氘代标记研究Cys转化为Dha中的蛋白化学反应机理
之前开发的DBHDA试剂可以高效选择性在蛋白中的Cys进行脱除反应生成Dha,然而其中的机制却不清楚,进一步利用这种氘代标记研究了Cys转化为Dha中的蛋白化学反应机理。先探究了与蛋白中的Cys反应生成的硫叶立德反应中间体的稳定性以及对随后的C-H交换反应活性的影响。发现中间体发生消除反应生成的Dha的过程中硫叶立德的生成和相应位点的脱除是密切相关的。还通过密度泛函理论对DBHDA将Cys转化为Dha过程的可能的过渡态能量进行计算,发现了在消除反应过程中硫叶立德中间体可能存在Swern-like分子内脱质子过程。
总之,开发了一种翻译后位点选择性无痕的氘代标记技术,并利用这种技术研究了蛋白质化学中的双烷基化的脱除试剂DBHDA将Cys脱除转化为Dha的机理。
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