoporous silica-modified CPE obviously lowers the oxidation potential of p-aminophenol, and remarkably increases its oxidation peak current. The effects of pH value, amount of mesoporous silica, accumulation potential and time were examined. As a result, a sensitive, rapid and convenient electroanalytical method was developed for p-aminophenol. The linear range is from 0.025?mg?L^?1 to 3?mg?L^?1, and the limit of detection is 0.01?mg?L^?1 after 2-min accumulation. Finally, the method was successfully used to determine p-aminophenol in water samples.     

Voltammetric study of nifuroxazide at unmodified and Sephadex-modified carbon paste electrodes

The electrooxidation of nifuroxazide was investigated by cyclic and differential-pulse voltammetry at carbon paste and Sephadex-modified carbon paste electrodes. Nifuroxazide is irreversibly oxidized at all pH values and gives rise to a well-defined oxidation peak. The modification of the carbon paste surface with Sephadex allowed a preconcentration process to take place for nifuroxazide such that higher sensitivity was achieved compared with the bare surface. The influence of the scan rate, time of accumulation, modifier loading, solution conditions and pH on the adsorptive step at the modified carbon paste electrodes was investigated. The direct determination of the drug in urine is also discussed.     

Electrochemical Study of Interaction Between Clozapine and DNA and Its Analytical Application

Abstract

The interaction between clozapine (CLZ) as an orally administrated antipsychotic drug with double stranded calf thymus DNA (dsDNA) was investigated at electrode surface using differential pulse voltammetry (DPV). Activated carbon paste electrode (CPE) was modified with dsDNA and used for monitoring the changes of the characteristics peak of CLZ in 0.05 M acetate buffer (pH 4.3). The adsorptive stripping voltammetry on dsDNA‐modified carbon paste electrode (dsDNA‐CPE) was used for determination of very low concentration of CLZ. Under optimal conditions, the oxidation peak current is proportional to CLZ concentration in the range of 7×10^?9?1.2×10^?6 mol l^?1 with a detection limit of 1.5×10^?9 mol l^?1 for 180 s accumulation time by DPV. The proposed dsDNA‐CPE was successfully used for determination of CLZ in human serum samples with recovery of 97.0±2.5%.     

Adsorptive anodic stripping voltammetry of zirconium(IV)-alizarin red S complex at a carbon paste electrode

A sensitive adsorptive anodic stripping procedure for the determination of trace zirconium at a carbon paste electrode (CPE) has been developed. The method is based on adsorptive accumulation of the Zr(IV)-alizarin red S(ARS) complex onto the surface of the CPE, followed by oxidation of adsorbed species. The optimal experimental conditions include the use of 0.10 mol · L⁻¹ ammonium acetate buffer (pH 4.3), ARS, an accumulation potential of 0.20 V (versus SCE), an accumulation time of 2 min, a scan rate of 200 mV · s⁻¹ and a second-order derivative linear scan mode. The oxidation peak for the complex appears at 0.69 V. The peak current is proportional to the concentration of Zr(IV) over the range of 1.0 × 10⁻⁹–2.0 × 10⁻⁷ mol · L⁻¹, and the detection limit is 3 × 10⁻¹⁰ mol · L⁻¹ for a 2 min adsorption time. The relative standard deviations (n = 8) for 5.0 × 10⁻⁸ and 5.0 × 10⁻⁹ mol · L⁻¹ Zr(IV) are 3.3 and 4.8%, respectively. The proposed method was applied to the determination of zirconium in ore samples with satisfactory results.     

Methanol electrooxidation on novel modified carbon paste electrodes with supported poly(isonicotinic acid) (sodium dodecyl sulfate)/Ni-Co electrocatalysts

Poly(isonicotinic acid) (PINA) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode (CPE). Ni(II) and Co(II) ions were incorporated into the electrode by immersion of the polymer-modified electrodes in Ni(II) and Co(II) ion solutions in different proportions. After the preparation of modified electrodes, their electrochemical behavior was studied by cyclic voltammetric experiments. Electrocatalytic oxidation of methanol at the surface of the modified electrodes was studied in 1?M NaOH solution. These modified electrodes exhibit high electrocatalytic activity and stability in alkaline solution, showing oxidation peaks at low potentials with high current densities. The electrooxidation of methanol was found to be more efficient on CPE/PINA(SDS)/Ni₈₀Co₂₀ than on CPE/PINA(SDS)/Ni and CPE/PINA(SDS)/Ni₅₀Co₅₀. The effects of various parameters such as scan rates and methanol concentration on the electrooxidation of methanol are also investigated.     

Selective determination of cysteine in the presence of tryptophan by carbon paste electrode modified with quinizarine

A sensitive and selective electrochemical method for the determination of L-cysteine was developed using a modified carbon paste electrode (MCPE) with quinizarine. Cyclic voltammetry was used to investigate the redox properties of this modified electrode at various solution pH values and at various scan rates. The apparent charge transfer rate constant, ks and transfer coefficient for electron transfer between quinizarine and carbon paste electrode (CPE) were calculated as 2.76 s^?1 and 0.6, respectively. This modified carbon paste electrode shows excellent electrocatalytic activity toward the oxidation of L-cysteine in a phosphate buffer solution (pH 7.0). The linear range of 1.0 × 10^?6 to 1.0 × 10^?3 M and a detection limit (3s) of 2.2 × 10^?7 M were observed in pH 7.0 phosphate buffer solutions. In differential pulse voltammetry, the quinizarine modified carbon paste electrode (QMCPE) could separate the oxidation peak potentials of L-cysteine and tryptophan present in the same solution, though at the unmodified CPE the peak potentials were indistinguishable. This work introduces a simple and easy approach to selective detection of L-cysteine in the presence of tryptophan. Also, the modified electrode was employed for the determination of L-cysteine in the real samples such as serum of blood and acetylcysteine tablet.     

Voltammetric study of glibenclamide at carbon paste and Sephadex-modified carbon paste electrodes

The oxidative behaviour of the antidiabetic agent glibenclamide on a bare carbon paste electrode (CPE) and a Sephadex-modified carbon paste electrode (SMCPE) was explored by cyclic and differential pulse voltammetry (DPV). The analysis procedure consisted of an open circuit accumulation step in stirred sample solution of Britton-Robinson buffer (0.04 mol L^–1, pH 2.0). This was followed by medium exchange to a clean solution of Britton-Robinson buffer (0.04 mol L^–1, pH 5.0), and subsequently an anodic potential scan was effected to obtain the voltammetric peak. The glibenclamide oxidation peak current obtained by DPV was proportional to the concentration of the glibenclamide in the range of 1.0×10^–9 mol L^–1 to 5.0×10^–8 mol L^–1 for 180 s accumulation time, with a detection limit of 4.0×10^–10 mol L^–1. A method was developed for the determination of glibenclamide in formulation and spiked human serum. Moreover, the proposed procedure was used to estimate the serum concentrations after oral administration of a 5 mg tablet of glibenclamide to three diabetic subjects.     

Preparation and characterization of a new carbon paste electrode based on ketotifen–hexacyanoferrate

A new type of carbon paste electrode (CPE) was made using ketotifen fumarate (C₂₃H₂₃NO₅S; an antiasthmatic/antianaphylactic drug) and hexacyanoferrate. This electrode was constructed using an acidic solution of ketotifen fumarate and potassium hexacyanoferrate. For this purpose, ketotifen fumarate was dissolved in acidic solution (pH 1) and hexacyanoferrate was added by agitation, resulting in ketotifen–hexacyanoferrate (Ket–HCF) precipitate. The obtained precipitate was separated and introduced into carbon paste. The electrochemical behavior of Ket–HCF CPE was studied by cyclic voltammetry. A modified electrode shows one pair of peaks with surface-confined characteristics, with a 0.1-M phosphate buffer as supporting electrolyte. The effects of pH, alkali metal cations, and anions of supporting electrolytes on the electrochemical characteristics of modified electrodes were studied. The diffusion coefficients of hydrated K⁺ in film (D), the transfer coefficient (α), and the transfer rate constant for electrons (k _s) were determined.     

Anodic stripping voltammetric determination of silver ion at a carbon paste electrode modified with carbon nanotubes

A carbon paste electrode (CPE) was modified with multi-wall carbon nanotubes and successfully applied to the determination of silver ion by differential pulse anodic stripping voltammetry. Compared to a conventional CPE, a remarkably improved peak current response and sensitivity is observed. The analytical procedure consisted of an open circuit accumulation step for 2?min in ?0.4?V, this followed by an anodic potential scan between +0.2 and?+?0.6?V to obtain the voltammetric peak. The oxidation peak current is proportional to the concentration of silver ion in the range from 1.0?×?10^?8 to 1.0?×?10^?5?mol?L^?1, with a detection limit of 1.8?×?10^?9?mol?L^?1 after an accumulation time of 120?s. The relative standard deviation for 7 successive determinations of Ag(I) at 0.1???M concentration is 1.99%. The procedure was validated by determining Ag(I) in natural waters.

Study on the adsorptive catalytic voltammetry of aloe-emodin at a carbon paste electrode

Recently, the studies and applications for the pola-rographic catalytic waves of organic compounds at dropping mercury electrode made considerable head-way. Tovopova et al.[1―4] reported the polarographic catalytic waves of the organic compounds containi…     

The electrochemical oxidation of pentachlorophenol and its sensitive determination at chitosan modified carbon paste electrode

We report on a novel electrochemical method to detect trace pentachlorophenol (PCP) by using a chitosan (CS) modified carbon paste electrode (CS/CPE). Compared with that at a bare carbon paste electrode (CPE), the current response was greatly improved at the CS/CPE due to the enhancement effect of CS. Under optimal working conditions, the oxidation peak current of PCP was proportional to its concentration in the range of 1.0 × 10^?7 to 5.0 × 10^?6 and 5.0 × 10^?6 to 1.0 × 10^?4 mol/L, with an extremely low detection limit of 4.0 × 10^?8 mol/L. Our method was successfully used to detect the PCP concentration in vegetable samples.     

Stripping voltammetry method for determination of manganese as complex with oxine at the carbon paste electrode with and without modification with montmorillonite clay

Oxine (8-hydroxyquinoline) was used as an efficient and selective ligand for stripping voltammetry trace determination of Mn(II). A validated square-wave adsorptive cathodic stripping voltammetry method has been developed for determination of Mn(II) selectively as oxine complex using both the bare carbon paste electrode (CPE) and the modified CPE with 7 % (w/w) montmorillonite-Na clay. Modification of carbon paste with montmorillonite clay was found to greatly enhance its adsorption capacity. Limits of detection of 45 ng l^?1 (8.19?×?10^?10 mol L^?1) and 1.8 ng l^?1 (3.28?×?10^?11 mol L^?1) Mn(II) were achieved using the bare and modified CP electrodes, respectively. The achieved limits of detection of Mn(II) as oxine complex using the modified CPE are much sensitive than the detection limits obtained by most of the reported electrochemical methods. The developed stripping voltammetry method using both electrodes was successfully applied for trace determination of Mn(II) in various water samples without interferences from various organic and inorganic species.