维生素B12和多壁碳纳米管修饰电极上蛋氨酸电氧化的研究

V. Shelkovnikov, A. Altyev, M. Fryanova
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摘要

本文研究了蛋氨酸在维生素B12和多壁碳纳米管修饰电极上的电化学行为。提出了在改性电极上发生氧化还原过程的可能机理。当电极形成时,维生素B12由于吸附作用被固定在多壁碳纳米管修饰的含碳电极表面。在阴极极化过程中,由于静电相互作用,钴胺素中的钴(III)被还原为钴(II),而蛋氨酸分子中部分带负电的硫原子附着在钴(II)上。在阳极极化过程中,配合物中的钴(II)被氧化为Co3+,蛋氨酸中的甲基被转移到钴胺素中,同型半胱氨酸进入溶液,拉曼光谱证实了这一点。通过研究电流和电位对扫描速度的依赖关系,发现氧化过程不可逆,限制阶段为吸附,一个质子和一个电子参与电化学阶段。选择了以下记录分析信号的最佳条件:背景电解质为pH = 4.01的酒石酸盐缓冲溶液;电解电位为1.6 V;累积时间可达180 s。评价了测定蛋氨酸方法的计量特性。准确度指标不超过29%,重复性和中间精密度指标分别不超过14%和16%。检测范围为(1-50)×10-7;检测限为5.0×10-8 M.结果表明,抗坏血酸、色氨酸、甘氨酸、半胱氨酸和酪氨酸的10倍过量对测定蛋氨酸的程序没有明显的扭曲作用。
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Study of the Methionine Electrooxidation at an Electrode Modified with Vitamin B12 and Multi-Walled Carbon Nanotubes
The electrochemical behavior of methionine at an electrode modified with vitamin B12 and multi-walled car-bon nanotubes has been studied in this work. A possible mechanism of redox processes occurring on the modified electrode is proposed. When the electrode is formed, vitamin B12 is fixed on the surface of a carbon-containing electrode modified with multi-walled carbon nanotubes due to adsorption. In the process of ca-thodic polarization, cobalt(III) in cobalamin is reduced to cobalt(II) to which a partially negatively-charged sulfur atom in the methionine molecule is attached due to electrostatic interactions. During anodic polariza-tion, cobalt(II) in the complex is oxidized up to Co3+, the methyl group from methionine is transferred to cobalamin, and homocysteine passes into the solution, which is proved by Raman spectra. Based on the study of the dependence of current and potential on the sweep speed, it was found that the oxidation process is not reversible, the limiting stage is adsorption, and one proton and one electron participate in the electrochemical stage. The following оptimal conditions for recording an analytical signal were selected: the background elec-trolyte is a tartrate buffer solution with pH = 4.01; the electrolysis potential is 1.6 V; the accumulation time is up to 180 s. The metrological characteristics of the procedure for determining methionine were estimated. The accuracy index did not exceed 29 %, the repeatability and intermediate precision indices did not exceed 14 % and 16 %, respectively. The range of detectable contents was (1–50)×10–7; the detection limit was 5.0×10–8 M. It was shown that a 10-fold excess of ascorbic acid, tryptophan, glycine, cysteine and tyrosine does not have a noticeable distorting effect on the procedure for determining methionine.
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