Kinetic Study of the Oxidation of Catechols in the Presence of Some Aza‐crown Ethers by Digital Simulation of Cyclic Voltammograms

The electrochemical oxidation of catechols ( 1 ) have been studied in the presence of diaza‐18‐crown‐6 (DA18C6) ( 3a ), diaza‐15‐crown‐5 (DA15C5) ( 3b ), and aza‐15‐crown‐5 (A15C5) ( 3c ) as nucleophiles in aqueous solution, by means of cyclic voltammetry and controlled‐potential coulometry. The results indicate the participation of electrochemically generated o‐benzoquinones ( 2 ) in Michael‐type reaction with aza‐crown ethers ( 3 ) to form the corresponding new o‐benzoquinone‐aza‐crown ether adducts ( 5 ). Based on ECE mechanism, the observed homogeneous rate constants (k_obs) of the reaction of o‐bezoquinones ( 2 ) with aza‐crown ethers ( 3 ) were estimated by comparing the experimental cyclic voltammograms with the digital simulated results. The calculated observed homogeneous rate constants (k_obs) was found to vary in the order DA18C6>DA15C5>A15C5.     

Electrochemical Oxidation of Catechols in the Presence of Triethyl Phosphite

The mechanism of electrochemical oxidation of catechol and some of its derivatives have been studied in the presence of triethyl phosphite as a nucleophile in aqueous solution. Voltammetric studies indicate that the quinones derived from catechol, and its derivatives, participate in Michael addition reaction with triethyl phosphite. The reaction mechanism consists of electron transfer followed by a chemical reaction which is named as an EC mechanism. The homogeneous rate constants (k_obs) were estimated by comparing the experimental cyclic voltammograms with the digitally simulated voltammograms based on EC mechanism. Also the effects of nucleophile concentration and substituted group of catechols on voltammetric behavior and the rate constants of chemical reactions were examined.     

Differential Pulse Voltammetric Determination of L-Cysteine After Cyclic Voltammetry in Presence of Catechol with Glassy Carbon Electrode

An electrochemical method of determination of cysteine has been developed in the solution containing catechol as the indicator. Nucleophilic addition of the thiol species to the electrogenerated o-quinone results in the formation of o-quinone-cysteine adducts that easily accumulate use at the surface of the electrode in the acidic solution. Therefore, the use of cyclic voltammetry leads to the amplification of the o-quinone-cysteine adduct's reductive current. As cyclic voltammetry was performed prior to differential pulse voltammetry, the peak of o-quinone-cysteine could be separated preferentially from o-quinone in the differential pulse voltammogram and the selectivity of the method has been assessed with no interference from ascorbic acid, glycine, L-tyrosine, or L-lysine. The magnitude of o-quinone-cysteine peak is proportional to the concentration of cysteine, and thus it can be exploited to determine cysteine within the injection. The results were consistent with those obtained by means of HPLC analysis.     

Electrochemical Oxidation of Catechols in the Presence of Pyrimidine-2-thiol: Application to Electrosynthesis

The electrooxidation of catechols (1a–d) in the presence of pyrimidine-2-thiol (3) as a nucleophile in aqueous solution is described. The mechanistic investigations using cyclic voltammetry and controlled potential coulometry indicate that the quinone derived from catechols participates in a Michael addition reaction with pyrimidine-2-thiol to form corresponding catechol derivatives of 6a–d (ECEC). The efficient electrosynthesis of 6a–d has been performed at carbon rod electrodes in an undivided cell in good yield and purity.     

An Extended Method for the Practical Evaluation of the Standard Rate Constant from Cyclic Voltammetric Data

The Nicholson's treatment for the evaluation of the heterogeneous standard rate constant k⁰ of electron transfer from cyclic voltammetric (CV) data is combined with the Klingler and Kochi method suitable to totally irreversible systems in order to use very large ΔE_p x n values, where n is the number of electrons involved in a simple electron‐transfer process O+n e^??R. An empirical relationship between the dimensionless parameter Ψ=k⁰ [πDnvF/(RT)]^?1/2 and ΔE_p x n which practically replaces the Nicholson's working curve up to about 200 mV is reported.     

Voltammetric Elucidation of Ion Transfer Through an Extremely Thin Membrane

Digital simulation of the cyclic voltammogram for the ion transfer through a liquid membrane of thickness from 1 mm to 10 nm was performed. The magnitude of current and the shape of the voltammogram simulated for extremely thin membrane (10 nm thick) were similar to those observed experimentally with a bilayer lipid membrane, BLM, of about 10 nm in thick, when the diffusion coefficient of an ion in the BLM was assumed to be extraordinary small (10^?13 to 10^?14 cm² s^?1).     

Voltammetric Study of Aminopurines on Pencil Graphite Electrode in the Presence of Copper Ions

Electrochemical oxidations of aminopurines (adenine, 2‐aminopurine, 2,6‐diaminopurine) and their complexes with Cu(I) on a pencil graphite electrode were investigated by means of linear sweep voltammetry (LSV) and elimination voltammetry with linear scan (EVLS). The anodic process of the Cu(I)‐aminopurine complex, corresponding to the oxidation of Cu(I) to Cu(II), takes place in the potential range between 0.4 and 0.5 V (vs. Ag/AgCl/3 M KCl). At more positive potentials the aminopurines provide voltammetric peaks resulting from the oxidation of the purine ring. The stability of the accumulated complex layer was investigated by the adsorptive transfer stripping technique.     

A Cyclic Voltammetric Study of Some Porphyrazines

Summary.  Some porphyrazines with dimethylamino- or trimethylammoniumethylsulfanyl substituents were studied in dichloromethane or dimethylsulfoxide solution by cyclic voltammetric methods. The cyclic voltammogram of metal free octakis-(dimethyl-aminoethylsulfanyl)-porphyrazine is characterized by three one-electron reduction waves which show quasi-reversible behaviour at all sweep rates observed; the same holds for its cobalt(II) derivative. The quaternized octacationic derivative, however, exhibits four one-electron reduction waves which are reversible at all sweep rates. The reaction mechanisms and diffusion coefficients were investigated. Received October 17, 2000. Accepted (revised) December 11, 2000     

耦联酶催化反应电化学体系的表面循环伏安行为的数字模拟

采用数字模拟法对耦联酶催化反应体系的表面循环伏安行为进行了研究,讨论了介体氧化还原动力学、酶催化动力学及介体催化酶动力学等参数对循环伏安图的影响,并用实验进行了验证。     

可逆,准可逆和不可逆表面反应循环伏安法的数字模拟

用数字模拟的方法研究了可逆、准可逆和不可逆表面反应的循环伏安法响应,与理论推导结果相一致,但数字模拟提供了更灵活、方便、通用性更强的研究表面反应机理的手段,本文建立了有关的数字模型,给出了不同动力学参数条件下的电流-电位关系曲线,讨论了动力学参数对电流函数的影响以及用于测定这些参数的方法。     

Nucleophilic Addition of Thiaproline to Electrochemically Derived o‐Quinone,Application to the Sensitive Voltammetric Detection of Thiaproline

The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10^?8 to 5×10^?6 M with a detection limit of 1×10^?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity.     

普鲁士蓝膜修饰电极循环伏安行为的研究

本文研究普鲁士蓝(PB)膜修饰电极的循环伏安行为,结果表明,膜中电活性中心间的相互作用导致PB膜电极的伏安行为偏离理想表面波.用有限扩散边界模型解释了高电位扫速下膜电极的伏安行为.在含钾离子的电解质溶液中测得PB膜中电荷传输扩散系数为10~(-9)～10~(-11)cm~2/s.     

Cyclic Voltammetric Study of the R-Nitroso Salt Application to the Indirect Determination of Iron(II)

Abstract

The electrochemical behaviour of the R-nitroso salt in 0.5 M HAc/NaAc at pH 4.7 is studied by cyclic voltammetry. The compound shows a very sharp reduction peak at -0.37 V vs SCE giving the corresponding amine derivative. The height of the peak is shown to be inversely proportional to the iron (II) concentration of the solution. A linear calibration plot is obtained between 0 and 56 ppm of iron (II) using, initially, 4.0 mM solution of the salt. A simple and fast procedure was developed for the analysis of standard samples of ferrous iron.     

Electrochemical Oxidation of Donepezil and Its Voltammetric Determination at Gold Electrode

The oxidative ability of donepezil, a frequently prescribed drug for the treatment of Alzheimer’s disease is reported for the first time at a gold electrode. It was oxidized by cyclic voltammetry and determined by square wave voltammetry in phosphate buffer electrolyte. Electrochemical degradation of donepezil was carried out by long term potential cycling. The identification and characterization of the major product, isolated by preparative high performance liquid chromatography, was performed by high resolution mass spectrometry and 1D and 2D nuclear magnetic resonance spectroscopy. Donepezil hydroxy derivative was identified as the major electrochemical oxidation product from donepezil.     

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.     

Cyclic Voltammetric Response of Tetrathiafulvalene-Glucose Oxidase-Modified Electrode and Results for Digital Simulation

Abstract

An amperometric enzyme electrode for the determination of glucose (<16mmol^?1) is constructed by incorporating electron mediators tetrathiafulvalene in Nafion and subsequently coating with immobilized glucose oxidase. The results obtained from measurements of glucose in fermentation samples containing biomass or molasses indicate the utility of the electrode for glucose assay in such media over at least 12 weeks. Digital simulation is employed to study the cyclic voltammetry (CV) of Tetrathiafulvalene-Glucose Oxidase-Modified Glassy Carbon Electrode (TTF-GOD-GCE); the digital model is built and the effects of kinetic parameters on CV-curves are discussed. The response process of the Tetrathiafulvalene-Glucose Oxidase-Modified Electrode is partly explained by the simulation results and further research is expected to guide the design of biosensors and improve the properties of the enzyme-mediator modified electrode.     

耦联一级随后化学反应的准可逆表面体系循环伏安法数字模拟研究

用数字模拟方法研究了耦联一级不可逆随后化学反应的可逆、准可逆及不可逆表面吸附体系的循环伏安响应.建立了有关数字模型.模拟计算得到不同无量纲动力学参数时电流函数-电位极化曲线.给出了测定电荷传递速率常数k和随后反应速率常数中k₁的方法.并研究了对甲氧基偶氮苯在酸性介质中的伏安响应,结果尚好.     

ECEC and ECE‐Type Mechanisms in Electrochemical Oxidation of 4‐Substituted Catechols in the Presence of 4‐Hydroxy‐6‐methyl‐2‐pyrone

Electrochemical oxidation of 3,4‐dihydroxybenzoic acid ( 1 ) and 4‐tert‐butylcatechol ( 5 ) in the presence of 4‐hydroxy‐6‐methyl‐2‐pyrone ( 2 ) as nucleophile in aqueous solution has been studied using cyclic voltammetry and controlled‐potential coulometry. The results indicate that 1 via Michael reaction under electro‐decarboxylation reaction converts to heterocyclic compound 4 , and the quinone derived from 4‐tert‐butylcatechol ( 5 ) participates in Michael reaction with 2 and through an ECE mechanism converts to the corresponding o‐quinone ( 6a ). The electrochemical synthesis of 4 and 6a has been successfully performed in an undivided cell.     

用银-色氨酸复合膜修饰玻碳电极循环伏安法测定去甲肾上腺素

在含有1.0mmol.L-1硝酸银、5.58×10-2 mol.L-1色氨酸的溶液中,于-0.8～1.8V(vs.Ag/AgCl)电位下,在玻碳电极表面电沉积一层银-色氨酸复合膜,制得银-色氨酸复合膜修饰玻碳电极(Ag-TRY/GCE)。采用扫描电镜对电极表面的性能进行表征,循环伏安法对其电化学性能进行研究。试验发现:在pH 6.0磷酸盐缓冲溶液中,去甲肾上腺素(NE)在修饰电极出现一对明显的氧化还原峰,氧化峰电位为0.306V,还原峰电位为0.368V,提出了用循环伏安法测定NE的方法。在试验条件下,氧化峰电流与去甲肾上腺素浓度在3.4×10-7～8.3×10-6 mol.L-1和8.3×10-6～1.1×10-4 mol.L-1两段范围内呈线性关系,检出限(3S/N)为4.3×10-8 mol.L-1。修饰电极用于药物中去甲肾上腺素的测定,加标回收率在95.6%～99.4%之间。     

纯水与自来水中氰离子的比色检测

设计合成了水溶性比色传感器磺酸功能化的偶氮水杨醛吖嗪(S),其结构经由1H NMR,ESI-MS确证.S在纯水与自来水中对氰离子(CN-)具有专一选择性的比色检测能力,最低检出限分别为0.16和0.63 μmol/L.可逆的质子转移检测机制赋予S循环再利用的优势,借助于检测试纸,实现了 CN-可逆的比色检测.该工作为纯...