多壁碳纳米管修饰玻碳电极伏安法测定氯霉素

研究了氯霉素(CAP)在多壁碳纳米管修饰玻碳电极上的电化学行为.发现在pH=2.0的0.1 mol/LKCl-HCl底液中,CAP在该修饰电极上有一灵敏的还原峰(Ep=-0.36 V vs.Ag/AgCl),峰电流与CAP浓度成正比,线性范围为6.0×10-6~2.7×10-4mol/L,检测限达3.0×10-6mol/L.该方法灵敏、准确,用于模拟样品和实际样品的测定,结果满意.     

维生素b12在多壁碳纳米管修饰玻碳电极上的电化学行为及其分析测定

维生素b12;多壁碳纳米管;循环伏安法;修饰电极     

血红蛋白在碳纳米管修饰碳糊电极上的直接电化学行为

利用吸附法将血红蛋白(Hb)固定在碳纳米管修饰碳糊电极表面,制成稳定的固载Hb碳纳米管修饰电极,研究了Hb在碳纳米管修饰电极上的直接电化学行为.固载Hb的碳纳米管修饰电极在pH=7.0的PBS（磷酸盐缓冲溶液）中有一对相当可逆的循环伏安氧化还原峰,为Hb血红素辅基Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰.式电位为－0.160 V(vs SCE),随扫描速度变化很小.电子转移数为1.021,近似为一个辅基发生电子转移.Hb在碳纳米管修饰电极表面的电子转移常数为0.0816 s－1,远大于亚甲蓝作媒介体时Hb的电子转移反应速率常数.应用于过氧化氢、三氯乙酸和硝基苯等的电催化还原,固定在碳纳米管修饰碳糊电极的血红蛋白表现出稳定且较高的催化活性.     

Direct Electrochemistry of Catalase at a Gold Electrode Modified with Single‐Wall Carbon Nanotubes

The direct electrochemistry of catalase (Ct) was accomplished at a gold electrode modified with single‐wall carbon nanotubes (SWNTs). A pair of well‐defined redox peaks was obtained for Ct with the reduction peak potential at ?0.414 V and a peak potential separation of 32 mV at pH 5.9. Both reflectance FT‐IR spectra and the dependence of the reduction peak current on the scan rate revealed that Ct adsorbed onto the SWNT surfaces. The redox wave corresponds to the Fe(III)/Fe(II) redox center of the heme group of the Ct adsorbate. Compared to other types of carbonaceous electrode materials (e.g., graphite and carbon soot), the electron transfer rate of Ct redox reaction was greatly enhanced at the SWNT‐modified electrode. The peak current was found to increase linearly with the Ct concentration in the range of 8×10^?6–8×10^?5 M used for the electrode preparation and the peak potential was shown to be pH dependent. The catalytic activity of Ct adsorbates at the SWNTs appears to be retained, as the addition of H₂O₂ produced a characteristic catalytic redox wave. This work demonstrates that direct electrochemistry of redox‐active biomacromolecules such as metalloenzymes can be improved through the use of carbon nanotubes.     

米吐尔在多壁碳纳米管修饰电极上的电化学行为及其应用

制备了多壁碳纳米管修饰玻碳电极(MWCNT/GCE),研究了该电极对米吐尔的电催化作用及测定溶液中米吐尔的分析条件。实验表明:在常见的支持电解质中,米吐尔在MWCNT/GCE上比裸玻碳电极(GCE)上氧化还原峰电位差要小,而峰电流显著增加,因此该电极对米吐尔有电催化作用;在pH=1.0的HCl-KCl支持电解质中,米吐尔的电流响应最佳;扫速增加,峰电流增加,但峰电位受溶液电阻的影响而发生位移,峰形变差,最佳扫描速度为0.12V/s;一些常见物质对测定无干扰,米吐尔浓度与峰电流的关系为:Ipc=0.1126C 1.393×10-4(r=0.9982);共存的对苯二酚(HQ)干扰测定,但可通过二次微分CV曲线方法消除干扰,在8.0×10-2~1.0×10-5mol/L范围内,其浓度与二次微分还原峰面积线性关系为:Apc=8.562×10-4C 1.801×10-6(r=0.9986);检出限达5.0×10-6mol/L。     

Sensitive Adsorption Stripping Voltammetric Determination of Reserpine by a Glassy Carbon Electrode Modified with Multi-Wall Carbon Nanotubes

Adsorption stripping voltammetry, a very sensitive electroanalytical method, was employed to determine reserpine, a kind of anti-hypertensive drug. In 0.1M phosphate buffer with a pH of 6.0, reserpine was accumulated at a multi-wall carbon nanotubes (MWNT)-modified glassy carbon electrode (GCE) surface under the condition of open-circuit. In the following anodic sweep from 0.20 to 1.00V, reserpine, adsorbed at the MWNT-modified GCE surface, was oxidized and yielded a sensitive oxidation peak at 0.64V. Due to its unique structure and extraordinary properties, MWNT shows a ten times higher accumulation efficiency toward reserpine, compared with a bare GCE. Hence, the amount of reserpine at the MWNT-modified GCE surface increases significantly, and finally the oxidation peak current improves greatly. The experimental conditions, such as supporting electrolyte, pH value, the amount of MWNT-DHP suspension, accumulation time and scan rate, were optimized for the measurement of reserpine, and a sensitive electroanalytical method was proposed for reserpine determination. The oxidation peak current varies linearly with the concentration of reserpine over the range of 2×10^–8 to 1×10^–5M, and the detection limit is 7.5×10^–9M after 4min open-circuit accumulation. The relative standard deviation at 1×10^–6M reserpine was about 4.7% (n=7), indicating excellent reproducibility. This new method was successfully demonstrated with reserpine injections and tablets.     

曲克芦丁在羧基化单壁碳纳米管修饰电极上的电化学氧化

研制了羧基化单壁碳纳米管修饰玻碳电极( SWCNTs - COOH/GCE).用交流阻抗谱法(EIS)和扫描电镜( SEM)研究了电极膜性能,应用循环伏安法(CV)考察了曲克芦丁在修饰电极上的电化学行为.结果表明,SWCNTs - COOH修饰电极对曲克芦丁的氧化有良好的电催化活性,其氧化反应为单电子单质子过程,结合恒...     

Electrochemical Determination of Tannins Using Multiwall Carbon Nanotubes Modified Glassy Carbon Electrode

A novel chemically modified electrode is prepared on the basis of the attachment of multiwall carbon nanotubes (MWNTs) to the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant. The electrochemical behavior of tannins at the MWNTs-modified GCE is investigated. Tannins yield a well-defined oxidation at about 0.30 V (SCE) at the MWNTs-modified GCE. MWNT-film shows remarkable enhancement effect on the oxidation peak current of tannins. The experimental parameters are optimized, and a direct electrochemical method to detect tannins is proposed. The oxidation peak current is proportional to the concentration of tannins over the range from 4 × 10^–7 to 2 × 10^–4 M, and the detection limit is 1 × 10^–7 mol/l after 5 min of accumulation. The relative standard deviation of 6% for determination of 2 × 10^–6 mol/l tannins indicates excellent reproducibility. The analysis method is demonstrated by using tea and Chinese gall samples.     

碳纳米管碳糊电极吸附伏安法测定西沙必利

用循环伏安法和差分脉冲伏安法研究了西沙必利在多壁碳纳米管碳糊电极上的伏安行为和反应机理。在pH6.09Britton-Robinson缓冲液中,西沙必利在 0.89V(vs.SCE)处产生一灵敏的氧化峰。该氧化峰是由吸附控制的两电子一质子不可逆过程。其峰电流与浓度在4.0×10?8~2.0×10?5mol/L范围内呈线性关系(r=0.997),检出限为1.0×10?8mol/L。对5×10?6mol/L西沙必利平行测定10次的相对标准偏差为3.68%。用本法测定了片剂中西沙必利的含量,加标回收率为94.0%~104%。     

Fabrication of a Multi-wall Carbon Nanotubes Modified Glassy Carbon Electrode and its Catalytic Effect on the Oxidation of Estradiol, Estrone and Estriol

 Multi-wall carbon nanotubes (MWNT) have been dispersed into water with the emulsification of oil of turpentine and emulsifier OP TX-100. An MWNT-modified glassy carbon electrode (GCE) has been achieved through solvent evaporation of MWNT- dispersion. In pH 2.0 phosphate buffer, MWNT- modified GCE has an obvious catalytic effect on the oxidation of estradiol, estrone and estriol. The oxidation peak current of these estrogens at the modified electrode increases significantly in contrast with that at the bare GCE. The experimental conditions which heavily affect the oxidation peak current of estradiol, such as the solution pH, the amount of MWNT, the scan rate, the adsorption potential and adsorption time, were optimized. The peak current is linear to the concentration in the range of 2.5 × 10⁻⁷ to 5 × 10⁻⁵ mol L⁻¹ estradiol. The detection limit is 1 × 10⁻⁸ mol L⁻¹ after 3 min open-circuit adsorption. The relative standard deviation (RSD) of six measurements using an electrode is 3.2% for 1 × 10⁻⁵ mol L⁻¹ estradiol. The effect of interferences of other organic compounds on the determination of estradiol was examined. Author for correspondence: Department of Chemistry, Wuhan University, Wuhan 430072, P.R. China. E-mail: sshu@whu.edu.cn Received June 19, 2002; accepted January 4, 2003 Published online April 11, 2003     

蒿甲醚在单壁碳纳米管修饰电极上的电催化还原

研制了单壁碳纳米管(SWCNTs)修饰玻碳电极。用交流阻抗谱法(EIS)和扫描电镜(SEM)研究了电极膜性能,应用循环伏安法(CV)、计时库仑法(CC)、计时电流法(CA)研究了蒿甲醚在修饰电极上的电化学行为。结果表明,SWCNTs修饰电极对蒿甲醚的还原有良好的电催化活性,其还原反应为双电子过程,电极反应的扩散系数及速率常数分别为6·67×10-4cm2·s-1及8·54×10-2mol·L-1·s-1。在优化实验条件下,还原峰的峰电位位于-0·85V,其峰电流与蒿甲醚浓度在6·71×10-7~2·45×10-4mol·L-1范围内呈良好线性,检出限达4·02×10-7mol·L-1,相对标准偏差(n=10)为4·2%,可用于蒿甲醚样品的含量测定。     

基于羧基化碳纳米管修饰电极伏安法同时测定痕量锢和铝

基于羧基化多壁碳纳米管(c-MWCNT),制备了可同时测定In3+和Al3+的新型碳材料修饰电极.利用循环伏安法(CV)和交流阻抗法(EIS)对此修饰电极进行了表征,用线性扫描伏安法(LSV)研究了In3+与Al3+共存于修饰电极上的电化学行为.与裸玻碳电极相比,新型碳材料修饰电极的电化学活性得到很大提高;In3+与A...     

对乙酰氨基酚在多壁碳纳米管修饰电极上的电化学行为

制备了多壁碳纳米管修饰玻碳电极,研究了对乙酰氨基酚在多壁碳纳米管修饰电极上的循环伏安行为,并建立了测定对乙酰氨基酚含量的电化学分析方法。在pH为6.89的磷酸盐缓冲液中,多壁碳纳米管修饰电极对对乙酰氨基酚有明显的电催化作用,其氧化峰电流与对乙酰氨基酚浓度在1.0×10-6～1.0×10-4mol·L-1范围内呈良好的线性关系,检测限为2.0×10-7mol·L-1。     

Modified Glassy Carbon Electrode with Multiwall Carbon Nanotubes as a Voltammetric Sensor for Determination of Leucine in Biological and Pharmaceutical Samples

Abstract

A simple and highly sensitive method is described for voltammetric determination of leucine in blood and urine samples; namely, a glassy carbon electrode with an effective method is modified with multiwall carbon nanotubes (MWNTs). The cyclic voltammetric results indicated that MWNTs remarkably enhanced electrocatalytic activity toward the oxidation of leucine. Under the optimum condition the calibration curve was linear in the concentration range 9.0 × 10^?6 ? 1.5 × 10^?3 mol L^?1, with the detection limit of 3.0 × 10^?6 mol L^?1 and a relative standard deviation (RSD%) lower than 3.0% (n = 5). Also, some kinetic parameters were determined and a multistep mechanism for oxidation of leucine was proposed.     

Electrochemistry and Adsorptive Stripping Voltammetric Determination of Amoxicillin on a Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

The study of electrochemical behavior of amoxicillin (AMX), a β‐lactam antibiotic, is described on a multiwalled carbon nanotubes (MWCNTs) modified electrode by electrochemical impedance spectroscopy (EIS) and adsorptive stripping voltammetry for sensitive determination of AMX in pharmaceutical and human urine samples within a wide pH range from 2.0 to 10.0. Also, studies by Fe₂O₃ nanoparticles modified carbon paste electrode show that iron oxide impurities in the MWCNTs are not active sites for sensing of amoxicillin. Under optimized conditions, the oxidation peak has two linear dynamic ranges of 0.6–8.0 and 10.0–80.0 μM with a detection limit of 0.2 μM and a precision of <4%.     

血红蛋白在纳米孔径氧化铝膜修饰电极上的直接电化学

运用电化学包埋法成功将血红蛋白(Hb)固定于纳米孔阳极氧化铝膜(AAO)修饰的玻碳电极(GC)表面, 制得Hb/PPy/AAO/GC修饰电极, 并对Hb/PPy/AAO/GC修饰电极的制备条件进行了优化. 研究了Hb/PPy/AAO/GC修饰电极在磷酸缓冲液(pH＝6.8)中的电化学行为, 探讨了血红蛋白在AAO修饰电极表面的直接电子转移机理. 结果表明阳极氧化铝膜不仅保持了血红蛋白的生物活性, 而且通过它的纳米尺寸效应, 实现了Hb与电极之间的直接电子转移. 其研究内容对生命科学和临床医学有着重要意义.     

血红蛋白在月桂酸修饰玻碳电极的电催化行为

研究血红蛋白在月桂酸修饰电极上的电化学行为,在0.02mol.L-1KH2PO4-Na2HPO4(pH=7)的缓冲液中,+0.6～-0.7V(vs.Ag/AgCl)电位范围内,Hb于该修饰电极产生不可逆还原电流峰.还原峰电流ip与v1/2呈线性关系,ip随溶液pH值和血红蛋白浓度的增加而增大,其浓度在1.00×10-8～5.00×10-9mol.L-1和1.92×10-6～2.06×10-7mol.L-1范围内分段呈线性变化关系.实验数据经进一步分析拟合,得到更精确的信息.该电极可作为检测血红蛋白的新型电化学生物传感器.     

肾上腺素在多壁碳纳米管修饰金电极上的电化学行为及测定

报道了一种测定肾上腺素的化学修饰电极和电化学分析方法。与裸金电极相比,刚果红改性的多壁碳纳米管修饰金电极可显著提高肾上腺素的氧化峰电流。实验优化了底液、pH值、修饰剂量、富集电位和富集时间等条件,建立了一种直接测定肾上腺素的高灵敏的电化学分析方法。该方法测定肾上腺素的线性范围为4.0×10-7~2.0×10-4mol.L-1;富集30 s后的检出限为8.5×10-8mol.L-1;对2.0×10-5mol.L-1的肾上腺素平行测定10次的相对标准偏差为4.9%。此方法已成功用于盐酸肾上腺素注射液中含量的测定。     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

Voltammetric Reduction of a 4‐Nitroimidazole Derivative on a Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

We report the electrochemical behavior of a 4‐nitroimidazole derivative, 1‐methyl‐4‐nitro‐2‐hydroxymethylimidazole (4‐NImMeOH), on glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNT). As dispersing agents, dimethylformamide (DMF) and water were used. The electrochemical response of the resulting electrodes was evaluated using linear sweep, cyclic and square‐wave voltammetry (LSV, CV and SWV). Several parameters such as medium pH, nature and concentration of the CNTs dispersion and accumulation time were tested. The optimal conditions determined for obtain better response were: pH 2, dispersion concentration=4 mg/mL of CNT in water, accumulation time=7 min. The MWCNT‐modified GCE exhibited attractive electrochemical properties producing enhanced currents with a significant reduction in the overpotential and good signal‐to‐noise characteristics, in comparison with the bare GCE. The modified electrode is highly repeatable for consecutive measurements, reaching a variation coefficient of 2.9% for ten consecutive runs.