Application of a palladium hexacyanoferrate film-modified aluminum electrode to electrocatalytic oxidation of hydrazine.

A palladium hexacyanoferrate (PdHCF) film as an electrocatalytic material was obtained at an aluminum (Al) electrode by a simple electroless dipping method. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of hydrazine. The electrocatalytic oxidation of hydrazine was studied by cyclic voltammetry and rotating disk electrode voltammetry techniques. A calibration graph obtained for the hydrazine consisted of two segments (localized at concentration ranges 0.39-10 and 20-75 mM). The rate constant k and transfer coefficient alpha for the catalytic reaction and the diffusion coefficient of hydrazine in the solution D, were found to be 3.11 x 10(3) M(-1) s(-1), 0.52 and 8.03 x 10(-6) cm2 s(-1) respectively. The modified electrode was used to amperometric determination of hydrazine in photographic developer. The interference of ascorbic acid and thiosulfate were investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level of stability during electrochemical experiments, making it particularly suitable for analytical purposes.     

Amperometric determination of thiosulfate at a surface-renewable nickel(II) hexacyanoferrate-modified carbon ceramic electrode

Graphite powder-supported nickel(II) hexacyanoferrate (NiHCF) was prepared by the in situ chemical deposition method and then dispersed into methyltrimethoxysilane-derived gels to form a conductive composite. The composite was used as electrode material to construct a surface-renewable three-dimensional NiHCF-modified carbon ceramic electrode. Electrochemical behavior of the chemically modified electrode was well characterized using cyclic and square-wave voltammetry. The electrode presented a good electrocatalytic activity toward the oxidization of thiosulfate and thus was used as an amperometric sensor for thiosulfate in the photographic waste effluent. In addition, the electrode exhibited a distinct advantage of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.     

硫代硫酸盐在铂电极上的电化学氧化行为

用循环伏安法测定了硫代硫酸盐在铂电极上的电化学氧化行为, 结果表明, 其电化学氧化行为与体系的pH和扫描速度密切相关. 当pH为5~6时, 硫代硫酸盐的循环伏安曲线出现三个氧化峰, 峰电位分别在0.05 V、0.58 V和1.02 V附近, 随pH值升高和扫描速度的降低, 0.05 V附近的氧化峰逐渐变得明显, 同时各氧化峰的峰电位与扫描速度的对数, 峰电流与扫描速度的平方根均成很好的线性关系；当pH为8~9时, 硫代硫酸盐的循环伏安曲线出现三个明显的氧化峰, 峰电位分别在0.05 V、0.91 V和1.22 V附近. 随扫描速度降低, 循环伏安曲线出现交叉, 体系呈现明显的电化学振荡行为；但当pH=10时, 1.22 V附近的氧化峰消失. 硫代硫酸盐的电化学氧化行为非常复杂, 电化学氧化机制随体系pH的变化而变化.     

乙酰胆碱酯酶催化水解产物的电化学行为

报道了乙酰硫代胆碱水解产物硫代胆碱在玻碳电极上的电化学行为。以乙酰硫代胆碱作底物,在一定条件下乙酰胆碱酯酶催化底物水解,生成电活性物质硫代胆碱。利用循环伏安法和线性扫描伏安法研究了酶催化水解产物硫代胆碱在玻碳电极上的电化学行为。结果表明:在0.1mol/L的B-R缓冲溶液(pH7.0)中,硫代胆碱有一灵敏的氧化峰,峰电位EP=0.32V(vs.SCE);该体系属具有吸附性的不可逆过程。实验测得电子转移数为2,电极反应速率常数k=0.29s-1。     

Simultaneous determination of oxalate, thiosulfate, and thiocyanate in urine by ion-exclusion chromatography with electrochemical detection

Summary A sensitive ion-exclusion chromatographic method has been developed for determination of oxalate, thiosulfate, and thiocyanate. The method is based on separation of these anions on a polymethacrylate-based, weakly acidic cation-exchange resin (TSKgel OApak-A) and detection by means of a glassy carbon (GC) electrode electrochemically modified with polyvinylpyridine (PVP), palladium, and iridium oxide (PVP/Pd/IrO₂). The electrochemical behavior of oxalate, thiosulfate, and thiocyanate at this chemically modified electrode (CME) have been investigated by cyclic voltammetry. The results indicated that electrocatalytic oxidation of these anions by the electrode was efficient and that the sensitivity, stability, and lifetime of the electrode were relatively high. Combined with ion-exclusion chromatography the PVP/Pd/IrO₂ electrode was used as the working electrode for amperometric detection of these anions. All linear ranges were over two orders of magnitude and detection limits, defined asS/N=3, were 9.0×10⁻⁷ mol L⁻¹ for oxalate, 6.7×10⁻⁷ mol L⁻¹ for thiosulfate, and 5.6×10⁻⁷ mol L⁻¹ for thiocyanate. Correlation coefficients were all>0.998. Coupled with microdialysis sampling the method has been successfully applied to the determination of oxalate, thiosulfate, and thiocyanate in urine.     

Electrochemical Behavior of Crystal Violet on Glassy Carbon Electrodes

The electrochemical behavior of Crystal Violet (CV) on the surface of a glassy carbon electrode in potassium chloride, nitrate, and iodide supporting electrolytes was studied using stripping voltammetry. It was demonstrated that an electroactive complex of CV with iodine was adsorbed on the electrode in a KI solution. This property can be used for determining iodide by adsorption–stripping voltammetry.     

Fundamental aspects of film formation in electrochemical polishing of silver and silver-copper alloys in thiosulfate solutions

The anodic behavior of silver and its alloys with copper in thiosulfate solutions was studied by cycling voltammetry. A scheme of an electrochemical polishing process including the stage of formation of a resistive layer of silver thiosulfate and the chemical stage of its dissolution is suggested.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1299–1302.Original Russian Text Copyright © 2004 by Grishina, Galanin, Ivanova.     

多壁碳纳米管-聚茜素红膜修饰电极测定多菌灵

制备了多壁碳纳米管-聚茜素红膜(MWNT-PAR)修饰电极,用循环伏安法和线性扫描伏安法、计时电量法等研究多菌灵在修饰电极上的电化学行为.结果表明,多菌灵在MWNT-PAR修饰电极上是扩散控制的不可逆电氧化过程.实验测定了部分电极过程参数,并发现多菌灵氧化峰电流的一阶导数值与其浓度在5.0×10~(-6)～1.0×10~(-4) mol/L范围内呈线性关系,回归方程为:I_p ′(A)=-3.112×10~(-6)-1.198c(mol/L),R=-0.9953,其检出限为2.0×10~(-7) mol/L,回收率为99.0%～105.6%.     

阿昔洛韦在硼掺杂金刚石电极上的电化学行为及其与DNA相互作用的研究

利用硼掺杂金刚石(BDD)电极通过循环伏安法和微分脉冲伏安法研究了阿昔洛韦在0.10 mol/L磷酸盐缓冲溶液(pH 7.4)中的电化学行为及其与DNA的相互作用.与玻碳电极相比,阿昔洛韦在BDD电极上的循环伏安曲线在1.17 V处的氧化峰电流更大,背景电流较低.根据峰电位随溶液pH值和扫描速率的变化趋势考察了阿昔洛韦...     

差分脉冲伏安法测定卡托普利

本文基于金电极表面对巯基化合物的吸附作用,提出了一种简便灵敏的测定抗高血压药物卡托普利的新方法.研究了卡托普利在金电极上的伏安响应,优化了差分脉冲伏安法测定卡托普利的实验条件.研究结果表明:在0.217～3.04 mg/L的范围内,卡托普利的氧化峰电流与其浓度呈良好的线性关系,检出限为0.152 mg/L.测定药物中卡...     

头孢哌酮在玻碳电极上的电化学行为及检测方法

应用循环伏安法、线性扫描伏安法和微分脉冲伏安法研究头孢哌酮在玻碳电极上的电化学行为,建立了应用伏安法定量检测头孢哌酮的新方法。头孢哌酮的电极过程为受吸附控制的不可逆过程,电极反应转移电子数和转移质子数均为2。头孢哌酮在pH1.0的1mol/LH3PO4-NaOH介质中,在+0.13V(vs.Ag/AgCl)电位处产生一灵敏的氧化峰,应用微分脉冲伏安法进行测定,该峰电流值Ip与头孢哌酮质量浓度在5.05×10-7～1.01×10-4g/mL范围内有良好的线性关系(R=0.9996),检出限为4.95×10-9g/mL,样品测定平均加标回收率达99.50%,相对标准偏差(RSD)为3.17%。     

3,4,5,6-四氯-2-三氯甲基吡啶在Ag电极上的电还原行为

应用循环伏安法研究了在乙腈和水的混合溶液中3,4,5,6-四氯-2-三氯甲基吡啶于银电极上的电化学行为及其脱氯反应.实验表明:3,4,5,6-四氯-2-三氯甲基吡啶在银电极上的电化学还原是扩散控制的不可逆过程,并有伴随后续化学反应的特征;温度对反应有促进作用.求得3,4,5,6-四氯-2-三氯甲基吡啶在乙腈和水的混合溶液(体积比5∶1)中的扩散系数D=3.0×10-5cm2/s.     

Polystyrene sulphonate wrapped multiwalled carbon nanotubes modified graphite electrode for simultaneous determination of ascorbic acid, dopamine and uric acid

Graphite electrode is modified by casting multi-walled carbon nanotubes (MWCNTs) wrapped with polystyrene sulphonate (PSS) onto the surface of the bare graphite electrode. The modified electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The behavior of the modified electrode towards the oxidation of ascorbic acid (AA), dopamine (DA) and uric acid (UA) has been determined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA). The modified electrode showed better electrocatalytic activity towards AA, DA and UA compared to bare graphite electrode. The electrochemical oxidation signals of AA, DA and UA are well separated into three distinct peaks with peak potential difference of 222, 128 and 350 mV between AA-DA, DA-UA and AA-UA respectively in CV studies and corresponding peak potential separation in DPV are 228, 120 and 348 mV. This modified electrode was successfully used for simultaneous determination of AA, DA and UA in ternary mixture.     

质子惰性介质中芳香族硝基化合物在铂微电极上的电化学行为

采用循环伏安法(CV)和电化学阻抗谱(EIS)技术,以铂微电极为工作电极,大面积铂丝为对电极,饱和甘汞电极为参比电极,研究了不同芳香族硝基化合物(NA)(硝基苯、硝基萘和间二硝基苯)在含有四丁基高氯酸铵(TBAP)电解质的N,N-二甲基甲酰胺(DMF)有机溶液中的电化学行为,并探讨了扫描速率、硝基数目和苯环数目等因素对硝基电化学还原特性的影响.结果表明:三种芳香族硝基化合物在铂微电极上的反应均为扩散控制的准可逆过程;苯环上硝基数目的增加容易使硝基在较低电位下还原;苯环数目的增加导致硝基的还原峰电流急剧减小.     

Studies on electrochemical oxidation of azithromycin and its interaction with bovine serum albumin

A novel nanoparticle film modified electrode has been constructed using a glassy carbon electrode (GCE) coated with a carbon nanotube-dihexadecylphosphate (DHP) film. This modified electrode exhibits an enhanced effectiveness for the oxidation of azithromycin. A method is also described for the evaluation of azithromycin-bovine serum albumin (BSA) interaction. The electrochemical behavior of azithromycin as well as its interaction with BSA at this nanoparticle film electrode has been investigated by cyclic voltammetry, linear sweep voltammetry, differential pulse voltammetry and chronocoulometry. The binding number and association constant between azithromycin and bovine serum albumin have been obtained.     

5-硝基-1,4-萘醌在玻碳电极上的电化学行为研究

采用循环伏安法和线性扫描伏安法,研究了5-硝基-1,4-萘醌在玻碳电极上的电化学行为.结果表明,在丙酮的稀硫酸溶液中,5-硝基-1,4-萘醌在0.0V、-0.8V(vs.SCE)处各有一个还原峰,分别为硝基、醌的不可逆电极反应;5-硝基-1,4-萘醌在电极表面的传质为线性扩散,电还原过程由扩散控制,并求得传递系数分别为...     

DNA Biosensor Based on Carbon Paste Electrodes Modified by Polymer Multilayer

An electrochemical DNA biosensor was developed by DNA immobilization at the electrode surface and its electrochemical behavior was studied in relation with different materials added in the paste. The aim was to study new materials for the development of new electrode surfaces, to be applied in the study of DNA – drug interactions. New electrochemical sensing materials using polymer multilayers were reported for the adsorption of DNA. These materials were prepared by mixing a polymer ion exchanger and graphite powder. The mixture was then used to render the modified carbon paste electrode (CPE), on the surface of which the dsDNA was adsorbed and studied by differential pulse voltammetry (DP voltammetry). The signal of guanine oxidation peak of DNA was followed. This modified biosensor was applied for the study of the interaction between DNA and the known intercalators Ethidium Bromide (EB) and Acridine Orange (AO). The established biosensor exhibited an improvement of its sensitivity and repeatability compared with the conventional CPE DNA biosensor.     

基于纳米银/碳纳米纤维复合材料的增强效应电化学测定多贝斯

将银纳米粒子(AgNPs)电沉积在碳纳米纤维(CNFs)修饰玻碳电极表面制备纳米银/碳纳米纤维修饰玻碳电极(AgNPs/CNFs/GCE).采用扫描电镜考察其表面形态,在K3[Fe(CN)6]-K4[Fe(CN)6]体系中用循环伏安法和电化学阻抗法研究AgNPs/CNFs/GCE的电化学行为.采用循环伏安法和方波伏安法...     

Selective electrooxidation of uric acid in presence of ascorbic acid at a room temperature ionic liquid/nickel hexacyanoferarrate nanoparticles composite electrode

A novel amperometric sensor for the determination of uric acid was fabricated using room temperature ionic liquid and nickel hexacyanoferrate nanoparticle composite which was immobilized on paraffin wax impregnated graphite electrode. The nickel hexacyanoferrate nanoparticle was characterized by UV-vis, X-ray diffraction and field emission scanning electron microscopy. The electrochemical behavior of the modified electrode was investigated in detail by electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. Various experimental parameters influencing the electrochemical behavior of the modified electrode were optimized by varying the supporting electrolyte, scan rate and pH. The apparent electron transfer rate constant (K(s)) and charge transfer coefficient (α) of the modified electrode were found to be 1.358(± 0.02)cm/s and 0.65, respectively from cyclic voltammetry. The sensor exhibited an excellent electrocatalytic activity towards the oxidation of uric acid. The interference from ascorbic acid was easily overcome by coating the modified electrode with PEDOT layer. Under optimal condition, the determination range for uric acid is from 1.0 × 10(-6)M to 2.6 × 10(-3)M and the detection limit was 3.3 × 10(-7)M (3σ). The proposed method has been used for the determination of uric acid in human urine samples.     

Electrochemical study of Azathioprine at thin carbon nanoparticle composite film electrode

Thin carbon nanoparticle/Nafion film (CNP/N), as a novel electrode material, is formed on the surface of the glassy carbon electrode in a simple solvent evaporation process. The electrochemical behavior of Azathioprine (Aza) at the CNP/N-modified electrode is investigated in detail by the means of cyclic voltammetry. During the electrochemical reduction of Aza, an irreversible cathodic peak is appeared. Cyclic voltammetric studies indicated that the reduction process has an irreversible and adsorption-like behavior. The observed reduction peak is attributed to a four-electron process referring to the reduction of nitro group to the corresponding hydroxylamine. The prepared electrode showed an excellent catalytic activity toward the electro-reduction of Aza leading to a significant improvement in sensitivity as compared to the bare glassy carbon electrode where the electrochemical activity for this compound is very weak.