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.     

用固体石蜡山梨酸碳糊电极电位法测定食品中山梨酸

制备了一种以山梨酸根与乙基紫形成的缔合物为电活性物的固体石蜡山梨酸碳糊电极,并对其性能做了测定。结果显示该电极对山梨酸有较好的能斯特响应。山梨酸的线性范围为2.2×10-5～1.0×10-1mol.L-1,检出限为1.6×10-5mol.L-1。该电极用于食品中山梨酸根的测定,结果与分光光度法结果相符。     

Determination of p-Nitrophenol in Synthetic Textile Wastewater Samples Using a Graphene Oxide/Palladium Nanoparticles Modified Carbon Paste Electrode

This work presents for the first time the incorporation of graphene oxide/palladium nanoparticles composite into a carbon paste electrode and its application in the quantification of p-nitrophenol, a very hazardous pollutant, in a synthetic wastewater sample. The composite presented a homogeneous particle distribution and narrow size distribution, averaging 4 nm. The resulting electrode presented improved shelf stability and prevented the adsorption of byproducts of p-nitrophenol on the electrode surface, which is an advantage when compared to other sensors, due to the presence of the polymer polyvinylimidazole inside the graphene oxide matrix. This work also explores the performance of the proposed sensor among other dyes which can be present simultaneously in industrial wastewater and free water bodies.     

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.     

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.     

Cu(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode; Application for Electrocatalytic Detection of Nitrite

Copper hexacyanoferrate (CuHCF) film‐modified carbon paste electrode (CPE) has been prepared from various electrolytic aqueous solutions using consecutive cyclic voltammetry. The cyclic voltammograms showed the direct deposition of CuHCF films from the mixing of Cu²⁺ and Fe(CN)₆^3? ions and each time with one of the six cations: H⁺, Na⁺, K⁺, NH₄⁺, Mg²⁺, and Al³⁺. The CuHCF film showed a single redox couple that exhibited a cation effect (Na⁺, K⁺, Mg²⁺, and NH₄⁺) and anion effect (Cl^?, NO₃^?, SO₄^2?, ClO₄^?, and BrO₃^?) in the cyclic voltammograms. Voltammetric studies have indicated that in presence of nitrite, the cathodic peak current of CuHCF increases, followed by a decrease in the corresponding anodic current. This indicated that nitrite was reduced by the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. The process of reduction and its kinetics were investigated by using cyclic voltammetry, differential pulse voltammetry, chronoamperometry and chronocoulometry techniques. The electrocatalytic ability about 800 mV can be seen. The rate constant of the catalytic reduction of nitrite was found to be 7.9×10⁵ cm³ mol^?1 s^?1. Linearity range obtained was 5×10^?5?8.4×10^?3 by cyclic voltammetry and 8×10^?6?1.3×10^?3 and 4×10^?3?2×10^?2 by differential pulse voltammetry.     

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.     

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.     

掺杂硒修饰碳糊电极伏安法测定对乙酰氨基酚

采用循环伏安法制备了掺杂硒修饰碳糊电极,用循环伏安法和差分脉冲伏安法研究了对乙酰氨基酚在掺杂硒修饰碳糊电极上的电化学行为,建立了掺杂硒修饰碳糊电极测定对乙酰氨基酚的电化学方法。在pH 4.6的0.1mol·L-1乙酸-乙酸钠缓冲溶液中,对乙酰氨基酚在+0.61V呈现一个灵敏的氧化峰。对乙酰氨基酚的浓度在6.0×10-7~1.5×10-4 mol·L-1范围内与其氧化峰电流呈线性关系,检出限(3s/k)为2.8×10-7 mol·L-1。方法用于药品中对乙酰氨基酚的测定,测定结果与药典法测定值相符,测定值的相对标准偏差(n=5)在2.1%~2.5%之间。     

A New Chemically Modified Carbon Paste Electrode Derived from Aloe Vera Xanthate Nanoparticles to Detect Mercury Ions

This environmentally benign work describes a simple electrochemical sensor constructed with a chemically modified carbon paste electrode (CMCPE) using aloe vera xanthate nanoparticles to detect mercury ions. The characterization and morphology of nanoparticles were thoroughly investigated using modern techniques. The CMCPE efficiently senses the mercury ions. The limit of detection of mercury ions wasexcellent to the order of 0.231 μg mL⁻¹. Real-time sample analysis showed promising results. The recovery range was between 99.4 % and 101.7 %. The activity of CMCPE was commendable even after fifty days.     

A Novel Strategy for Simultaneous Determination of Dopamine and Uric Acid Using a Carbon Paste Electrode Modified with CdTe Quantum Dots

A novel CdTe quantum dots‐modified carbon paste electrode (QDMCPE) was fabricated and used to study the electrooxidation of dopamine and uric acid and their mixtures by electrochemical methods. Using square wave voltammetry (SWV), a highly sensitive and simultaneous determination of dopamine and uric acid was explored at the modified electrode. SWV peak currents of dopamine and uric acid increased linearly with their concentrations in the ranges of 7.5×10^?8–6.0×10^?4 M, and 7.5×10^?6–1.4×10^?3 M, respectively. Finally this new sensor was used for determination of dopamine and uric acid in some real samples.     

Electrocatalytic Determination of Vitamin C Using Calixarene Modified Carbon Paste Electrodes

Effect of in situ complexation of some ions with variable valencies, like Co(II), Ni(II), Mn(II), Cu(II) and Pb(II) on the the electrooxidation of Vitamin C (L ‐ascorbic acid) was studied by cyclic voltammetry using carbon paste electrodes modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene in perchloric acid, acetic acid and ammonium acetate media. Pb(II) was found to bind strongly with p‐tert‐butylcalix[4]arene in acetate medium, resulting in its being retained at the electrode surface and catalyzing the oxidation of ascorbic acid. The overpotential was reduced by about 200 mV with an increase in the peak currents. Linearity was observed over the range of 0.07–400 ppm with a detection limit of 30 ppb by differential pulse voltammetry. Interferences of some common substances like sugars and amino acids were studied and the modified electrode was used for the determination of vitamin C in commercial samples.     

TBP碳糊修饰电极三元络合物体系测定痕量铅（Ⅱ）

研制了磷酸三丁酯（ＴＢＰ）碳糊修饰电极，在含１－苯基－３－甲基－４－苯甲酰基－５－吡唑酮（ＰＭＢＰ）的ＨＣｌ－ＫＣｌ底液中，通过电位富集，将三元络合物Ｐｂ（ＰＭＢＰ）２（ＴＢＰ）２中的铅富集在电极上，用２．５次微分阳极溶出伏安法测定铅．铅浓度在１．０×１０－９～２．５×１０－７ｍｏｌ·Ｌ－１范围内与峰高呈良好的线性关系．该电极用于铜合金和废水中铅的测定，获得满意结果．     

Electrochemical Determination of Tyrosine in the Presence of Dopamine and Uric Acid at the Surface of Gold Nanoparticles Modified Carbon Paste Electrode

A gold nanoparticles modified carbon paste electrode (GN‐CPE) was used as a highly sensitive electrochemical sensor for determination of tyrosine (Tyr), dopamine (DA) and uric acid (UA) in phosphate buffer solution (PBS). The study and measurements were carried out by using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry methods. In DPV, the GN‐CPE could separate the oxidation peak potentials of DA and UA present in the same solution, though at the unmodified CPE the peak potentials were indistinguishable. The prepared electrode showed voltammetric responses with high sensitivity and selectivity for Tyr, DA and UA in optimal conditions, which makes it very suitable for simultaneous determination of these compounds. The calibration curves for Try, DA and UA were linear for the concentrations of each species. The proposed voltammetric approach was also applied to the determination of Tyr concentration in human serum as a real sample.     

Catalytic Determination of Perchlorate Using a Modified Carbon Paste Electrode

Abstract

A method for the catalytic voltammetric determination of perchlorate using a carbon paste electrode modified with a liquid anion exchanger is presented. The fundamental catalytic effect is based on the chemical reoxidation of electrochemically generated Tl(O) by perchlorate which can be monitored by an increase of the corresponding current flow. Perchlorate can be preconcentrated, together with tetrachlorothallate(III) as a catalyst, from hydrochloric acid solutions onto the modified carbon paste electrode under open circuit conditions. For analytical purposes, the increase of the current response for the reoxidation of Tl(O) to Tl(I) is exploited for quantifications. Methodical parameters such as pH, ionic strength of the media, preconcentration time and thallium concentration are investigated; the influence of interferents is studied. The dependence of the current increase on the concentration of perchlorate with different accumulation times is presented. The detection limit (3σ) is 50 μg˙l^?1 ClO₄ ^? (12 min accumulation). To show the applicability of the method to the analysis of real samples spiked drinking water was investigated.     

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%。     

Determination of Ascorbic Acid in the Presence of Uric Acid and Folic Acid by a Nanostructured Electrochemical Sensor Based on a TiO2 Nanoparticle Carbon Paste Electrode

A carbon paste electrode (CPE), modified with novel hydroquinone/TiO₂ nanoparticles, was designed and used for simultaneous determination of ascorbic acid (AA), uric acid (UA) and folic acid (FA). The magnitude of the peak current for modified TiO₂-nanoparticle CPE (MTNCPE) increased sharply in the presence of ascorbic acid and was proportional to its concentration. A dynamic range of 1.0–1400.0 μM, with the detection limit of 6.4 × 10^?7 M for AA, was obtained using the DPV technique (pH = 7.0). The prepared electrode was successfully applied for the determination of AA, UA, and FA in real samples.     

Electrochemical Determination of Dopamine Using a Novel Perylenediimide-Derivative Modified Carbon Paste Electrode

A novel perylenediimide derivative, N,N′-bis(4-{2-[2-(2-methoxyethoxy ethoxy]ethoxy}phenyl)-3,4:9,10-perylene tetracarboxydiimide, was utilized for the modification of a carbon paste electrode to develop a practical and sensitive electrochemical sensor for dopamine detection. The effects of experimental parameters (modifier amount, pH, and scan rate) on the dopamine peak current were examined. The performance of the modified carbon paste electrode was evaluated under optimum conditions and 4.6-fold increase in the peak current was obtained compared to an unmodified carbon paste electrode. The linear range was between 1 and 100?µM dopamine and the limits of detection and quantification were 0.011 and 0.036?µM, respectively. The developed sensor was also applied for the quantitative determination of dopamine in injections and promising results were obtained.     

酸性铬蓝K固体石蜡碳糊修饰电极溶出伏安法测定痕量铅

在pH为8．5,0．2mol/L氨性缓冲底液中,以酸性铬蓝K（ACBK）为修饰剂,固体石蜡为粘合剂,制备了ACBK修饰碳糊电极。Pb2+以Pb-ACBK络合物的形式吸附在电极上,在-1．0V电位下电解,以阳极溶出伏安法测定Ph2+,在0．11V（vs.SCE）处有灵敏的氧化峰,其一次微分峰电流与Pb2+浓度在1．0×10-11～1．0×10-5mol/L范围内的对数呈良好的线性关系。此法的检测限为5．0×10-12mol/L。     

纳米二氧化铈修饰碳糊电极线性扫描伏安法测定苯酚

在0.01mol.L-1硼砂溶液(pH 9.18)中,用纳米二氧化铈修饰碳糊电极作为工作电极,线性扫描伏安法测定苯酚。伏安图上出现一灵敏的氧化峰,其峰电位为+0.56V(vs.SCE),峰电流与苯酚的浓度在1.0×10-7～2.0×10-4 mol.L-1范围内呈线性关系,检出限(3s/k)为5.0×10-8 mol.L-1。富集时间为30s,同时采用线性扫描伏安法研究苯酚在纳米二氧化铈修饰碳糊电极上的氧化还原反应,结果表明此电极反应为一不可逆的吸附过程。