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首页> 外文期刊>Electroanalysis >On-line electrochemistry/electrospray ionization mass spectrometry (EC/ESI-MS) for the generation and identification of nucleotide oxidation products
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On-line electrochemistry/electrospray ionization mass spectrometry (EC/ESI-MS) for the generation and identification of nucleotide oxidation products

机译：在线电化学/电喷雾电离质谱（EC / ESI-MS）用于生成和鉴定核苷酸氧化产物

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摘要

The oxidation behavior of DNA and RNA nucleotides is studied by an on-line set-up consisting of an electrochemical thin-layer cell (EC) directly coupled to electrospray ionization mass spectrometry (ESI-MS). This set-up allows the generation of nucleotide oxidation products in the electrochemical cell at increasing potentials. Moreover, the products are determined directly, without isolation or derivatization steps, by electrospray ionization time of flight mass spectrometry (ESI-ToF/MS). The dependence of the mass spectra on the applied potential is displayed as 'mass voltammograms'. An advanced set-up, consisting of the electrochemical cell coupled to electrospray ionization tandem mass spectrometry (EC/ESI-MS/MS) allows further structure elucidation based on fragmentation experiments. The electrochemical conversion is performed using a boron doped diamond (BDD) working electrode, which is known to generate hydroxyl radicals at high potentials. The capability of the EC-MS system to generate highly relevant oxidation products which also occur upon oxidative damage in vivo is demonstrated in this study by the formation of well known biomarkers for DNA damage, including 2'-deoxy-8-oxo-guanosine 5'-monophosphate.
机译：通过在线设置研究DNA和RNA核苷酸的氧化行为，该设置由直接耦合到电喷雾电离质谱（ESI-MS）的电化学薄层电池（EC）组成。这种设置允许在电化学电池中以增加的电势产生核苷酸氧化产物。此外，通过电喷雾电离飞行时间质谱（ESI-ToF / MS），无需分离或衍生化步骤即可直接确定产物。质谱对所施加电势的依赖性显示为“质量伏安图”。先进的设置由与电喷雾电离串联质谱（EC / ESI-MS / MS）耦合的电化学电池组成，可基于碎片实验进一步阐明结构。使用硼掺杂金刚石（BDD）工作电极进行电化学转化，已知该工作电极会在高电势下产生羟基自由基。这项研究通过形成众所周知的DNA损伤生物标志物，包括2'-deoxy-8-oxo-guanosine 5，证明了EC-MS系统产生高度相关的氧化产物的能力，这种氧化产物也会在体内发生氧化损伤时发生。 '-单磷酸酯。

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