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。     

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。     

网络法数字模拟电活性物种吸附体系的循环伏安曲线

使用指数扩展的网络方法对电活性物质吸附与扩散共存的电化学体系进行了模拟,包括吸附为平衡和非平衡态的情形,所得结果跟文献报道一致并有所补充。该方法具有简便、直观、灵活性强等优点。     

对位叠式循环方波伏安法：Ⅰ.简单可逆电极体系

本文提出叠式循环方波伏安法和对位叠式循环方波伏安法，对简单可逆电极体系的理论作了推导和验证，经对各种电流的比较，发位叠式循环方波伏安法有较多的优点。较之其它方波伏安法灵敏。     

叠式循环阶梯脉冲伏安法：Ⅰ.简单可逆电极体系

本文提出循环阶梯脉冲伏安法和对位叠式循环阶梯脉冲伏安法，推导出简单可逆电极体系的电流方程，研究了峰电流与诸因素的关系，并进行了实验验证，发现对位叠式循环阶梯脉冲伏安法有较多的优点     

络合吸附体系叠式循环方波伏安法的理论研究Ⅱ．不受前行化学反应控制

推导出不受前行化学反应控制的络合吸附不可逆过程叠式循环方波伏安法的电流及其卷积和导数方程，系统地研究了各电流峰形，各峰电流与有关参数的关系，给出了峰电势表达式，并进行了实验验证。该理论同样适用于简单吸附不可逆过程。     

快速循环伏安法及其近期发展

对超微电极快速循环伏安法作了综述。讨论了该法的主要原理、特点和仪器关键性部分。并扼要介绍其主要应用。     

络合吸际体系叠式循环方波伏安法的理论研究

推导出不受前行化学反应控制的络合吸附不可逆过程叠式循环方波伏安法的电流及其卷积和导数方程，系统地研究了各电流一有关参数的关系，给出了峰电势表达式，并进行了实验验证。该理论同样适用于简单吸陵不可逆过程。     

用循环伏安法研究醌亚胺的脱氨反应

用循环伏安法研究了N,N-二乙基对苯二胺,N,N,N′,N′-四乙基对苯二胺,N,N-二乙基氨基酚三类化合物的电化学氧化及其氧化产物的后继化学反应,求算了脱氨反应速率常数,揭示了苯环上甲基取代基和氮原子上不同取代基对脱氨反应的影响。 脱氨反应为OH^-或水进攻醌亚胺的亲核反应。由于甲基的斥电子效应,当苯环上引进甲基取代基时,环上负电荷增大,带正电荷的醌亚胺趋于稳定,水解反应速度减慢。 苯环上引进二个甲基取代基,其相应的苯胺化合物的半波电位下降大约120mV。二乙基对苯二胺的苯环上每引进一个甲基取代基,其氧化产物与彩色成色剂偶合生成的染料的吸收峰向长波方向移动20-30nm。     

化学修饰电极循环伏安法的数值模拟

用ＣＮ法对化学修饰电极（ＣＭＥ）的循环伏安法（ＣＶ）进行了数值模拟。建立了ＣＭＥ的有限扩散理论模型,引入了活度系数比、扩散系数校正因子及动力学参数等。模拟的普鲁士兰（ＰＢ）修饰电极与文献相符很好。     

氨基比林的循环伏安测定及其电化学行为研究

在0.05 mol/L Tris-HCI(pH=8.5)的底液中,采用循环伏安法测定氨基比林,得到一良好的氧化峰,峰电位Ep=0.25 V,峰电流Ip与氨基比林的浓度在8.0×10-7～1.6×10-5mol/L范围内呈线性关系,相关系数r=0.9969,检出限为9.0×10-8mol/L.采用本法测定安痛定注射液中氨基比林的含量,回收率在95.0%～106.2%相对标准偏差(RSD)为1.68%.研究了氨基比林在玻碳电极上的电化学行为,结果表明氨基比林的电极过程具有吸附性和不可逆性.     

Characterization of a Novel Dioxomolybdenum Complex by Cyclic Voltammetry

Metalloenzymes that carry a pterin-based molybdenum cofactor in their center catalyze numerous reactions in the human body and play a crucial role in its metabolism. Specifically, these enzymes promote redox reactions and oxygen transport in the body. Their absence may cause many problems leading to disability or even death in early childhood. Therefore, model compounds need to be synthesized and analyzed to investigate the reactivity, redox potential, and geometry of these cofactors. This study focused on electrode processes and determined the redox potentials of the new bis-(4-mercapto-5-(p-tolyl)-3H-1,2-dithiole-3-thione)-dioxomolybdenum complex by cyclic voltammetry. The 4-mercapto-5-(p-tolyl)-3H-1,2-dithiole-3-thione ligand underwent irreversible oxidation and reduction at thiol and thione functional groups. The new dioxomolybdenum complex showed a quasi-reversible two-stage electrode process.     

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.     

冬凌草甲素的电化学性质及电分析方法研究

研究了抗癌药物冬凌草甲素在悬汞电极上的电化学行为。在NaAc-NaOH(pH 7.8)的缓冲溶液中,冬凌草甲素有一受吸附控制的还原峰,峰电位为-1.150 V,峰电流与冬凌草甲素浓度在7.25×10-7~1.01×10-5mol/L范围内有良好的线性关系,检出限为1.45×10-7mol/L(S/N=3)。对冬凌草片剂实际样品中冬凌草甲素含量测定,结果满意。     

Determination of Minocycline by Semi-Differential Cyclic Voltammetry at a Liquid/Liquid Interface

Abstract

The voltammetric behaviour of minocycline at a water/nitrobenzene interface has been studied by normal, semi-differential and semi-integral cyclic voltammetry. The semi-differential cyclic voltammetry can be used as a rapid, simple method for determination of the antibiotic minocycline in the range of 5–200 ug/ml and the relative standard deviation is within 3%. Drug samples were analyzed and satisfactory results were found as compared with US Pharmacopoeia method.     

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.     

循环伏安法研究大黄素的电化学行为

采用循环伏安法研究了大黄素在滴汞电极上的电化学行为,应用线性扫描法提出了药用植物大黄中大黄素不需分离的直接测定方法。大黄素在pH 5.72 B-R缓冲溶液中,在-0.434 V(vs.Ag/AgCl)处产生一灵敏的极谱峰,峰电流与大黄素浓度在1×10-6~1.5×10-5mol.L-1范围内呈线性关系。试验结果表明:该体系属具有吸附性的准可逆过程体系。