A Selective and Sensitive Method for Simultaneous Determination of Traces of Paracetamol and p‐Aminophenol in Pharmaceuticals Using Carbon Ionic Liquid Electrode

A reliable and simple electrochemical method has been proposed for the simultaneous determination of paracetamol (PAR) and p‐aminophenol (PAP) in pharmaceutical formulations. The oxidation and reduction peak potentials in cyclic voltammetry (CV) for PAR on carbon ionic liquid electrode (CILE) were occurred at 370 and 225 mV vs. Ag/AgCl, respectively at pH 7.0, while those for PAP on CILE appeared at 128 mV and 68 mV, respectively at the scan rate of 0.05 V s^?1. In comparison to the conventional carbon paste electrode, the apparent reversibility and kinetics of the electrochemical reactions of PAR and PAP were significantly improved on CILE. In differential pulse voltammetric technique, the peak potentials for PAR and PAP appeared at 345 and 130 mV, respectively, with the peak separation of 215 mV, sufficient for their simultaneous determination in samples containing these two species. The proposed method was used for simultaneous determination of PAR and PAP in tablets. PAR and PAP can be determined in the ranges of 2.0×10^?6–2.2×10^?3 M and 3.0×10^?7–1.0×10^?3 M, with the detection limits of 5.0×10^?7 and 1.0×10^?7 M (calculated by 3σ), respectively. The relative standard deviations for the determination of PAR and PAP were less than 2%.     

Electrochemical investigation and determination of ceftazidime in pharmaceutical dosage forms and human urine

A voltammetric study of the oxidation of Ceftazidime (CEFT) has been carried out at the glassy carbon electrode by cyclic, differential pulse (DPV) and square wave (SWV) voltammetry. The oxidation of CEFT was irreversible and exhibited diffusion controlled process depending on pH. The oxidation mechanism was proposed and discussed. According to the linear relationship between the peak current and concentration, DPV and SWV voltammetric methods for CEFT assay in pharmaceutical dosage forms and human urine were developed. For analytical purposes, a well resolved diffusion controlled voltammetric peak was obtained in 0.1 M H₂SO₄ at 1.00 and 1.02 V for differential pulse and square wave voltammetric techniques, respectively. The linear response was obtained within the range of 4 × 10^?6?8 × 10^?5 M with a detection limit of 6 × 10^?7 M for differential pulse and 4 × 10^?6–2 × 10^?4 M with a detection limit of 1 × 10^?6 M for square wave voltammetric technique. The determination of CEFT in 0.1 M H₂SO₄ was possible over the 2 × 10^?6–1 × 10^?4 M range in urine sample for both techniques. The standard addition method was used for the recovery studies.     

Voltammetric Determination of Trace Antiepileptic Gabapentin with a Silver‐Nanoparticle Modified Multiwalled Carbon Nanotube Paste Electrode

For the first time, a novel carbon nanotube bed electrode impregnated with silver–nanoparticles (AgNPs) for the determination of trace amounts of gabapentin (GBP) is described. We synthesized the AgNPs via a new procedure. The voltammetric behavior of the electrode was investigated by cyclic voltammetry. There were linear relationships in the ranges from 3.1×10^?9 to 2.9×10^?2 M and from 1.0×10^?8 to 1.0×10^?2 GBP with square wave and differential pulse voltammetric peak currents, respectively. The detection limits were 5.6×10^?10 and 9.7×10^?9 M, respectively. The electrode showed excellent response over a period of 2 months and was successfully applied in human plasma and pharmaceutical capsular products.     

Electrochemical Behaviour and Rapid Determination of L‐Dopa at Electrochemically Pretreated Screen Printed Carbon Electrode

A simple and rapid voltammetric method based on a disposable electrochemically pretreated screen‐printed carbon electrode is proposed for the determination of L ‐dopa. Under optimum differential pulse voltammetry conditions a limit of detection of 3.6×10^?7 M for L ‐dopa was obtained. The method was successfully applied to the determination of L ‐dopa in a commercial pharmaceutical formulation.     

Voltammetric Determination of Proguanil in Malarone and Spiked Urine with a Renewable Silver Amalgam Film Electrode

Electrochemical properties of proguanil were investigated by a voltammetric method (SWV) using a renewable silver amalgam film electrode. The influence of buffer pH as well as potential amplitude, frequency, and step potential was studied. The repeatability, precision and recovery of the developed method were examined. The reduction peak current was used for proguanil voltammetric determination in the range 1×10^?7–6×10^?6 mol L^?1, LOD=2.9×10^?8 mol L^?1, LOQ=9.7×10^?8 mol L^?1. The standard addition method was used to determine proguanil in a commercial formulation (Malarone) and in spiked urine.     

Adsorptive stripping voltammetric determination of the anti-inflammatory drug tolmetin in bulk form, pharmaceutical formulation and human serum

The electro-reduction of tolmetin at the hanging mercury drop electrode was studied in different supporting electrolytes using cyclic voltammetry and square-wave stripping voltammetry techniques. Voltammograms of tolmetin exhibited a single well-defined 2-electron irreversible cathodic peak in media of pH < 4, which may be attributed to reduction of the >C=O double bond of the analyte molecule. Adsorption of tolmetin onto the surface of the hanging mercury electrode was identified and each adsorbed tolmetin molecule was found to occupy an area of 0.23 nm². A square-wave adsorptive cathodic stripping voltammetric procedure was described for the direct determination of tolmetin in bulk form and pharmaceutical formulation (Rumatol® capsules) with a limit of quantitation of 2 × 10^?9 M and a mean percentage recovery of 98.35 ± 1.21% to 99.57 ± 1.23. Moreover, the described procedure was successfully applied for the direct assay of tolmetin in spiked human serum without pretreatment or extraction prior to the analysis while a quantitation limit of 5 × 10^?9 M tolmetin was achieved.      

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.     

Zeolite-Modified Carbon-Paste Electrode as a Selective Voltammetric Sensor for Detection of Tryptophan in Pharmaceutical Preparations

Abstract

Several synthetic zeolites such as mazzite, mordenite, zeolite L, zeolite beta, and MCM-41 were tested as electrode modifiers in voltammetric determination of tryptophan. It was found that addition of zeolite beta to the carbon paste would generate the peak current of Trp because of its catalytic effect. The anodic peak currents were proportional to Trp concentrations in the range of 5.0 × 10^?7 to 5.0 × 10^?3 M. The detection limit was 1.0 × 10^?7 M. The influence of several species, especially other amino acids, were tested. The proposed method was applied successfully to the determination of tryptophan in pharmaceutical formulations.     

Voltammetric Investigation and Determination of Mefloquine

The electrochemical reduction behavior of mefloquine HCl (MEF), the antimalarial drug, was studied in aqueous alcoholic media at a hanging mercury drop electrode. Cyclic voltammetric studies showed one well‐defined reduction peak and one ill‐defined reduction wave between pH 1.5 and 12.03. The reduction was found as irreversible or quasireversible depending on pH and exhibited diffusion controlled process. The mechanism of reduction process was discussed. A systematic study of the experimental parameters that affect the differential pulse and square wave response was carried out and the optimized experimental conditions were obtained. The calibration plots were derived for the determination of MEF in pharmaceutical dosage forms and biological samples. DPV and SWV techniques for the determination of MEF in Britton–Robinson buffer at pH 11.10, which allows quantitation over the 6×10^?6 to 8×10^?5 M range in the supporting electrolyte, were proposed. The linear response was obtained in samples in the ranges of 6×10^?6 to 6×10^?5 M for both techniques. These methods are fully validated. The standard addition method was used in the biological media. No electroactive interferences from the excipients and endogenous substances were found in tablets and biological fluids.     

Electrochemical reduction and quantification of menadione in sodium dodecyl sulfate micellar media

Menadione cyclic voltammograms show a pair of redox steps on glassy carbon electrode in 0.1 M H₃PO₄ with potential separation of 343 mV. Cationic, nonionic, and anionic surfactants micellar media significantly decrease the menadione peak potential separation. Statistically significant increase of menadione reduction current (3- and 4.4-fold) has been observed in Triton X 100 and sodium dodecyl sulfate (SDS) micellar media, respectively. Electrochemical reduction of menadione in 9 mM SDS micellar media is reversible diffusion-controlled one-electron process corresponding to formation of relatively stable semiquinone anion radical. The linear dynamic ranges of menadione determination are 7–560 and 600–2,550 μM with the limits of detection and quantification of 1.66 and 5.53 μM, respectively. The current concentration sensitivity is (8.6?±?0.2)?×?10³ μA μM^?1. The voltammetric method for the determination of menadione in pharmaceutical “Aekol” based on preliminary extraction with ethanol has been developed.     

Electrochemical Behavior of Graphene‐Based Sensors on the Redox Mechanism of Aspirin

The electrochemical behavior of aspirin at a graphene modified glassy carbon electrode has been investigated using cyclic and differential pulse voltammetric techniques. The dependence of the current on pH, concentration and scan rate was investigated to optimize the experimental conditions for determination of aspirin. A plausible oxidation mechanism was proposed. Under the optimum conditions, the oxidation peak current was linearly proportional to the concentration of aspirin in the range from 1.00×10^?6 to 2.00×10^?4 M with a detection limit of 20.2 nM. The proposed method was successfully applied to aspirin determination in pharmaceutical and real samples.     

Voltammetric determination of theophylline in pharmaceutical formulations using aligned carbon nanotubes (ACNTs) film modified electrode

A novel rapid, convenient and sensitive electrochemical method has been described for the determination of theophylline in pharmaceutical formulations, based on the extraordinary properties of an aligned carbon nanotubes (ACNTs) thin film. The voltammetric results suggest that the ACNTs-coated glass carbon electrode can exhibit excellent electrochemical activity for direct electrochemical oxidation of theophylline. Various experimental parameters such as solution pH value, amount of ACNTs suspension, accumulation conditions and scan rate were optimized for the determination of theophylline. Furthermore, it was found that the peak current increased linearly with the concentration of theophylline in the range of 8.0 × 10^?8?1.0 × 10^?5 M and the detection limit was 1.6 × 10^?8 M using differential pulse voltammetry. This newly proposed method has been applied successfully to the determination of theophylline in drugs.     

Polymer-modified glassy carbon electrode for the electrochemical detection of quinine in human urine and pharmaceutical formulations

Glassy carbon electrode was modified by electropolymerization of 4-amino-3-hydroxynaphthalene sulfonic acid. Cyclic voltammetric study of quinine showed higher current response at the modified electrode compared to the bare and activated glassy carbon electrodes in pH 7.0 phosphate buffer solution. Under optimized conditions, a calibration curve was obtained by square wave voltammetry at the modified electrode. The linear relationship between the peak current and the concentration of quinine in the range of 1.0?×?10^?7 to 1.0?×?10^?5 M was I _pa (in microamperes)?=?6.26C (in micromolars)?+?0.2997 (R ²?=?0.999). The detection limit calculated (S/N?=?3) was 1.42?×?10^?8 M, which is much lower than similar reports. The method was successfully applied for the determination of quinine in spiked human urine, and pharmaceutical formulations and recovery values >90 % were obtained.     

Anodic Voltammetric Behavior and Determination of Antihistaminic Agent: Fexofenadine HCl

Abstract

A voltammetric study of the oxidation of fexofenadine HCl (FEXO) has been carried out at the glassy carbon electrode. The electrochemical oxidation of FEXO was investigated by cyclic, linear sweep, differential pulse (DPV), and square wave (SWV) voltammetry using glassy carbon electrode. The oxidation of FEXO was irreversible and exhibited diffusion‐controlled process depending on pH. The dependence of intensities of currents and potentials on pH, concentration, scan rate, nature of the buffer was investigated. Different parameters were tested to optimize the conditions for the determination of FEXO. For analytical purposes, a very well resolved diffusion‐controlled voltammetric peak was obtained in Britton‐Robinson buffer at pH 7.0 with 20% constant amount of methanol for DPV and SWV techniques. The linear response was obtained in supporting electrolyte in the ranges of 1.0×10^?6–2.0×10^?4 M with a detection limit of 6.6×10^?9 M and 5.76×10^?8 M and in serum samples in the ranges of 2.0×10^?6–1.0×10^?4 M with a detection limit of 8.08×10^?8 M and 4.97×10^?8 M for differential pulse and square wave voltammetric techniques, respectively. Only square wave voltammetric technique can be applied to the urine samples, and the linearity was obtained in the ranges of 2.0×10^?6–1.0×10^?4 M with a detection limit of 2.00×10^?7 M. Based on this study, simple, rapid, selective and sensitive two voltammetric methods were developed for the determination of FEXO in dosage forms and biological fluids. For the precision and accuracy of the developed methods, recovery studies were used. The standard addition method was used for the recovery studies. No electroactive interferences were found in biological fluids from the endogenous substances and additives present in tablets.     

Salicylate Ion‐Selective Electrode Based on a Calix[4]arene as Ionophore

A salicylate‐selective electrode based on calix[4]arene derivative was developed and its response characteristics were investigated. The optimum membrane composition was 1 % ionophore, 30 % PVC, 69 % DOS. The electrode exhibited a Nernstian slope of 58.8±0.5 mV/pSal in the range of 1.0×10^?5–1.0×10^?1 M with a detection limit of 4.3×10^?6 M at pH 4.0, 20±1 °C. The potentiometric response of the electrode in the presence of different anions was investigated by the separate solution method. The lifetime was found at least 4 months, and its response time was 5–10 s. It was successfully used for the potentiometric determination of salicylate in pharmaceutical preparations.     

Electrochemical Studies and Square‐Wave Adsorptive Stripping Voltammetry of Spironolactone Drug

Abstract

A sensitive and reliable stripping voltammetric method was developed to determine Spironolactone drug. This method is based on the adsorptive accumulation of the drug at a hanging mercury drop electrode and then a negative sweep was initiated, which yield a well defined cathodic peak at ?1000 mV versus Ag/AgCl reference electrode. To achieve high sensitivity, various experimental and instrumental variables were investigated such as supporting electrolyte, pH, accumulation time and potential, drug concentration, scan rate, frequency, pulse amplitude, convection rate and working electrode area. The monitored adsorptive current was directly proportional to the concentration of Spironolactone and it shows a linear response in the range from 1×10^?8 to 2.5×10^?7 mol l^?1 (correlation coefficient=0.999) and the detection limit (S/N=3) is 1.72×10^?10 mol l^?1 at an accumulation time of 90 sec. The developed AdSV procedure shows a good reproducibility, the relative standard deviation RSD% (n=8) at a concentration level of 1.5×10^?7 mol l^?1 was 1.4%, whereas the method accuracy was indicated via the mean recovery of 97.5%±2.04. Possible interferences by several substances usually present in the pharmaceutical formulations have been also evaluated. The applicability of this approach was illustrated by the determination of Spironolactone in pharmaceutical preparation and biological fluids such as serum and urine.     

Voltammetric Determination of Chlorpheniramine Maleate Based on the Enhancement Effect of Sodium‐dodecyl Sulfate at Carbon Paste Electrode

The voltammetric oxidation and determination of chlorpheniramine maleate (CPM) was studied at a carbon paste electrode (CPE) in the presence of sodium‐dodecyl sulfate (SDS) by cyclic and differential pulse voltammetry. The results indicated that the voltammetric response of chlorpheniramine maleate was markedly increased in the low concentration of SDS, suggesting that SDS exhibits observable enhancement effect to the determination of chlorpheniramine maleate. Under the optimal conditions the peak current was proportional to chlorpheniramine maleate concentration in the range of 8.0×10⁻⁶ to 1.0×10⁻⁴ M with detection limit of 1.7×10⁻⁶ M by differential pulse voltammetry. The proposed method was successfully applied to the determination of chlorpheniramine in pharmaceutical and urine samples.     

Preconcentration of Rutin at a Poly Glutamic Acid Modified Electrode and its Determination by Square Wave Voltammetry

Abstract

The voltammetric determination of rutin in 0.04 mol l^?1 B‐R buffer (pH 4.0) by square wave voltammograms (+0.41 V vs. Ag/AgCl_(sat.)) at a poly glutamic acid modified glassy carbon electrode was found to be several orders of magnitude lower than that on a bare glassy carbon electrode. Rutin can be preconcentrated on the films of poly glutamic acid and presented linear relationship from concentration of 7×10^?7 to 1×10^?5 mol l^?1 in 0.04 mol l^?1 B‐R buffer pH 4.0. The method was successfully applied to the determination of rutin in pharmaceutical formulation without any pretreatment.     

Voltammetric Analysis of Oxymetazoline Hydrochloride at Zeolite – Modified Carbon Paste Electrode in Micellar Medium

Simple, sensitive, accurate and inexpensive differential pulse (DPV) and square wave (SWV) voltammetric methods utilizing zeolite modified carbon paste electrode (ZMCPE) were developed for the determination of Oxymetazoline hydrochloride (OXM) in nasal drops. Various experimental parameters were optimized using cyclic voltammetry (CV). Calibration curves were linear over the concentration ranges 9.8×10⁻⁸–3.6×10⁻⁶ M and 9.8×10⁻⁶–9×10⁻⁵ M for DPV and SWV, respectively. The DPV method showed a limit of detection (LOD) of 1.04×10⁻⁷ M. The method was applied for the determination of OXM in pharmaceutical formulation with an average recovery of 101.18 % (%RSD=0.41, n=9).     

Electrochemical Determination of Methotrexate at a Disposable Screen-Printed Electrode and Its Application Studies

Methotrexate is widely used for treatment of various neoplastic diseases. The present work details the voltammetric analysis of Methotrexate at a multi-walled carbon nanotube (MWNT) modified screen-printed electrode (SPE). The fabrication and evaluation of MWNT-derived screen-printed electrochemical sensors based on a MWNT ink are reported. The fabricated MWNT strips combine the attractive advantages of CNT materials and disposable screen printed electrodes. The anodic voltammetric behavior of methotrexate was studied using cyclic and square-wave voltammetric techniques in tris-HCl (pH = 7.5) solution. The oxidation of methotrexate was an irreversible adsorptive-driven process. The experimental conditions such as carbon ink, MWNT, pH, the concentration, and nature of buffer were investigated to optimize the determination of methotrexate. Under optimum conditions, the square-wave voltammetric peak currents were in a linear relationship to methotrexate concentrations in the range of 5.0 × 10^?7M–1.0 × 10^?4 M with a detection limit of 1.0 × 10^?7 M. The MWNT/SPE showed good stability, selectivity, and was successfully used to quantify methotrexate in pharmaceutical formulations.