卡马西平在nano-TiO2/[BnMIM] PF6修饰碳糊电极上的电催化氧化及电分析方法

运用循环伏安法(CV)、计时电流法(CA)、计时库仑法(CC)、方波伏安法(SWV)研究了卡马西平(CBZ)在纳米二氧化钛(nano-TiO2)与离子液体1-苄基-3-甲基咪唑六氟磷酸盐([BnMIM]PF6)复合修饰碳糊电极(nano-TiO2-[BnMIM] PF6/CPE )上的电化学行为、电化学动力学性质及电分...     

Fabrication of a renewable syringe carbon paste electrode with a motor rotary blade and using for voltammetric measurement of dipyridamole

In this work, we fabricated a new renewable syringe carbon paste electrode (SCPE) equipped with a motor rotary cutting blade and used for voltammetric determination of dipyridamole (DIP) in aqueous solution, at room temperature. The cutter rotates by a small electrical motor and easily renews the surface of the carbon paste electrode by removing the spotty surface. Electrochemical performance of the constructed electrode was investigated with cyclic voltammetry (CV) and compared to some other previously reported works. The new sensor showed several advantages such as excellent repeatability, high stability, good sensitivity and easily surface renewable. The results indicated that the presence of methyltrioctyl ammonium chloride (MTOAC) could remarkably enhance the oxidation of DIP due to feasible electrical conductivity properties in a phosphate buffer solution. At optimum conditions for the new syringe CPE, the square wave voltammetry (SWV) was used to measure the concentration of DIP in a linear range of 0.08–30.0 µM and a detection limit of 0.02 µM was obtained after 100 s of accumulation time. The sensor was then tested for the simple, rapid and sensitive electrochemical determination of DIP in real samples such as pharmaceutical formulations.     

替硝唑在碳糊电极上的电化学性质及电分析方法研究

运用循环伏安法(CV)、方波伏安法(SWV)研究替硝唑(TNZ)在碳糊电极(CPE)上的电化学行为、电化学动力学性质及可能的电极反应机理.TNZ在CPE上的伏安行为是一受扩散控制的不可逆电化学还原过程,还原峰电位(Epc)为-0.557 V.用方波伏安法(SWV)测定TNZ线性范围为1.0×10-5～1.0×10h-3mol/L,检出限3.3×10-7mol/L.RSD 1.3%～2.8%,加样回收率99.2%～100.6%.据此建立了TNZ含量的电化学测定方法.     

甲氧苄啶在多壁碳纳米管-Nafion修饰电极上的电催化氧化及电分析方法

用循环伏安法(CV),计时库仑法(CC),计时电流法(CA),线性扫描伏安法(LSV)及电流-时间曲线研究了甲氧苄啶(trimethoprim, TMP)在碳纳米管-Nafion修饰电极(MWCNTs-Nafion/GCE)上的电化学行为,电化学动力学性质以及电分析方法.结果表明,TMP在GCE上有一个极弱的氧化峰,而在MWCNTs-Nafion/GCE上出现一个敏锐的氧化峰,表明MWCNTs-Nafion/GCE对TMP电化学氧化具有良好的催化作用.在扫描速度为10～800 mV/s时其氧化峰电流与扫描速度平方根(v1/2)呈良好线性关系,表明TMP在MWCNTs-Nafion/GCE上的伏安行为是受扩散控制的电化学过程.TMP在MWCNTs-Nafion/GCE上氧化峰电流与浓度在5.0×10-6～1.0×10-3 mol/L范围内呈良好线性关系;检出限为6.6×10-7 mol/L;RSD在0.75%～1 69%之间;加标回收率在98.1%～101.1%之间.本方法简便快捷,测定结果令人满意,可用于TMP的电化学定量测定.     

阳离子表面活性剂溶液的临界胶束浓度及扩散系数

在无探针分子条件下用循环伏安法(CV)研究了DTAB,TTAB,CTAB,OTAB水溶液体系胶束在玻碳电极(GCE)上的电化学行为,并用电位阶跃计时库仑法(CC)测定了胶束的扩散系数,进而得到第一与第二CMC,该方法简捷、快速、准确。对离子型表面活性剂的第二CMC提供了新的测定方法。     

十六烷基三甲基溴化铵修饰碳糊电极线性扫描伏安法测定尿液中尿酸

本文提出了以十六烷基三甲基溴化铵修饰碳糊电极（CTAB／CPE）直接测定尿酸（UA）的新方法,用线性扫描伏安法（LSV）研究尿酸的电化学行为。在0.1mol／L磷酸盐缓冲溶液（PBS,pH=7.4）中,尿酸在CTAB／CPE上于0.160V处产生一个灵敏的氧化峰,氧化峰电流Ip与尿酸浓度（CuA）在1.0×10^-5—1.0×10^-3mol／L范围内呈良好的线性关系,相关系数为0.9940,检出限为1.0×10^-6mol／L。该方法简单实用,可以直接用于人体尿液中尿酸的检测。     

Enhanced reduction and determination of trace thyroxine at carbon paste electrode in the presence of trace cetyltrimethylammonium bromide.

The electrochemical response of thyroxine (T4) at a carbon paste electrode (CPE) in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. It gave a well-defined oxidation peak at 0.80 V and a sensitive reduction peak at 0.40 V. Compared with the indiscernible signal in the absence of CTAB, the reduction current of T4 at CPE was greatly enhanced in the presence of CTAB, due to the interactions between T4, CTAB and the hydrophobic electrode surface. The electrode process of T4 was explored by cyclic voltammetry and chronocoulometry. The effect of surfactants on the reduction reaction proved that bromide ions (Br(-)) in CTAB might form special ion complexes with T4 via a special interaction with the iodine atoms on T4, which would activate the reduction of T4. The sensitive and selective reduction of T4 in this system was applied to the determination of T4 in drugs; a detection limit of 6.5 x 10(-9) M was obtained (sigma= 3).     

The influence of cetyltrimethyl ammonium bromide on electrochemical properties of thyroxine reduction at carbon nanotubes modified electrode

The effect of cetyltrimethyl ammonium bromide (CTAB) on the electrochemical behaviors of thyroxine at a glassy carbon electrode (GCE) modified with single-walled carbon nanotubes (SWNTs) was investigated. At the SWNTs film-coated GCE, a well-defined oxidation peak of thyroxine at 0.78 V was obtained, but the reduction peak of thyroxine was indiscernible. When trace CTAB was added to the working solution, the reduction current could be greatly enhanced and the oxidation current remained stable. The reaction mechanisms for the reduction of thyroxine were explored by chronocoulometry. Thyroxine might form particular ion complex with CTAB via the interaction between iodine atoms on thyroxine and bromide ions in CTAB, which made the concentration of thyroxine at the surface of the modified electrode increased and the electron transfer rate enhanced. The proper mechanisms for the enhanced reduction of thyroxine in the present of CTAB were explored by several electrochemical techniques including cycle voltammetry linear sweep voltammetry and others. It was concluded that the special interactions between the thyroxine CTAB and SWNTs resulted in the increase of the reduction peak current. All results indicated that two iodine atoms on the thyroxine and four electrons were involved the reduction process which was irreversible and two iodine ions produced. In this system, the sensitive reduction peak of thyroxine at 0.3 V was employed to determine thyroxine and a low detection limit of 2x10(-8) mol/L was obtained for 2 min accumulation at 0.9 V. The SWNTs coated GCE had good stability and reproducibility.     

基于十二烷基苯磺酸钠增敏效应电化学方法检测苏丹红Ⅰ

采用线性扫描法、连续循环伏安法和计时库仑法研究了苏丹红Ⅰ在碳糊电极（CPE）上的电化学氧化过程,在痕量阴离子表面活性剂十二烷基苯磺酸钠（SDBS）存在下苏丹红Ⅰ的氧化峰电流得到最大增敏。苏丹红Ⅰ的浓度在2.0×10-7~ 1.5×10-5mol/L范围内,其氧化峰电流与浓度呈现出良好的线性关系。在开路条件下富集180 s后,苏丹红Ⅰ的检出限为6.0×10-8mol/L。该方法适用于辣椒制品及番茄酱等食品中苏丹红Ⅰ的测定     

Electrochemical behavior of phenol at acetylene black-dihexadecyl hydrogen phosphate composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide

The electrochemical response of phenol at acetylene black (AB)-dihexadecyl hydrogen phosphate (DHP) composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. In this system, a sensitive oxidation peak at 0.62 V (SCE) was obtained. The electrode process and the influence of CTAB on the oxidation of phenol were explored by chronocoulometry and linear sweep voltammetry (LSV). Experimental conditions for the determination of phenol were optimized. In the range of 5.0 × 10⁻⁷ to 1.2 × 10⁻⁵ M, the phenol concentration was linear with the oxidation peak current and the detection limit was found to be 1.0 × 10⁻⁷ M for 3 min accumulation. The method was applied for the determination of phenol in lake water and the results were satisfactory. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 222–229. The text was submitted by the authors in English.     

Voltammetric determination of ethinylestradiol at a carbon paste electrode in the presence of cetyl pyridine bromine

Electrochemical behaviors of ethinylestradiol at a carbon paste electrode (CPE) in the presence of cetyl pyridine bromide (CPB) are investigated by electrochemical techniques. Compared with that at a CPE without CPB, the oxidation peak potential of ethinylestradiol shifts negatively and the peak current is increased significantly, due to the enhanced accumulation of ethinylestradiol via electrostatic interaction with CPB at the hydrophobic electrode surface. It is verified by the influences of different kinds of surfactants on the electrochemical signals of ethinylestradiol. Some parameters such as pH, scan rate, accumulation potential and accumulation time on the oxidation of ethinylestradiol are optimized. Under optimal conditions, the oxidation peak current is proportional to ethinylestradiol concentration in the range of 5.0 x 10(-8) to 2.0 x 10(-5) mol L(-1) with a detection limit of 3.0 x 10(-8) mol L(-1) for 150 s accumulation by linear sweep voltammetry (LSV). The proposed procedure is successfully applied to determine ethinylestradiol in pharmaceutical formulation (Levonorgestrel and Etinylestradiol tablets) and the results are satisfying compared with that of high-performance liquid chromatography (HPLC).     

Electrochemical behaviors of adrenaline at acetylene black electrode in the presence of sodium dodecyl sulfate

The electrochemical behaviors of adrenaline at the acetylene black electrode in the presence of sodium dodecyl sulfate (SDS) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results indicated that the electrochemical responses of adrenaline were apparently improved by SDS, due to the enhanced accumulation of protonated adrenaline via electrostatic interaction with negatively charged SDS at the hydrophobic electrode surface. This was verified by the influences of different kinds of surfactants on the electrochemical signals of adrenaline. The electrochemical parameters of the adrenaline oxidation were explored by chronocoulometry. Under optimal working conditions, the oxidation peak current at 0.57 V was proportional to adrenaline concentration in the range of 5.0x10(-8) to 7.0x10(-6) mol/L, with a low detection limit of 1.0x10(-8)mol/L for 70s accumulation by differential pulse voltammetry (DPV). This method was applied to determine adrenaline in the hydrochloride injection sample. The results are satisfying compared with that by the standardized method of high performance liquid chromatography (HPLC).     

CTAB存在下双酚A在纳米氧化锌/碳纳米管复合材料修饰电极上的电化学行为及测定

利用水热法合成了纳米氧化锌/碳纳米管复合材料,将该复合材料滴涂在玻碳电极表面,制得纳米氧化锌-碳纳米管复合材料修饰电极(ZnO-MWCNTs/GCE)。在阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)存在下,利用循环伏安法研究了双酚A在修饰电极上的电化学行为。考察了溶液pH值、CTAB浓度和富集时间等对测定的影响。结果表明,在pH 7.0的含8.0×10-5mol/L CTAB的磷酸盐缓冲液中,该修饰电极对双酚A具有良好的电化学响应,双酚A在修饰电极上的氧化峰电流为裸电极上的7倍。在优化条件下,采用差分脉冲伏安法对双酚A进行测定。双酚A的峰电流在5.0×10-8~1.5×10-5mol/L浓度范围内呈良好的线性关系,检出限(S/N=3)为1.0×10-8mol/L。对1.0×10-5mol/L双酚A平行测定8次的相对标准偏差为4.6%。该法用于塑料制品中溶出双酚A的测定,回收率为99%~107%,结果满意。     

基于表面活性剂增敏有序介孔SiO2修饰碳糊电极测定L-色氨酸

利用水热法合成得到有序介孔二氧化硅( OMS),采用X射线衍射、N2吸附-脱附、透射电镜等技术对其进行了表征。制备OMS修饰碳糊电极( OMS/CPE),采用循环伏安和交流阻抗技术考察了修饰电极的电化学性能,发现与裸碳糊电极(CPE)相比,OMS/CPE具有更大的电活性面积和更快的电子传导速率。研究了L-色氨酸(L-Trp)在表面活性剂十二烷基磺酸钠(SDS)存在下,在OMS/CPE上的电化学行为和动力学性质,结果表明,OMS和SDS具有良好的协同作用,能明显增加L-Trp的响应信号; SDS存在下,L-Trp在修饰电极上的电化学氧化是2电子和2质子参加的不可逆过程,电极过程受吸附控制。优化了表面活性剂浓度、富集时间、富集电位、介质 pH 值等测定参数,在最优条件下, L-Trp 氧化峰电流与其浓度在8.0×10-8~4.0×10-6 mol/L范围内呈良好线性关系,检出限为7.0×10-8 mol/L(S/N=3)。本方法用于氨基酸口服液样品的加标回收检测,回收率为99.6％~102.6％。     

Studies on electrochemical oxidation of azithromycin and its interaction with bovine serum albumin

A novel nanoparticle film modified electrode has been constructed using a glassy carbon electrode (GCE) coated with a carbon nanotube-dihexadecylphosphate (DHP) film. This modified electrode exhibits an enhanced effectiveness for the oxidation of azithromycin. A method is also described for the evaluation of azithromycin-bovine serum albumin (BSA) interaction. The electrochemical behavior of azithromycin as well as its interaction with BSA at this nanoparticle film electrode has been investigated by cyclic voltammetry, linear sweep voltammetry, differential pulse voltammetry and chronocoulometry. The binding number and association constant between azithromycin and bovine serum albumin have been obtained.     

Electrochemical oxidation of selenocystine and selenomethionine

Electrochemical oxidation of selenocystine (SeCys) and selenomethionine (SeMet), on a gold electrode was studied by cyclic voltammetry (CV), rotating disk electrode technique (RDE) and chronocoulometry (CC). In 0.2 mol/L HAc-NaAc (pH = 3.90) supporting electrolyte, anodic peak I potential of SeCys and SeMet was 810 mV and 638 mV, respectively, and this electrode process was diffused controlled. The electrochemical oxidation process of SeCys, in which six electron-transfers were involved, yielded selenocystine selenoxide. The electrochemical oxidation process of SeMet, in which two electron-transfers were involved, yielded selemethionine selenoxide.     

Electrochemical determination of homocysteine using carbon nanotubes modified paste electrode and isoprenaline as a mediator

Homocysteine (HCy) is an important amino acid containing thiol group and is known as a risk factor in relation to ischemic heart disease and stroke. In this study the electrochemical determination of homocysteine (HCy) has been described using isoprenaline hydrochloride (ISP) as a mediator on multiwall carbon nanotubes modified paste electrode (MWCNTPE). Electrochemical behavior of homocysteine was investigated by cyclic voltarrtmetry and chronoamperometry. The cyclic voltammograms showed that the electrocatalytic oxidation of homocysteine occurs in the presence of ISP on the surface of MWCNTPE at a potential about 640 mV. Also, results showed that the oxidatation peak current of HCy at the modified carbon nanotubes electrode was more than unmodified electrode. The diffusion coefficient and the kinetic parameters including electron transfer coefficient and rate constant of electrocatalytic reaction were determined using electrochemical approaches. Linear sweep voltammetry results showed that electrocatalytic oxidation peak current of HCy had linear dynamic range in the range of 5.0 to 800 μmol L^?1 with a detection limit of 3.3 μmol L^?1 in pH 3.5 (universal buffer).     

硫脲在10-甲基吩噻嗪修饰碳糊电极上的电催化氧化及电分析方法研究

研究了硫脲(Thiourea,Tu)在10-甲基吩噻嗪修饰碳糊电极(MPT/CPE)上的电催化氧化行为.结果表明,Tu在裸碳糊电极(CPE)上的直接电化学氧化过程十分迟缓,MPT/CPE对Tu的电化学氧化具有良好的催化作用.用计时电流法(CA)测定了Tu在MPT/CPE上的电极过程动力学参数,测得电荷传递系数α=0.61,电催化氧化反应的速率常数k=(1.96±0.10)×104(mol/L)-1·s-1.用方渡伏安法(SWV)测得催化氧化峰电流与Tu浓度在1.0×10-6～8.0×10-3mol/L范围内呈良好的线性关系,线性回归方程为,Ips(μA)=10.836c(10-3mol/L)+5.326,R=0.9984,检出限为2.2×10-7mol/L(S/N=3).方法可用于Tu的电化学法测定.     

萘乙酸在多壁碳纳米管-离子液体复合修饰电极上的电催化氧化及电分析方法

运用循环伏安法(CV),计时库仑法(CC),计时电流法(CA)研究了萘乙酸(NAA)在玻碳电极(GCE),多壁碳纳米管修饰玻碳电极(MWCNTs/GCE)和多壁碳纳米管-离子液体修饰玻碳电极(MWCNTs-IL/GCE)上的电化学行为及电化学动力学性质.实验结果表明,NAA在GCE电极上于1.00V附近有一不可逆氧化峰...     

Simple and low-cost electrochemical sensor based on nickel nanoparticles for the determination of cabergoline

Cabergoline (CAB) is an ergot alkaloid derivative with dopamine agonist activity. In this work for the first time the electrocatalytic oxidation of CAB was carried out with nickel nanoparticles-modified carbon paste electrode using cyclic voltammetry, chronoamperometry, chronocoulometry and amperometry methods. At first, nickel nanoparticles were synthesized by non-aqueous polyol method and these nanoparticles were mixed with graphite powder to form modified carbon paste electrode. The resulting modified electrode was characterized by scanning electron microscope images. In the presence of 0.1 M NaOH a good redox behavior of the Ni(III)/Ni(II) couple at the surface of the electrode can be observed. CAB was successfully oxidized at the surface of the modified electrode. The electrocatalytic oxidation peak current of this drug was linearly dependent on its concentration. The proposed sensor exhibited a high sensitivity and was successfully applied for the determination of CAB in real samples.