络合吸附催化循环叠式方波伏安法

对受前行化学反应控制的络合吸附催化体系循环叠式方波伏安法进行了理论推导和实验验证，讨论了电流的特性。结果表明，对于络合吸附催化体系的测定，循环叠式方波伏安法的灵敏度比现行方波伏安法高约２５倍。     

络合吸附体系叠式循环方波伏安法的理论研究：Ⅰ.受前行化学反应控制

推导出受前行化学反应控制的络合吸附不可逆体系叠式循环方波伏安法的电流方程及其各阶导数卷积方程,研究了各峰电流与诸因素的关系,并推导出峰电势表达式。理论推导与实验结果一致。     

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。     

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。     

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。     

吸附方波伏库仑法研究 Ⅱ络合吸附体系

对络合吸附体系分别推导了前行化学反应平衡常数Ｋ１和Ｋ１两种情况的方波伏库仑法的电量方程及作了实验验证，获得判别这两种络合吸附体系的理论依据。讨论了各种因素对伏库仑曲线的影响，并由实验比较了方波伏库仑法和方波伏安法的检测限。     

吸附方波伏库仑法研究：II.络合吸附体系

对络合吸附体系分别推导了前行化学反应平衡常数Ｋ〈〈１和Ｋ〉〉１两种情况的方波伏库仑法的电量方程及作了实验验证，获得判别这两种络合吸附体系的理论依据，讨论了各种因素对估库仑曲线的影响，并由实验比较皮伏库仑法和方波伏安法的检测限。     

对位叠式循环方波伏安法：Ⅱ.平行催化体系

本文提出平行催化体系的对位叠式循环方波伏安法，并对共作了系统的研究，推导了这一方法的催化电流理论方程，并用验验证这理论的正确性，得到其各脉冲电流皆为同方向，对位叠式循环催化电流相当于将电流叠加４次，而波形不受方波幅度大小的影响，因而灵敏度和分辨率有较大提高，优于其它方波伏安法。     

维生素K3电化学反应机理的紫外光谱电化学研究

用薄层池循环伏安法和现场薄层池紫外光谱电化学法研究了维生素Ｋ３（ＶＫ３）在铂电极上的电化学反应机理。薄层池循环伏安实验结果表明：ＶＫ３的电化学反应为二步１ｅ准可逆过程，现场薄层池紫外光谱电化学的实验结果和Ｎｅｒｎｓｔ图解分析表明：电解还原反应的最后产物为２－甲基－１，４－萘酚。该反应偶合有前行化学反应；还原产物经电解氧化的产物为２－甲基－１，４－萘酚。该反应偶合有前行化学反应；还原产物经电解氧化的     

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     

不可逆电极过程方波伏安法动力学研究 Ⅰ.平行催化体系

本文报道了在不可逆电极过程的强催化体系中，当采用快速方波扫描时，正、逆向电流将出现峰形。依据实验结果，提出了“迁出－进入”的等浓度面理论模型，推导了并讨论了电流方程式。结果表明，文中提出的理论能较好地说明实验结果。     

方波伏安法评估聚苯胺膜修饰电极的电荷传输速度

研究导电聚合物的电荷传输机制与速度对于其在应用方面的研究极为重要［‘］．例如在电池的研究中，充放电的速度决定于导电聚合物的电荷传输速度；在电致变色器件的研究中，响应时间也是决定于导电聚合物在氧化还原态间的变化速度，即电荷传输速度．显然较低的电荷传输速度不利于器件的实用化，因此人们必须找到一种能够迅速准确评价电荷传输速度的方法，由于导电聚合物是一个特殊的体系，用一般的电化学方法对其电荷传输速度进行测定时常常遇到这样或那样的问题［‘j．一般说来，导电聚合物的氧化还原过程中均伴随着抗衡离子的运动．体系…     

Study on the Electrochemical Behavior of Melatonin with an Activated Electrode

It was found that melatonin could be incorporated and accumulated on the surface of the glassy carbon electrode which was activated electrochemically by pretreatment in sodium hydroxide solution by means of cycling the potential well into the positive limit of the solvent. In Britton‐Robinson buffer solution (pH 6.7), melatonin gave a sensitive oxidation wave at a potential of +0.65 V (vs.Ag/AgCl) by using Osteryoung square‐wave stripping voltammetry (OSWSV). The oxidation process has been shown to be irreversible and adsorption‐controlled at this electrode by means of cyclic voltammetry and linear sweep voltammetry. A chronocoulometric characterization of the adsorption characteristics of melatonin at this electrode is also presented. The factors affecting the peak current were optimized, and the dependence of peak currents on the concentration of melatonin was found to be linear in the range 8.0×10^?7?1.0×10^?5 mol L^?1. A detection limit of 5.0×10^?8 mol L^?1 was obtained (signal‐to‐noise ratio of 3). This method was applied to the assay of melatonin in tablets and capsules with good recoveries (98–100%).     

Theoretical Contribution towards Understanding Specific Behaviour of “Simple” Protein‐film Reactions in Square‐wave Voltammetry

Surface reactions of uniformly adsorbed redox molecules at working electrode surface are seen as adequate models to studying chemical reactivity of many lipophilic enzymes. When considered under pulse voltammetric techniques, these systems show several uncommon features, whose origin is still not completely clear. The phenomena of “quasireverible maximum”, “splitting” of the net peak in square‐wave voltammetry, and the very steep descent of Faradaic currents of simple surface redox reactions exhibiting fast electron transfer are just some of the features that make these systems quite interesting for further elaborations. In this work, we present a set of theoretical calculations under conditions of square‐wave voltammetry in order try to explain some of aforementioned phenomena. The major goal of our work is to get insight to some voltammetric and chrono‐amperometric features of two considered surface reactions, i. e. (1) the “simple” surface redox reaction, and (2) surface redox reaction coupled to follow‐up irreversible chemical reaction of electrochemically generated redox species (or surface ECirr). We focus on the role of created Red(ads) (here in the reduction pulses only) to the current components of calculated square‐wave voltammograms exhibiting fast electrode reaction. We show that the irreversible chemical removal of electrochemically generated Red(ads) species, created in the potential pulses where half‐reaction of reduction Ox(ads)+ne‐?→Red(ads) is “defined” to take place, causes significant increase of all square‐wave current components. The results presented in this work show how complex the chrono‐amperometric features of surface redox reactions under pulse voltammetric conditions might be. In addition, we point out that both half reactions of a given simple surface redox process can occur, at both, “only reduction” and “only oxidation” potential pulses in square‐wave voltammetry. This, in turn, contributes to the occurrence of many phenomena observed in simple protein‐film voltammetry reactions. The effects of chemical reaction rate to the features of calculated square‐wave voltammograms of surface ECirr systems with fast electrode reaction are reported for the first time in this work.     

Electroanalytical Characteristics of Amisulpride and Voltammetric Determination of the Drug in Pharmaceuticals and Biological Media

The electrochemical oxidation of antipsychotic drug amisulpride (AMS) has been studied in pH range 1.8–11.0 at a stationary glassy carbon electrode by cyclic, differential pulse and square‐wave voltammetry. Two oxidation processes were produced in different supporting electrolyte media. Both of the oxidation processes were irreversible and exhibited diffusion controlled. For analytical purposes, very resolved voltammetric peaks were obtained using differential pulse and square‐wave modes. The linear response was obtained in the range of 4×10^?6 to 6×10^?4 M for the first and second oxidation steps in Britton‐Robinson buffer at pH 7.0 and pH 3.0 (20% methanol v/v), respectively, using both techniques. These methods were used for the determination of AMS in tablets. The first oxidation process was chosen as indicative of the analysis of AMS in biological media. The methods were successfully applied to spiked human serum, urine and simulated gastric fluid samples.     

双氯芬酸钠在石墨烯和室温离子液体复合修饰电极上的电化学行为及其测定

运用循环伏安法研究了双氯芬酸钠(DS)在石墨烯(Gene)和室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合修饰电极上的电化学行为。DS在该复合电极上于0.65V处有一不可逆氧化峰。在40～200 mV/s范围内,其氧化峰电流与扫描速率平方根(v1/2)呈良好线性关系,表明电极过程是受扩散控制。测定了部分电极过程参数,优化了方波溶出伏安法(SWSV)的实验参数,DS浓度在1.0×10-7～1.0×10-4mol/L范围内与峰电流Ipa呈良好线性关系,检出限为8.0×10-8mol/L(S/N=3),加标回收率为95.7%～101.7%。     

An electroanalytical study of the drug proflavine

A square wave adsorptive stripping voltammetric (SWAdSV) method was developed for the determination of proflavine. The electrochemical behaviour of proflavine was investigated by cyclic (CV) and square wave voltammetry (SWV) at the hanging mercury drop electrode (HMDE) and carbon paste electrode (CPE). Different parameters were tested to optimize the conditions of the determination. Better results were obtained by square wave voltammetry using CPE where two oxidation and a reduction peak, appeared, at 0.19, 0.94 and 0.20 V, respectively. The peak at 0.19 V is quasi-reversible and deposition dependent. Linearity was observed in the range of (0.2–23.4) × 10⁻⁸ M (r = 0.998) during the anodic scan and in the range of (1.17–117) × 10⁻⁸ M (r = 0.999) during the cathodic scan. The second peak at 0.94 V is irreversible and deposition independent. The linearity of this peak was observed in the range of (1.29–11.7) × 10⁻⁸ M (r = 0.998). The method was applied to the analysis of bovine serum and gave satisfactory results. Correspondence: S. Th. Girousi, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124, Greece