方波伏安法测定酚酞片含量

研究了酚酞在0.5 mol/L氨水-氯化铵缓冲溶液(pH 10)介质中汞膜电极上的电化学行为,并依此建立了酚酞含量的方波伏安法测定.酚酞于-0.98 V(VS.Ag/AgCl)处出现一灵敏的阴极还原峰,峰高与酚酞的浓度在3.0×10-7-5.0×10-5mol/L范围内有良好的线性关系.方法的最低检出限为1.0×10-7mol/L,方法用于酚酞片中酚酞含量的测定,结果满意.     

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。     

络合吸附催化不可逆循环叠式方波伏安法

研究了络合吸附催化不可逆体系受前行化学反应控制（Ｋ＜＜１）和不受前行化学反应控制（Ｋ＞＞１）两种情况下的循环叠式方波伏安法的电流理论，并进行了实验验证，讨论了电流特性，获得区分Ｋ＜＜１和Ｋ＞＞１的判据。对于上述体系的测定，循环叠式方波伏安法的灵敏度比普通差式采样方波伏安法高一个数理级以上。     

Disposable Pencil Graphite Electrode for Ciprofloxacin Determination in Pharmaceutical Formulations by Square Wave Voltammetry

In this work, a new electrochemical sensor based on pencil graphite with interesting features, such as low cost (US$ 0.01 per electrode), ease manufacture, and portability was developed. The sensor showed an adequate manufacturing reproducibility with RSD <5.3 %. Under this electrochemical platform, ciprofloxacin underwent an irreversible oxidation process at 1.03 V, characterized by the diffusion of electroactive species. A simple method by square wave voltammetry (SWV) has been optimized for the determination of ciprofloxacin in pharmaceutical formulations using a pencil graphite electrode (PGE). The method showed satisfactory analytical performance, with a wide linear range (12 to 55 μmol L⁻¹), low detection limit (5.6 μmol L⁻¹), adequate precision (RSD <3.2 %), and accuracy with an average recovery of (102±15)%. Samples of pharmaceutical formulations were evaluated, obtaining levels of ciprofloxacin close to those established by the manufacturers. In addition, the samples were analyzed by liquid chromatography and there was no significant difference between the methods at the 95 % confidence level. In this sense, the method developed proved to be reliable and promising for the quality control of pharmaceutical formulations.     

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。     

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。     

方波伏安法测定孔雀石绿上染率

采用循环伏安法和方波伏安法研究了阳离子染料孔雀石绿(MG)在H2SO4底液(pH 1.0)中的电化学行为.在0.1 V/s的扫描速率下,MG在碳糊电极上显示一个不可逆氧化峰:0.82 V(Pa,2);一对准可逆氧化还原峰:0.51 V(Pa,1)、0.48 V(Pc)(Ep vs.SCE).在0.05～0.9 V/s的扫速范围内,3个峰的峰电流与扫速的平方根都成正比,表明MG的电氧化还原过程均受扩散控制.计时库仑法测得MG的扩散系数为2.31×10-7cm2/s,表面覆盖度是1.18×10-11mol/cm2.还原峰Pc的峰电流与MG的浓度在8.00×10-6～1.00×10-4 mol/L范围内呈线性关系,检出限为6.6 μmol/L(S/N=3),染色工艺中常用的匀染剂"平平加O"和MG染色体系中常见的无机离子不干扰测定.本方法用于测定MG上染腈纶的上染率,结果与分光光度法一致.     

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…     

Comparison of Boron-Doped Diamond and Glassy Carbon Electrodes for Determination of Terbinafine in Pharmaceuticals Using Differential Pulse and Square Wave Voltammetry

This paper examines the electrochemical oxidation of terbinafine with the boron doped diamond and glassy carbon electrodes. The studies were performed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and square-wave voltammetry (SWV). The supporting electrolytes, solution pH, the range of potentials, and the scan rates were optimized. Terbinafine was irreversibly oxidized in all electrolytes, yielding well-defined peaks in the positive potential range. The peak potential shifted towards less positive values as the solution pH increased. Voltammetric determination of terbinafine was performed under the optimized conditions. Using the boron doped diamond electrode, a linear relationship between current and concentration was obtained between 5.44 × 10^?7 and 5.18 and 10^?6 mol/L with SWV and between 7.75 · 10^?7 and 8.55 · 10^?6 mol/L by DPV. At the glassy carbon electrode, a linear relationship between 7.75 · 10^?7 and 8.55 · 10^?6 mol/L was obtained by SWV and between 7.75 · 10^?7 and 1.05 · 10^?5 mol/L by DPV. The sensitivity, precision, and selectivity of the procedures were evaluated. In order to check the practical application of the developed methods, the concentration of terbinafine was determined in pharmaceutical preparations.     

卡那霉素注射液含量的电化学测定

研究了卡那霉素（Kalamycin）在汞膜电极上的电化学行为，并建立了导数阴极溶出方波伏安法测定卡那霉素含量的方法，在PH4．7的HA-NaAc缓冲溶液中，于0.126V（.SCE)左右处出现汞－卡那霉素络合物还原峰，卡那霉素浓度在0．02－－1.5mg.mL^-1之间与导数方波伏安图的峰高存在良好的线性关系，相关系数r=0.9920。方法用于注射液中卡那霉素含量的测定，结果满意。     

Electroanalytical Determination of Promethazine Hydrochloride in Pharmaceutical Formulations on Highly Boron‐Doped Diamond Electrodes Using Square‐Wave Adsorptive Voltammetry

The electrochemical oxidation of promethazine hydrochloride was made on highly boron‐doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square‐wave adsorptive voltammetry results obtained in BR buffer showed two well‐defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s^?1, step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96×10^?7 to 4.76×10^?6 mol L^?1, and calculated detection limits of 2.66×10^?8 mol L^?1 (8.51 μg L^?1) for peak 1 and of 4.61×10^?8 mol L^?1 (14.77 μg L^?1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.     

Electrocatalytic Oxidation and Direct Determination of L-Tyrosine by Square Wave Voltammetry at Multi-wall Carbon Nanotubes Modified Glassy Carbon Electrodes

The electrochemical behavior of L-tyrosine was investigated at a multi-wall carbon nanotubes modified glassy carbon electrode. L-tyrosine itself showed a poor electrochemical response at the bare glassy carbon electrode; however, a multi-wall carbon nanotubes film fabricated on the glassy carbon electrode can directly enhance the electrochemical signal of L-tyrosine when applying cyclic voltammetry and square wave stripping voltammetry without any mediator. Cyclic voltammetry was carried out to study the electrochemical oxidation mechanism of L-tyrosine, which shows a totally irreversible process and an oxidation potential of 671 mV at the modified electrode and 728 mV at the bare electrode, ΔE_p = 57 mV. The anodic peak current linearly increases with the square root of scan rate in the low range, suggesting that the oxidation of L-tyrosine on the multi-wall carbon nanotubes modified electrode is a diffusion-controlled process. The square wave stripping voltammetry currents of L-tyrosine at the multi-wall carbon nanotubes modified electrodes increased linearly with the concentration in the range of 2.0 × 10⁻⁶–5.0 × 10⁻⁴ mol L⁻¹. The detection limit was 4.0 × 10⁻⁷ mol L⁻¹. The method is simple, quick, sensitive and accurate.     

Trace Determination of Chromium by Square‐Wave Adsorptive Stripping Voltammetry on Bismuth Film Electrodes

This works reports the use of adsorptive stripping voltammetry (AdSV) for the trace determination of chromium on a rotating‐disk bismuth‐film electrode (BFE). During the reductive accumulation step, all the chromium species in the sample were reduced to Cr(III) which was complexed with cupferron and the complex was accumulated by adsorption on the surface of a preplated BFE. The stripping step was carried out by using a square‐wave (SW) potential‐time voltammetric signal. Electrochemical cleaning of the bismuth film was employed, enabling the same bismuth film to be used for a series of measurements in the presence of dissolved oxygen. The experimental variables as well as potential interferences were investigated and the figures of merit of the method were established. Using the selected conditions, the 3σ limit of detection for chromium was 100 ng L^?1 (for 120 s of preconcentration) and the relative standard deviation was 3.6% at the 2 μg L^?1 level (n=8). Finally, the method was applied to the determination of chromium in real samples with satisfactory results.     

超微盘电极上阶梯扫描伏安法可逆波理论

本文报道超微盘电极上阶梯扫描伏安法可逆波理论,对电流-电位曲线的性质进行了讨论.利用K₄Fe(CN)₆·KCl体系进行了验证,实验结果与理论相符.     

Determination of Cysteine at Bismuth Nanostructure – Carbon Ionic Liquid Electrode by Square Wave Voltammetry

Bismuth nanostructure‐carbon ionic liquid electrode has been employed for sensitive determination of cysteine (Cys). Bismuth nanostructure was incorporated into the carbon ionic liquid electrode (CILE) and applied for determination of cysteine. An interaction was taking place between bismuth nanostructure and the thiol group of cysteine. The bismuth cysteinate complex oxidation potential occurred at more negative potential compared to the cysteine oxidation peak obtained at bare carbon ionic liquid electrode (CILE). Square wave voltammetry (SWV) was used for the determination of the cysteine and satisfactory results were obtained. The calibration curve was linear in the concentration range of 1 to 500 µM and 0.5–2 mM of Cys. A low detection limit of 0.5 µM was achieved for Cys. The electrode showed a good selectivity for determination of cysteine in the presence of other amino acids. The proposed electrode was satisfactory applied for the determination of cysteine in human serum plasma sample.     

铋膜电极方波吸附溶出伏安法测定纺织品中痕量钴和镍

本文建立了在铋膜修饰电极上采用方波吸附溶出伏安法同时测定纺织品中痕量Co2+和Ni2+的方法.以NH3-NH4Cl作为缓冲液,在丁二酮肟浓度为10 μmol/L的体系中,Co2和Ni2+的还原峰电位分别为-1.13 V和-1.03 V.当缓冲溶液pH为9.2,富集电位为-0.7V,富集时间为200 s时,C02 +和Ni2+在0.5～50 μg/L范围呈现良好的线性关系,相关系数R2＞0.99,其检出限分别为0.79 μg/L和0.96 μg/L,其它金属离子的干扰较小.采用标准加入法测定纺织品中Co>和Ni2+,回收率在94.88％～104.14％之间.     

Optimization of Square Wave Voltammetry (SWV) Parameters by Design of Experiment (DoE) Methodologies for the Determination of Mifepristone at Glassy Carbon Electrode (GCE)

In the present study, an electroanalytical method that permits the optimization of factors affecting SWV for sensitive detection of mifepristone at glassy carbon electrode (GCE) using response surface methodology (RSM) with desirability function (DF) is presented. Factors selected for optimization after screening using full factorial design were frequency (X₁), amplitude (X₂), and pH (X₃). The central composite design as a response surface methodology with desirability function (DF) was applied for obtaining the optimum level. The optimum conditions were obtained as follows: Frequency (X₁=50 Hz), amplitude (X₂=33.4 mV), and pH (X₃=9.4), with an overall desirability function of 0.97. Subsequently, confirmatory experiments were performed in triplicates to validate the optimum conditions. The results obtained were satisfactory and agreed well with less only 11.9 % deviation from the values predicted by the model. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.54 and 1.80 ppm, respectively. The proposed method was applied for a quantitative determination of mifepristone in spiked tap water samples. The recovery tests showed that the detection of mifepristone at GC could be evaluated on environmental samples.     

A Nitrite Electrochemical Sensor Based on Boron‐Doped Diamond Planar Electrochemical Microcells Modified with a Monolacunary Silicotungstate Polyoxoanion

A new boron doped diamond microcells (BDD) was modified, for rapid, selective and highly sensitive determination of nitrite, using a coating film of polyoxometalates (POMs), formed by cyclic voltammetry on the molecular p‐phenylenediamine (PPD) functionalized BDD. The scanning electron microscopy (SEM) technique was used to examine the morphology of (PPD/SiW₁₁) modified (BDD) electrode. It was found that (SiW₁₁) layer was uniformly formed on the electrode surface. It was observed that (BDD/PPD/SiW₁₁) showed excellent electrocatalytic activities towards nitrite ion. Under the selected conditions, the anodic peak maximum at ?0.6 V was linear versus nitrite concentration in the 40 µM–4 mM range, and the detection limit obtained was 20 µM. The newly developed electrode has been successfully applied to the determination of nitrite content in real river water samples.     

方波悬汞吸附伏安法测定八氧化三铀中的钛

U_3O_3用HNO_3溶解,用TBP萃淋树脂分离铀,水溶液用HClO_4蒸干,残渣溶于10ml、pH=6.1的0.1mol/L EDTA、lmol/L的NaAc溶液中,加入1％铜铁试剂0.5ml,于-0.6V～-1.1V的电位范围内用方波伏安法测定钛。标准偏差约为5％,最低检出限为0.5ng/ml。