Development of mechanistic probes for the detection of radical and radical ionic intermediates in enzymatic reactions

在几种辅酶B12催化的消除酶反应中，如核糖核苷酸还原酶、丙二醇和甘油脱水酶、乙醇胺解氨酶等，中性和离子自由基都是重要的机械中间体。虽然原则上可以使用自由基时钟反应来测试中性自由基，但目前还没有可靠的工具来探索短寿命离子自由基的中介作用。因此，建议开发一类新的电子转移探针，通过产物分析研究和EPR检测，直接识别酶过程中的自由基离子中间体。

In several coenzyme B12 catalyzed eliminase reactions, such as the Ribonucleotide Reductase, the Propanediol and Glycerol dehydratase and the Ethanolamine Ammonia Lyase, neutral and ionic radicals have been invoked as mechanistically important intermediates. While neutral radicals can in principle be tested using radical clock reactions, there is no reliable tool yet to probe for the intermediacy of short-lived ion radicals. Hence, it is proposed to develop a new class of electron transfer probes that allow to recognize radical ionic intermediates directly in enzymatic processes by using product analysis studies and EPR detection.