水溶性锰卟啉模拟酶体系快速混合停流谱研究

摘要

采用快速混合停流技术,考察了不同pH值条件下水溶性锰卟啉MnⅢ(TMPyP)与四种单氧给体m-CPBA、KHSO5、NaOCl及H2O2构建的细胞色素P-450模拟酶体系催化氧化活性物种的生成及催化烯烃环氧化过程.低pH值时,主要生成四价锰氧中间体2;而在高pH值时,首先生成五价锰氧中间体1,该中间体再向四价中间体2转化.%The reaction of water-soluble Manganese porphyrin complex,MnⅢ (TMPyP) with a variety of oxidants(m-CPBA,KHSO5,NaOCl and H2O2) under ambient conditions at different pH was investigated by stopped-flow techniques.Oxo-manganese(IV) porphyrin complex intermediate (2) was the main product at lower pH.High-valent oxo-manganese(V) porphyrin (1) was fully formed and subsequently decayed to oxoMn(Ⅳ ) at higher pH.It was shown that oxo-manganese(V) porphyrin was the reactive complex with reducing substrates.