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.     

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.     

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.     

Acetylferrocene Modified Carbon Paste Electrode; A Sensor for Electrocatalytic Determination of Hydrazine

The electrocatalytic oxidation of hydrazine at a carbon paste electrode spiked with acetylferrocene as a mediator was studied by cyclic voltammetry, differential pulse voltammetry, and chronoamperometry. In contrast to other ferrocenic compounds, acetylferrocene exhibits a chemical irreversible behavior, but it can act as an effective mediator for electrocatalytic oxidation of hydrazine, too. The heterogeneous electron transfer rate constant between acetylferrocene and the electrode substrate (carbon paste) and the diffusion coefficient of spiked acetylferrocene in silicon oil were estimated to be about 3.45×10^?4 cm s^?1 and 4.45×10^?9 cm² s^?1, respectively. It has been found that under the optimum conditions (pH 7.5) the oxidation of hydrazine occurs at a potential of about 228 mV less positive than that of an unmodified carbon paste electrode. The catalytic oxidation peak current of hydrazine was linearly dependent on its concentration and the obtained linear range was 3.09×10^?5 M–1.03×10^?3 M. The detection limit (2σ) has been determined as 2.7×10^?5 M by cyclic voltammetry. Also, the peak current was increased linearly with the concentration of hydrazine in the range of 1×10^?5 M–1×10^?3 M by differential pulse voltammetry with a detection limit of 1×10^?5 M. This catalytic oxidation of hydrazine has been applied as a selective, simple, and precise new method for the determination of hydrazine in water samples.     

Electrochemical Behavior of Chloranil Chemically Modified Carbon Paste Electrode. Application to the Electrocatalytic Determination of Ascorbic Acid

A p‐chloranil modified carbon paste electrode was constructed and the electrochemical behavior of this electrode was studied in the aqueous solution with different pH. From the E_1/2–pH diagram for this compound the values of formal potential E^0' and pK_a of some different redox and acid‐base couples depending on the solution pH were estimated. The diffusion coefficient, D, value for p‐chloranil was estimated 1.5×10^?7 cm² s^?1. It has been shown by direct current cyclic voltammetry and double potential step chronoamperometry, that this p‐chloranil incorporated carbon paste electrode, can catalyze the oxidation of ascorbic acid in the aqueous buffered solution. Under the optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such an electrode occurs at a potential about 325 mV less positive than that at an unmodified carbon past electrode. The catalytic oxidation peak currents was linearly dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 7×10^?5 M–4×10^?3 M of ascorbic acid with a correlation coefficient of 0.9998. The limit of detection (3σ) was determined as 3.5×10 ^?5 M. This method was used as simple, selective and precise voltammetric method for determination of ascorbic acid in pharmaceutical preparations.     

Electrocatalytic Oxidation and Determination of Cysteamine by Poly‐N,N‐dimethylaniline/Ferrocyanide Film Modified Carbon Paste Electrode

Functionalized poly‐N,N‐dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrocatalytic ability of poly‐N,N‐dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of cysteamine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. Results showed that pH 7.00 is the most suitable for this purpose. It is found that the catalytic reaction rate constant, (k_h), is equal to 2.142×10³ M^?1 s^?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the cysteamine concentration and the linearity range obtained was 8.00×10^?5 M–1.14×10^?2 M. Detection limit was determined 7.97×10^?5 M (2σ). This method has been successfully employed for quantification of cysteamine in real sample.     

麦饭石修饰碳糊电极伏安法测定克林霉素

在pH=9的磷酸盐缓冲溶液(PBS)中,用麦饭石修饰碳糊电极循环伏安法研究了克林霉素的电化学性质,并讨论了影响克林霉素测定的各种因素,得到了其测定的最佳实验条件。克林霉素的氧化峰电位是0.80V,氧化峰电流与克林霉素的浓度在3.25×10-6～1.10×10-4 mol.L-1范围内呈良好的线性关系。该测定方法的检出限(S/N=3)为5.0×10-7 mol.L-1。用标准加入法测定回收率范围在94.9%～101.4%。克林霉素在0.80V处的氧化为1电子、1质子参加的受扩散控制的不可逆过程。克林霉素的电化学测定方法能很好地用于实际样品的测定而且结果与药典法一致。     

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.     

Electrocatalytic Determination of 6‐Tioguanine at a p‐Aminophenol Modified Carbon Paste Electrode

A p‐aminophenol modified carbon paste electrode (p‐APMCPE) was constructed for determination of an anticancer drug 6‐thioguanine (6‐TG). The cyclic voltammogram showed that the electrocatalytic oxidation of 6‐TG at the surface of p‐APMCPE occurs at a potential about 840 mV less positive than at an unmodified electrode. Square‐wave voltammetry results presented that the electrocatalytic oxidation peak currents of 6‐TG in pH 9.0 had two linear dynamic ranges in the range of 0.2 to 8.0 and 8.0 to 350.0 μM 6‐TG with a detection limit of 0.08 μM. The kinetic parameters such as electron transfer coefficient (α) and rate constant were determined for the chemical reaction between 6‐TG and p‐aminophenol. Finally, this method was evaluated for the determination of 6‐TG in 6‐thioguanine tablets and urine samples.     

Poly(ortho‐toluidine) Modified Carbon Paste Electrode: A Sensor for Electrocatalytic Reduction of Nitrite

The electrocatalytic reduction of nitrite has been studied by poly(ortho‐toluidine) films modified carbon paste electrode (P‐OT/MCPE). Cyclic voltammetry and chronoamperometry techniques were used to investigate the suitability of poly(ortho‐toluidine) as a mediator for the electrocatalytic nitrite reduction in aqueous solution with various pH. Results showed that pH 0.00 is the most suitable for this purpose. In the optimum pH, the reduction of nitrite occurs at a potential about 600 mV more positive than unmodified carbon paste electrode. The catalytic reaction rate constant, (k_h), was calculated 8.68×10² M^?1 s^?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the nitrite concentration and the linearity range obtained was 5.00×10^?4 M–1.90×10^?2 M. Detection limit has been found to be 3.38×10^?4 M (2σ). This method has been successfully employed for quantification of nitrite in real sample.     

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.     

Electrocatalytic Oxidation of Some Carbohydrates by Nickel/Poly(o‐Aminophenol) Modified Carbon Paste Electrode

This study investigates the electrocatalytic oxidation of glucose and some other carbohydrates on nickel/poly(o‐aminophenol) modified carbon paste electrode as an enzyme free electrode in alkaline solution. Poly(o‐aminophenol) was prepared by electropolymerization using a carbon paste electrode bulk modified with o‐aminophenol and continuous cyclic voltammetry in HClO₄ solution. Then Ni(II) ions were incorporated to electrode by immersion of the polymeric modified electrode having amine group in 1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode; a good redox behavior of Ni(OH)₂/NiOOH couple at the surface of electrode can be observed, the capability of this modified electrode for catalytic oxidation of glucose and other carbohydrates was demonstrated. The amount of α and surface coverage (Γ*) of the redox species and catalytic chemical reaction rate constant (k) for each carbohydrate were calculated. Also, the electrocatalytic oxidation peak currents of all tested carbohydrates exhibit a good linear dependence on concentration and their quantification can be done easily.     

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.     

碳糊电极阳极溶出法测定单宁酸的研究

用碳糊电极阳极溶出法研究了单宁酸的测定方法。实验表明,在1.0 mol/LHCl介质中,富集120 s,单宁酸在0.65 V(vs.SCE)处出现阳极溶出峰,在5.0×10-7~6.0×10-5mol/L范围内,其峰电流的大小与单宁酸的浓度呈线性关系,相关系数为0.9991,检出限为1.0×10-7mol/L。该法灵敏度较高,操作简便,可用于啤酒中单宁酸的测定,平均回收率为99.8%。     

靛红在碳糊电极上的阴极吸附伏安法研究

利用极谱分析仪,在0.40 mol/L的HAc-NaAc(pH 6.0)缓冲液中,发现靛红在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-0.44 V(vs.SCE)。该还原峰的二阶导数峰电流与靛红的浓度在4.0×10-8~1.0×10-7mol/L(富集90 s)范围内成良好的线性关系,相关系数为0.9954,检出限为8.0×10-9mol/L(S/N=3,富集110 s)。探讨了靛红在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药青黛中靛红含量的测定。     

碳糊电极阳极吸附伏安法测定卡托普利

在0.40 mol/L的HAc-NaAc(pH=4.8)缓冲溶液中,卡托普利(Captopril,CPT)在碳糊电极(CPE)上有一灵敏的吸附氧化峰,峰电位为0.23 V(vs.SCE)。该氧化峰的二阶导数峰电流与卡托普利的浓度在2.0×10-8～1.0×10-6mol/L(富集90 s)范围内呈良好的线性关系,相关系数为0.9966,检出限为8.0×10-9mol/L,并成功应用于卡托普利片含量的测定。探讨了卡托普利在碳糊电极上的伏安性质和电极反应机理。     

Electrochemical Reduction and Voltammetric Determination of Metronidazole Benzoate at Modified Carbon Paste Electrode

Abstract

A metalloporphyrin incorporated carbon paste sensor has been developed for the determination of metronidazole benzoate (MTZB). Zn(II) complex of 5,10,15,20-tetrakis (3-methoxy-4-hydroxy phenyl) porphyrin (TMHPP) was used as the active material. The MTZB gave a well-defined reduction peak at?0.713 V in 0.1 mol l^?1 phosphate buffer solution of pH around 7. Compared with bare carbon paste electrode (CPE), the TMHPP Zn(II) modified electrode significantly enhanced the reduction peak current of MTZB as well as lowered its reduction potential. Under optimum conditions the reduction peak current was proportional to MTZB concentration over the range 1 × 10^?3 mol l^?1 to 1 × 10^?5 mol l^?1. The detection limit was found to be 4.36 × 10^?6 mol l^?1. This sensor has been successfully applied for the determination of MTZB in pharmaceutical formulations and urine samples.     

Electrocatalytic Oxidation of Catechol at Multi‐Walled Carbon Nanotubes Modified Electrode

In 0.05 mol/L phosphate buffer solution (pH 7.0), carbon nanotubes modified electrode exhibits rapid response, strong catalytic activity with high stability toward the electrochemical oxidation of catechol. The electrochemical behavior of catechol on both the multi‐walled and single‐walled carbon nanotubes modified electrode was investigated. The experimental conditions, such as pH of the solution and scan rate were optimized. The currents (measured by constant potential amperometry) increase linearly with the concentrations of catechol in the range of 2.0×10^?5–1.2×10^?3 mol/L. Moreover, at the multi‐walled carbon nanotubes modified electrode the electrochemical responses of catechol and ascorbic acid can be separated clearly.