Electrocatalytic Oxidation and Voltammetric Determination of Hydrazine on the Tetrabromo‐p‐Benzoquinone Modified Carbon Paste Electrode

The electrochemical properties of hydrazine studied at the surface of a carbon paste electrode spiked with p‐bromanil (tetrabromo‐p‐benzoquinone) using cyclic voltammetry (CV), double potential‐step chronoamperometry and differential pulse voltammetry (DPV) in aqueous media. The results show this quinone derivative modified carbon paste electrode, can catalyze the hydrazine oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 10.00), the oxidation of hydrazine at the surface of this carbon paste modified electrode occurs at a potential of about 550 mV less positive than that of a bar carbon paste electrode. The electrocatalytic oxidation peak current of hydrazine showed a linear dependent on the hydrazine concentrations and linear analytical curves were obtained in the ranges of 6.00×10^?5 M–8.00×10^?3 M and 7.00×10^?6 M–8.00×10^?4 M of hydrazine concentration with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 3.6×10^?5 M and 5.2×10^?6 M by CV and DPV methods. This method was also used for the determination of hydrazine in the real sample (waste water of the Mazandaran wood and paper factory) by standard addition method.     

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.     

Carbon Paste Electrode Incorporating 1‐[4‐(Ferrocenyl Ethynyl) Phenyl]‐1‐Ethanone for Electrocatalytic and Voltammetric Determination of Tryptophan

A carbon paste electrode spiked with 1‐[4‐ferrocenyl ethynyl) phenyl]‐1‐ethanone (4FEPE) was constructed by incorporation of 4FEPE in graphite powder‐paraffin oil matrix. It has been shown by direct current cyclic voltammetry and double step chronoamperometry that this electrode can catalyze the oxidation of tryptophan (Trp) in aqueous buffered solution. It has been found that under optimum condition (pH 7.00), the oxidation of Trp at the surface of such an electrode occurs at a potential about 200 mV less positive than at an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α and rate constant for the chemical reaction between Trp and redox sites in 4FEPE modified carbon paste electrode (4FEPEMCPE) were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of Trp showed a linear dependent on the Trp concentrations and linear calibration curves were obtained in the ranges of 6.00×10^?6 M–3.35×10^?3 M and 8.50×10^?7 M–6.34×10^?5 M of Trp concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 1.80×10^?6 M and 5.60×10^?7 M by CV and DPV methods. This method was also examined as a selective, simple and precise new method for voltammetric determination of tryptophan in real sample.     

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.     

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.     

Electrochemical Analysis of D‐Penicillamine Using a Carbon Paste Electrode Modified with Ferrocene Carboxylic Acid

The electrochemical behavior of D ‐penicillamine (D ‐PA) studied at the surface of ferrocene carboxylic acid modified carbon paste electrode (FCAMCPE) in aqueous media using cyclic voltammetry and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00), the oxidation of D ‐PA at surface of such an electrode is occurred about 420 mV less positive than that an unmodified carbon paste electrode (CPE). The catalytic oxidation peak current was linearly dependent on the D ‐PA concentration and a linear calibration curve was obtained in the ranges 7.5×10^?5 M – 1.0×10^?3 M and 6.5×10^?6 M?1.0×10^?4 M of D ‐PA with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 6.04×10^?5 M and 6.15×10^?6 M. This method was also used for the determination of D ‐PA in pharmaceutical preparation (capsules) by standard addition method.     

The Electrochemical Behavior of α‐Ketoglutarate at the Hanging Mercury Drop Electrode in Acidic Aqueous Solution and Its Practical Application in Environmental and Biological Samples

The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and k_s=0.72 1/s. There was a linear relationship between peak current i_{p, α‐KG} and α‐KG concentration in the range of 2×10^?6–8×10^?4 M α‐KG. The detection limit was 8×10^?7 M and the relative standard deviation was 2.0% (C_α‐KG=8×10^?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δi_p and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10^?6–2.5×10^?4 M. The detection limit was 2.2×10^?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10^?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of Al^III on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD⁺+H₂O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD⁺ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.     

Captopril Modified Silver Electrode and Its Application to the Electroanalysis of Hemoglobin

Abstract

Captopril, 1-[(2S)-3-mercapto-2-methyl-1-oxopropyl]-L-Proline, can be deposited onto a silver electrode by a covalent bonding method to give a long-lived and stable chemically modified electrode(CME). Since the CME is prepared with a reaction between captopril and the substrate silver, the CME being prepared by this method is very stable. Furthermore, Hemoglobin(Hb) exhibits excellent voltammetric response at the modified electrode. Differential pulse voltammetric(DPV) measurements of the protein with this CME reveal the existence of a linear relationship between the anodic peak current and the concentration of Hb in the range of 2×10^?6 ～ 5×10^?5 mol/L. The detection limit is 8×10^?7 mol/L and the relative standard deviation of results is 5% for 6 successive determinations at 2×10_-5 mol/L. The determination of Hb for a real example is carried out.     

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.     

Simultaneous Determination of Dopamine and Ascorbic Acid at an In‐Site Functionalized Self‐Assembled Monolayer on Gold Electrode

The in‐site functionalization of 4‐aminothiophenol (4‐ATP) self‐assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4′‐mercapto‐N‐phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well‐defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0×10^?6?1.25×10^?4 M and 8.0×10^?6?1.3×10^?4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3σ) for DA and AA were found to be 1.2×10^?6 M and 2.4×10^?6 M, respectively. The modified electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Electroanalytical Characterization of Verapamil and its Voltammetric Determination in Pharmaceuticals and Human Serum

Abstract

The electrooxidative behavior and determination of Verapamil HCl, one of the class IV anti‐arrhythmic agent, on a glassy carbon disc electrode were investigated for the first time by using cyclic, differential pulse (DPV), and Osteryoung square wave voltammetry (OSWV). Verapamil showed an irreversible oxidation behavior at all pH values and buffers studied. From the electrochemical response, the main oxidation step was found to be related to the methoxy group on the phenyl ring. DPV and OSWV were used to generate peak current versus concentration curves for verapamil. A linear response was obtained in the range comprised between 8×10^?7 and 1×10^?4 M for both techniques with detection limit of 1.61×10^?7 M for DPV and 1.33×10^?7 M for OSWV. The repeatability and reproducibility of the methods for all investigated media (such as supporting electrolyte and serum samples) were determined. Precision and accuracy were also checked in all media. The methods were proposed for the determination of verapamil in dosage forms adopting both DPV and OSWV modes. The methods were extended to the in vitro determination of verapamil in spiked serum samples. No electroactive interferences from the endogenous substances were found in human plasma.     

Electrocatalytic Oxidation and Voltammetric Determination of L‐Cysteic Acid at the Surface of p‐Bromanil Modified Carbon Paste Electrode

The electrochemical properties of L ‐cysteic acid studied at the surface of p‐bromanil (tetrabromo‐p‐benzoquinone) modified carbon paste electrode (BMCPE) in aqueous media by cyclic voltammetry (CV) and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00) in cyclic voltammetry, the oxidation of L ‐cysteic acid at the surface of BMCPE occurs at a half‐wave potential of p‐bromanil redox system (e.g., 100 mV vs. Ag|AgCl|KCl_sat), whereas, L ‐cysteic acid was electroinactive in the testing potential ranges at the surface of bare carbon paste electrode. The apparent diffusion coefficient of spiked p‐bromanil in paraffin oil was also determined by using the Cottrell equation. The electrocatalytic oxidation peak current of L ‐cysteic acid exhibits a linear dependency to its concentration in the ranges of 8.00×10^?6 M–6.00×10^?3 M and 5.2×10^?7 M–1.0×10^?5 M using CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (2σ) were determined as 5.00×10^?6 M and 4.00×10^?7 M by CV and DPV methods. This method was used as a new, selective, rapid, simple, precise and suitable voltammetric method for determination of L ‐cysteic acid in serum of patient's blood with migraine disease.     

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%.     

Selective determination of L-dopa in the presence of ascorbic acid and uric acid using a 3D graphene foam

Three-dimensional interconnected network graphene foam (GF) was synthesized by chemical vapor deposition. The GF was transferred onto indium tin oxide glass, acting as an electrode for the selective determination of L-dopa in the presence of ascorbic and uric acid. Using differential pulse voltammetry (DPV) method, the oxidation peak current is well linear with L-dopa concentration in the range of 0.05–1 μM with a sensitivity of 2.64 μA μM^?1 and in the range of 1–40 μM with a sensitivity of 1.82 μA μM^?1. The detection limit of this electrode for L-dopa is about 20 nM. The proposed electrode can also effectively avoid the interference of ascorbic acid and uric acid, making the proposed sensor suitable for the accurate determination of L-dopa in human urine fluids. This electrode will have a wide range of potential application prospect in electrochemical detection.     

Determination of Benzoyl Peroxide Levels in Wheat Flour and Pharmaceutical Preparations by Differential Pulse Voltammetry in Nonaqueous Media

Abstract

Benzoyl peroxide (BP) was determined by differential pulse voltammetry (DPV) using a glassy carbon electrode in a dichloromethane‐acetic acid (1.5×10^?2 mol l^?1) solution and tetrabutyl ammonium perchlorate (0.01 mol l^?1) as the supporting electrolyte. The peak potential was ?0.045 V (vs. Ag/AgCl). There was a good linear relationship between the peak current and the benzoyl peroxide concentration in the range of 2.5×10^?6–1.0×10^?4 mol l^?1. The detection limit of the method was 2.5×10^?7 mol l^?1. The recovery was 94.8–106.0%. The samples of wheat flour and the pharmaceutical preparations for the treatment of acne vulgaris were directly detected with desired results. The reaction mechanism of benzoyl peroxide on the electrode was also discussed, which was two electrons and two protons irreversible reaction.     

Electrochemical study of vinylsulphone azo dye Reactive Black 5 and its determination at a glassy carbon electrode

The electrochemical oxidation of vinylsulphone azo dye, Reactive Black 5 (RB5), at a glassy carbon electrode has been carried out in phosphate buffer solutions in the pH range 2.85?C11.79 employing cyclic voltammetry (CV) and differential pulse voltammetry (DPV). RB5 showed one well-defined oxidation peak at 0.560 V vs. Ag-AgCl using DPV. The oxidation process was shown to be irreversible over the pH range 2.85?C8.39 and was diffusion controlled. The linear relationship between the peak current height and RB5 concentrations allowed the differential pulse voltammetric determination of the dye over a wide concentration range, from 6.0 × 10^?7 to 1.5 × 10^?6 M with a detection limit of 4.0 × 10^?7 M. The precision and recovery did not exceed 4.9 and 98.2%, respectively. A UV-Vis spectrophotometry method was also proposed for the determination of the RB5 in concentration range from 5.0 × 10^?6 M to 1.0 × 10^?5 M at ??_max = 600 nm with limit of detection of 4.7 × 10^?6 M and RSD of 1.8% for RB5 concentration of 1.0 × 10^?5 M.     

Voltammetric study of the hydrolysis product of fenthion at the Nafion®-modified glassy carbon electrode

The differential pulse voltammetric (DPV) method is proposed for the determination of phosphorothioate insecticide (fenthion) based on the oxidation of its hydrolysis product. A single peak at +0.65 V (vs. Ag/AgCl) is observed at the Nafion®-modified glassy carbon electrode in 0.1 M Britton-Robinson buffer solution (pH 4.0) as a supporting electrolyte. The voltammetric behavior of fenthion was investigated over a wide range of pH (2.0–8.0). The effect of the solution and operational parameters on the sensitivity of the DPV peak was carefully examined in order to select the optimum conditions for the determination of fenthion. Under optimum conditions, the oxidation response gives a linear calibration plot over a concentration range of 8.41 × 10^?7?5.98 × 10^?6 M and the detection limit is found to be 7.6 × 10^?7 M. The effects of some diverse metal ions, anions, and some other organic molecules on the determination of fenthion were studied. The applicability of DPV for the determination of fenthion insecticide in a commercial sample as well as in some water samples was demonstrated.     

Selective Detection of Uric Acid in the Presence of Ascorbic Acid and Dopamine Using Polymerized Luminol Film Modified Glassy Carbon Electrode

Electrochemically polymerized luminol film on a glassy carbon electrode (GCE) surface has been used as a sensor for selective detection of uric acid (UA) in the presence of ascorbic acid (AA) and dopamine (DA). Cyclic voltammetry was used to evaluate the electrochemical properties of the poly(luminol) film modified electrode. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been used for surface characterizations. The bare GCE failed to distinguish the oxidation peaks of AA, DA and UA in phosphate buffer solution (pH 7.0), while the poly(luminol) modified electrode could separate them efficiently. In differential pulse voltammetric (DPV) measurements, the modified GCE could separate AA and DA signals from UA, allowing the selective determination of UA. Using DPV, the linear range (3.0×10^?5 to 1.0×10^?3 M) and the detection limit (2.0×10^?6 M) were estimated for measurement of UA in physiological condition. The applicability of the prepared electrode was demonstrated by measuring UA in human urine samples.     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

Wide linear range nanomaterial/ionophore-based electrode used for determination of lead in environmental and biological samples with differential pulse voltammetry

A new chemically modified carbon paste electrode is fabricated to determine lead ion concentration in its trace level in aqueous media with differential pulse voltammetry (DPV). The best performance is obtained by the carbon paste electrode composition including 20% of dithiodibezoic acid (DDA), 80% of high purity graphite powder and 60?µL of colloidal gold nanoparticle (AuNP) solution. The proposed electrode has a wide linear calibration response from 1?×?10^?9 to 6?×?10^?5 M with a detection limit of 6.6?×?10^?10?M, at pH 3.5. Seven replicate determination of 5?×?10^?8?M of lead ion concentration gives a relative standard deviation of 3.33%. The modified sensor is applied to determine lead contents in some environmental and biological Samples with satisfactory results.