Electroanalytical Characteristics of Lercanidipine and its Voltammetric Determination in Pharmaceuticals and Human Serum on Boron-Doped Diamond Electrode

The electrooxidative behavior and determination of lercanidipine (LRC) were investigated in aqueous acetonitrile medium at a boron-doped diamond electrode using voltammetric techniques. The LRC in selected supporting electrolyte presents a well-defined anodic response at 0.944 V, studied by the proposed method. The linear response was obtained in the ranges of 4 × 10^?6 to 2 × 10^?4 mmol L^?1 range in 0.5 mmol L^?1 sulfuric acid supporting electrolyte and 1 × 10^?5 to 8 × 10^?5 mmol L^?1 range in spiked serum sample for square wave voltammetric technique. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage form and in the biological sample, respectively.     

Electrochemical Determination of Anti-Hyperlipidemic Drug Ezetimibe Based on its Oxidation on Solid Electrodes

Ezetimibe is the first of a new class of drugs that selectively inhibits cholesterol absorption in the small intestine and reduces plasma LDL cholesterol. In this study, electrochemical oxidation of ezetimibe was investigated on carbon based electrodes and a single and irreversible peak at both electrodes was observed. A linear response was detected between 2 × 10^?6 and 8 × 10^?5 M with glassy carbon electrode and between 2 × 10^?6 and 2 × 10^?4 M with a boron-doped diamond electrode in 0.1 M H₂SO₄ supporting electrolyte. The proposed methods were successfully applied for the determination of ezetimibe from pharmaceutical dosage forms and human serum samples.     

三种碳基电极材料的电化学性质对比研究(英文)

对硼掺杂纳米金刚石(BDND),硼掺杂微米金刚石(BDMD)和玻碳(GC)电极的电化学性质做了对比研究.利用扫描电子显微镜表征了BDMD和BDND电极,其表面粒子大小分别为1-5μm和20-100nm.利用Raman光谱对两种金刚石薄膜的成分进行了表征,结果表明利用热丝化学气相沉积法得到了高质量的BDND和BDMD薄膜.采用0.5mol·L-1H2SO4溶液测定了三种电极的电化学窗口,BDND和BDMD电极的电化学窗口分别为3.3和3.0V,远比GC电极(2.5V)的要宽.[Fe(CN)6]3-/[Fe(CN)6]4-溶液的循环伏安和交流阻抗测定表明,在BDND、BDMD和GC电极上的峰间距(△Ep)分别为73、92和112mV,且其电子传递电阻(Ret)分别为(98±5)、(260±19)和(400±25)Ω.我们也研究了0.1mmol·L-1双酚A在三种电极上的电化学氧化行为.上述的电化学测定结果表明,两种金刚石电极均比GC电极表现出了更宽的电化学窗口、更好的电化学可逆性质、更快的电子传递速度和更高的电化学稳定性,更为重要的是与BDMD相比BDND的电化学性质有进一步的提高.     

Square‐wave Voltammetric Determination of Propyphenazone,Paracetamol, and Caffeine: Comparative Study between Batch Injection Analysis and Conventional Electrochemical Systems

In this work, the performance of two methods for simultaneous determination of propyphenazone (PRO), paracetamol (PAR), and caffeine (CAF) were compared. One is based on the use of a conventional electrochemical cell (steady‐state condition) and the other on the use of a batch injection analysis (BIA) cell; both systems were associated with square‐wave voltammetric detection (SWV). Three well separated (▵E ≥ 0.25 V) oxidation peaks were obtained for PRO, PAR, and CAF using 0.1 mol L⁻¹ H₂SO₄ as electrolyte and a boron‐doped diamond (BDD) as working electrode. In addition, the electrochemical oxidation mechanism of PRO is being proposed for the first time. The average relative standard deviations of CB and BIA methods were 4.1 % and 3.1 %, respectively. The conventional system presented better limits of detection and the BIA system a significantly greater throughput (four times faster). Statistical comparison between the results obtained with both proposed methods and those obtained by chromatography was carried out and no significant differences were observed (95 % confidence level).     

褪黑素的电化学氧化行为及伏安法测定

采用电化学方法研究了褪黑素在金电极上的不可逆氧化行为.结果表明：其伏安过程为受弱吸附和扩散共同控制的过程,氧化反应电荷转移数为2.采用伏安法对褪黑素进行测定,方法的检出限可达10^-10ml/L数量级.方法可用于脑白金胶囊中褪黑素含量的测定.     

裸玻碳电极伏安测定甲氰咪胍

提出了裸ＧＣＥ不需任何处理测定甲氰咪胍的方法，浓度在３×１０＾－７－６×１０＾－５ｇ／ｍＬ，范围内与峰电流呈线性关系，ＲＳＤ为２．２％，回收率为９６％－１０２％。该方法操作简便快速，大多数金属离子和多种有机生化物质不干扰测定，方法用于片剂和加标尿样中甲氰咪胍的测定与药典方法对照，获得满意结果，并对电极反应进行了初步探讨。     

兴奋剂马钱子碱的电化学氧化及其伏安法测定

以玻碳电极为工作电极，硫酸钾为支持电解质，在合适的ｐＨ条件下，通过循环伏安法，首次观测到了马钱子碱的不可逆氧化峰。在浓度为２０×１０－４～４０×１０－３ｍｏｌ／Ｌ范围内其峰电流与浓度呈线性关系，检测限为１０×１０－５ｍｏｌ／Ｌ。在正常人体的尿样中，采用标准加入法进行回收实验，其平均回收率为１００８％。该法简便、快速，用５０×１０－４ｍｏｌ／Ｌ的马钱子碱溶液重复测定１０次，相对标准偏差为１８％。对其反应机理作了初步探讨。     

Electroanalytical characteristics of antipsychotic drug ziprasidone and its determination in pharmaceuticals and serum samples on solid electrodes

Ziprasidone is a psychotropic agent used for the treatment of schizophrenia. Its oxidation was investigated electrochemically at boron-doped diamond and glassy carbon electrodes using cyclic, differential pulse, and square wave voltammetry. The dependence of the peak current and peak potentials on pH, concentration, nature of the buffer, and scan rate were examined. The process was diffusion and adsorption controlled for boron-doped diamond and glassy carbon electrodes, respectively. The possible mechanism of oxidation was discussed with some model compounds that have indole and piperazine oxidations. A linear response was obtained between 8 × 10⁻⁷ and 8 × 10⁻⁵ M for the first peak in acetate buffer (pH 5.5) and between 2 × 10⁻⁶ and 2 × 10⁻⁴ M for the second peak in 0.1 M H₂SO₄ with boron-doped diamond electrode for differential pulse and square wave voltammetric techniques. The reproducibility and accuracy of the proposed methods were found between 0.31 and 1.20, 99.27 and 100.22, respectively. The recovery studies were also achieved to check selectivity and accuracy of the methods. The proposed methods were applied for the determination of ziprasidone from pharmaceutical dosage forms and human serum samples without any time-consuming extraction, separation, evaporation or adsorption steps prior to drug assay except precipitation of the proteins using acetonitrile. The results were statistically compared with those obtained through an established LC-UV technique, no significant differences were been found between the voltammetric and LC methods.     

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.     

吡哌酸在玻碳电极上的伏安测定

本文应用线性扫描伏安法，微分脉冲伏安法，循环伏安法对吡哌酸在ＧＣＥ上的伏安行为进行了研究，发现在磷酸盐缓冲溶液中＋１．２Ｖ左右有一氧化峰，ＰＰＡ的浓度２－１００μｇ／ｍｌ与峰电流呈良好的线性关系。测定了胶囊和片剂中ＰＰＡ的含量，ＲＳＤ２．１％，回收率在９７％－１０４％之间，方法操作简单快速。ＰＰＡ在ＧＣＥ上的电极反应属于不可逆过程。     

Electroanalytical Characterization of Verapamil and its Voltammetric Determination in Pharmaceuticals and Human Serum

Abstract

The electrooxidative behavior and determination of Verapamil HCl, one of the class IV anti‐arrhythmic agent, on a glassy carbon disc electrode were investigated for the first time by using cyclic, differential pulse (DPV), and Osteryoung square wave voltammetry (OSWV). Verapamil showed an irreversible oxidation behavior at all pH values and buffers studied. From the electrochemical response, the main oxidation step was found to be related to the methoxy group on the phenyl ring. DPV and OSWV were used to generate peak current versus concentration curves for verapamil. A linear response was obtained in the range comprised between 8×10^?7 and 1×10^?4 M for both techniques with detection limit of 1.61×10^?7 M for DPV and 1.33×10^?7 M for OSWV. The repeatability and reproducibility of the methods for all investigated media (such as supporting electrolyte and serum samples) were determined. Precision and accuracy were also checked in all media. The methods were proposed for the determination of verapamil in dosage forms adopting both DPV and OSWV modes. The methods were extended to the in vitro determination of verapamil in spiked serum samples. No electroactive interferences from the endogenous substances were found in human plasma.     

Electroanalytical investigation and determination of pefloxacin in pharmaceuticals and serum at boron-doped diamond and glassy carbon electrodes

The anodic behavior and determination of pefloxacin on boron-doped diamond and glassy carbon electrodes were investigated using cyclic, linear sweep, differential pulse and square wave voltammetric techniques. In cyclic voltammetry, pefloxacin shows one main irreversible oxidation peak and additional one irreversible ill-defined wave depending on pH values for both electrodes. The results indicate that the process of pefloxacin is irreversible and diffusion controlled on boron-doped diamond electrode and irreversible but adsorption controlled on glassy carbon electrode. The peak current is found to be linear over the range of concentration 2 × 10⁻⁶ to 2 × 10⁻⁴ M in 0.5 M H₂SO₄ at about +1.20 V (versus Ag/AgCl) for differential pulse and square wave voltammetric technique using boron-doped diamond electrode. The repeatability, reproducibility, precision and accuracy of the methods in all media were investigated. Selectivity, precision and accuracy of the developed methods were also checked by recovery studies. The procedures were successfully applied to the determination of the drug in pharmaceutical dosage forms and humans serum samples with good recovery results. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage forms and biological samples, respectively.     

Electrochemical Redox Behaviour of Temozolomide Using a Glassy Carbon Electrode

The electrochemical behaviour of temozolomide on a glassy carbon electrode has been investigated. The reduction of temozolomide is an irreversible process, pH dependent, and the mechanism involves the addition of one electron and one proton to C5 to form an anion radical, causing the irreversible breakdown of the tetrazinone ring. The oxidation mechanism of temozolomide is an irreversible, adsorption‐controlled process, pH dependent up to value close to the pK_a and occurs in two consecutive charge transfer reactions, with the formation of the hydroxylated product. The electroanalytical determination of TMZ led to a detection limit of 1.1 µM.     

Determination of Platinum in Plant Samples by Voltammetric Analysis

A voltammetric method using solid electrode of glassy carbon as a working electrode is describes for determination of platinum in grass samples taken from the vicinity of a motorway. Standard addition was used for quantitative analysis of Pt in 0.05 M H₂SO₄. The analyte concentration in plant tissues reached 19.1±1.6 ng g^?1 for leaves of samples collected from the least polluted areas, and up to 136±2 ng g^?1 for roots of sample taken from the area of heavy road‐traffic.     

Electrochemical Investigation of Ruxolitinib: Sensitive Voltammetric Assay in Drug Product and Human Serum by Using Different Solid Electrodes

Ruxolitinib (RUX), a compound of the pyrrolopyrimidines class with activity as a tyrosine kinase inhibitory drug, is used to treat myelofibrosis. This study is reported for the detailed electrochemical behavior of RUX. The effects of supporting electrolyte, pH, and scanning rate on the peak potentials and currents of RUX were investigated by BDDE and GCE using different voltammetric techniques. Under optimum experimental conditions, calibration curves for RUX were obtained as 4 μM–80 μM and 1 μM–80 μM with a limit of detection (LOD) of 0.517 μM and 0.192 μM by the GCE and BDDE, respectively using DPV.     

隐丹参酮的电化学行为及其测定

采用循环伏安法研究隐丹参酮在电极上的电化学行为及建立差示脉冲伏安对其测定的新方法。在pH 4.0乙酸盐缓冲液中,氧化峰电流与隐丹参酮浓度在3.0×10-8~2.0×10-7mol/L范围内呈良好的线性关系,检出限为2.0×10-9mol/L。玻碳电极可有效消除样品中其它组分对隐丹参酮测定的干扰,已用于实际样品中隐丹参酮的直接测定。该方法灵敏度高、检测范围宽。     

A Sensitive Sensor Based on Single‐walled Carbon Nanotubes: Its Preparation,Characterization and Application in the Electrochemical Determination of Drug Clorsulon in Milk Samples

Within this paper, a glassy carbon electrode modified with single‐walled carbon nanotubes (SWCNTs?GCE) was prepared, and employed for the determination of clorsulon (Clo), which is a frequently used veterinary drug against common liver fluke. The comprehensive topographical and electrochemical characterizations of bare GCE and SWCNTs?GCE were performed by atomic force microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. Significantly enhanced electrochemical characteristics of SWCNTs?GCE toward a ferrocyanide/ferricyanide redox couple was observed when compared to bare GCE. Further, the prepared sensor was applied for the voltammetric determination of Clo, which was electrochemically investigated for the first time in this work. Voltammetric experiments were performed using square‐wave voltammetry with optimized parameters in phosphate buffer solution, pH 6.8, which was selected as the most suitable medium for the determination of Clo. The corresponding current at approx. +1.1 V increased linearly with Clo concentration within two linear dynamic ranges of 0.75–4.00 μmol L^?1 (R²=0.9934) and 4.00–15.00 μmol L^?1 (R²=0.9942) with a sensitivity for the first calibration range of 0.76 μA L μmol^?1, a limit of detection of 0.19 μmol L^?1, and a limit of quantification of 0.64 μmol L^?1. The developed method was subsequently applied for quantitative analysis of Clo in milk samples with results proving high repeatability and recovery.     

Electrochemical Determination of Natural Drug Colchicine in Pharmaceuticals and Human Serum Sample and its Interaction with DNA

Colchicine (COLC) is a natural toxic product and secondary metabolite most commonly used to treat gout. In this study, its electrochemical behavior and determination was investigated by employing modification‐free boron‐doped diamond electrode (BDDE). Besides, its interaction with DNA was monitored using electrochemical methods. It was found that oxidation of this compound proceeds in two steps, where first sharp and well defined oxidation peak occurs at potential of around 1.19 V, and second one at around 1.37 V, in Britton‐Robinson buffer solution at pH 7.5. Wide dynamic range from 1 to 100 μM was obtained with a detection limit (3σ_intercept/slope) of a 0.26 μM, based on the evaluation of first oxidation peak using differential pulse voltammetry. The proposed method was also found to be suitable for monitoring interaction of this drug with DNA as important segment for medical use. Concerning the validation, the analytical procedure shows excellent selectivity and sensitivity toward COLC detection and after method development it was successfully used for its quantification in pharmaceutical preparation and human serum sample, with satisfactory recovery. Obviously, this approach can be promising replacement for time‐consuming and expensive separation methods.     

Electrochemical Determination of Sulphur‐containing Pharmaceuticals Using Boron‐doped Diamond Electrodes

N‐acetylcysteine (NAC) and gentamicin sulfate (GS) are biologically and pharmaceutically relevant thiol‐containing compounds. NAC is well known for its antioxidant properties, whereas GS is an aminoglycoside that is used as a broadband antibiotic. Both pharmaceuticals play a significant role in the treatment of bacterial infections by suppressing the formation of biofilms. According to the European Pharmacopeia protocol, GS is analyzed by high performance liquid chromatography (HPLC) using gold electrodes for electrochemical detection. Here, we report the electrochemical detection of these compounds at NH₂‐terminated boron‐doped diamond electrodes, which show significantly reduced electrode passivation, an issue commonly known for gold electrodes. Cyclic voltammetry experiments performed for a period of 70 minutes showed that the peak current decreased only by 1.6 %/7.4 % for the two peak currents recorded for GS, and 6.6 % for the oxidation peak of NAC, whereas at gold electrodes a decrease in peak current of 14.2 % was observed for GS, and of 64 %/30 % for the two peak currents of NAC. For their quantitative determination, differential pulse voltammetry was performed in a concentration range of 2–49 µg/mL of NAC with a limit of detection (LOD) of 1.527 µg/mL, and a limit of quantification (LOQ) of 3.624 µg/mL, respectively. The quantification of GS in a concentration range of 0.2–50 µg/mL resulted in a LOD of 1.714 µg/mL, and a LOQ of 6.420 µg/mL, respectively.     

Electrochemical Characterization and Voltammetric Determination of Methylisothiazolinone on a Boron-Doped Diamond Electrode

The electrochemical properties of methylisothiazolinone (MIT), the most widely used preservative, were investigated by cyclic (CV) and differential pulse voltammetry (DPV) to develop a new method for its determination. To our knowledge, this is the first demonstration of a voltammetric procedure for the determination of MIT on a boron-doped diamond electrode (BDDE) in a citrate–phosphate buffer (C-PB) environment. The anodic oxidation process of methylisothiazolinone, which is the basis of this method, proved to be diffusion-controlled and proceeded with an irreversible two-electron exchange. The radical cations, as unstable primary products, were converted in subsequent chemical reactions to sulfoxides and sulfones, and finally to more stable final products. Performed determinations were based on the DPV technique. A linear calibration curve was obtained in the concentration range from 0.7 to 18.7 mg L⁻¹, with a correlation coefficient of 0.9999. The proposed procedure was accurate and precise, allowing the detection of MIT at a concentration level of 0.24 mg L⁻¹. It successfully demonstrated its suitability for the determination of methylisothiazolinone in household products without the need for any separation steps. The proposed method can serve as an alternative to the prevailing chromatographic determinations of MIT in real samples.