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柱上电化学氧化还原衍生化用于提高液相色谱的分离选择性——利用氧化还原反应作为二级化学平衡

On-column electrochemical redox derivatization for enhancement of separation selectivity of liquid chromatography use of redox reaction as secondary chemical equilibrium.

作者信息

Saitoh Kazunori, Koichi Kohta, Yabiku Fumiko, Noda Yumiko, Porter Marc D, Shibukawa Masami

机构信息

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, 1-2-1 Izumi-cho, Narashino 275-8575, Japan.

出版信息

J Chromatogr A. 2008 Feb 8;1180(1-2):66-72. doi: 10.1016/j.chroma.2007.12.003. Epub 2007 Dec 8.

Abstract

An on-column electrochemical redox derivatization for enhancement of high-performance liquid chromatography (HPLC) separation selectivity is presented using electrochemically modulated liquid chromatography (EMLC) and porous graphitic carbon (PGC) as the packing material. PGC therefore serves two purposes: it acts both as a chromatographic stationary phase and as a working electrode. The capability of on-column electrochemical redox derivatization was evaluated using hydroquinone and catechol as model compounds. By manipulation of the applied potential, hydroquinone and catechol will migrate as equilibrium mixtures, hydroquinone and p-benzoquinone and catechol and o-benzoquinone in the potential region of 25-125 mV and 150-200 mV (vs. Ag/AgCl), respectively. These redox reactions can be used as secondary chemical equilibria so that the corresponding equilibrium mixtures elute as single peaks and their retention times can be controlled by alterations in the potential applied to the PGC stationary phase. Homogeneity of the redox activity of the PGC stationary phase applied potential was also demonstrated.

摘要

本文介绍了一种柱上电化学氧化还原衍生化方法,用于提高高效液相色谱(HPLC)的分离选择性,该方法采用电化学调制液相色谱(EMLC)和多孔石墨化碳(PGC)作为填充材料。因此,PGC具有两个作用:它既作为色谱固定相,又作为工作电极。以对苯二酚和邻苯二酚为模型化合物,评估了柱上电化学氧化还原衍生化的能力。通过控制施加的电位,对苯二酚和邻苯二酚将分别以平衡混合物的形式迁移,对苯二酚和对苯醌以及邻苯二酚和邻苯醌在25 - 125 mV和150 - 200 mV(相对于Ag/AgCl)的电位区域中。这些氧化还原反应可作为二级化学平衡,使得相应的平衡混合物以单峰形式洗脱,并且它们的保留时间可以通过改变施加到PGC固定相的电位来控制。还证明了PGC固定相施加电位的氧化还原活性的均匀性。

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