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用钌配合物修饰的可再生溶胶-凝胶碳陶瓷电极用于安培法检测L-半胱氨酸和谷胱甘肽。

Renewable sol-gel carbon ceramic electrodes modified with a Ru-complex for the amperometric detection of l-cysteine and glutathione.

作者信息

Salimi Abdollah, Pourbeyram Sima

机构信息

Department of Chemistry, Faculty of Science, Kurdistan University, P.O. Box 416, Sanandaj, Iran.

出版信息

Talanta. 2003 May 28;60(1):205-14. doi: 10.1016/S0039-9140(03)00125-5.

Abstract

A renewable three-dimensional chemically modified carbon ceramic electrode containing Ru [(tpy)(bpy)Cl] PF(6) was constructed by sol-gel technique. It exhibits an excellent electro-catalytic activity for oxidation of l-cysteine and glutathione at pH range 2-8. Cyclic voltammetry was employed to characterize the electrochemical behavior of the chemically modified electrode. The electrocatalytic behavior is further exploited as a sensitive detection scheme for l-cysteine and glutathione by hydrodynamic amperometry. Optimum pH value for detection is 2 for both l-cysteine and glutathione. The catalytic rate constants for l-cysteine and glutathione were determined, which were about 2.1x10(3) and 2.5x10(3) M(-1)s(-1), respectively. Under the optimized condition the calibration curves are linear in the concentration range 5-685 and 5-700 muM for l-cysteine and glutathione determination, respectively. The detection limit (S/N=3) and sensitivity is 1 muM, 5 nA/muM for l-cysteine and 1 muM, 7.8 nA/muM for glutathione. The relative standard deviation (RSD) for the amperogram's currents with five injections of l-cysteine or glutathione at concentration range of linear calibration is <1.5%. The advantages of this amperometric detector are: high sensitivity, good catalytic effect, short response time (t<3 s), remarkable long-term stability, simplicity of preparation and reproducibility of surface fouling (RSD for six successive polishing is 3.31%). This sensor can be used as a chromatographic detector for analysis of l-cysteine and glutathione.

摘要

通过溶胶 - 凝胶技术构建了一种含有Ru[(tpy)(bpy)Cl]PF(6)的可再生三维化学修饰碳陶瓷电极。它在pH值为2 - 8的范围内对l - 半胱氨酸和谷胱甘肽的氧化表现出优异的电催化活性。采用循环伏安法表征化学修饰电极的电化学行为。通过流体动力学安培法进一步将这种电催化行为用作l - 半胱氨酸和谷胱甘肽的灵敏检测方案。l - 半胱氨酸和谷胱甘肽检测的最佳pH值均为2。测定了l - 半胱氨酸和谷胱甘肽的催化速率常数,分别约为2.1×10(3)和2.5×10(3) M(-1)s(-1)。在优化条件下,用于l - 半胱氨酸和谷胱甘肽测定的校准曲线在浓度范围5 - 685和5 - 700 μM内分别呈线性。l - 半胱氨酸的检测限(S/N = 3)和灵敏度为1 μM,5 nA/μM;谷胱甘肽的检测限和灵敏度为1 μM,7.8 nA/μM。在直线校准浓度范围内对l - 半胱氨酸或谷胱甘肽进行五次进样时,安培图电流的相对标准偏差(RSD)<1.5%。这种安培检测器的优点是:灵敏度高、催化效果好、响应时间短(t<3 s)、长期稳定性显著、制备简单以及表面污垢重现性好(连续六次抛光的RSD为3.31%)。该传感器可用作色谱检测器用于分析l - 半胱氨酸和谷胱甘肽。

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