细胞色素P-450模拟酶的快速混合停流时间分辨吸收谱研究 Ⅱ.Mn~Ⅲ(Por.)Cl-PhIO体系  

Time resolved Stopped Flow Studies of Cytochrome P 450 Enzyme Mimic Systems Ⅱ. Mn Ⅲ(Por.)Cl PhIO Systems

作　　者：夏春谷[1] 尉迟力[1] 马红竹[1] 李树本[1] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室

出　　处：《分子催化》1999年第1期27-34,共8页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金

摘　　要：采用快速混合停流技术，考察了在实际反应条件下，不同锰卟啉配合物ＭｎⅢ（Ｐｏｒ．）Ｃｌ（Ｐｏｒ．＝ＴＰＰ、ＴＭＯＰＰ和ＴＦＰＰ）与单氧给体ＰｈＩＯ构建的细胞色素Ｐ－４５０模拟酶体系催化活性物种的生成及催化烯烃环氧化过程．在氧给体ＰｈＩＯ作用下，ＭｎⅢ（Ｐｏｒ．）Ｃｌ均生成了高价锰氧卟啉配合物和双核μ－氧锰卟啉配合物；但ＭｎⅢ（ＴＰＰ）Ｃｌ和ＭｎⅢ（ＴＭＯＰＰ）Ｃｌ存在严重的氧化分解，而ＭｎⅢ（ＴＦＰＰ）Ｃｌ不易氧化分解，且它的催化环氧化活性最高．The reaction of a variety of manganese porphrin complexes such as Mn Ⅲ(TPP)Cl, Mn Ⅲ(TMOPP)Cl and Mn Ⅲ(TFPP)Cl with oxidant iodosobenzenePhIO under ambient conditions has been investigated by stopped flow spectrophotometry. It is shown that the high valent oxomanganese porphyrin complexes and dimeric μ oxo manganese(Ⅳ) porphrin complex intermediates were produced in the reaction between Mn Ⅲ(Pro.)Cl and PhIO. The oxomanganese porphrin complexes in the reaction of Mn Ⅲ(TFPP)Cl with PhIO almost completely decompsed to the corresponding Mn Ⅲ(TFPP)Cl species. Epoxidization of 1,4 diphenylbutadiene DPBD by Mn Ⅲ(Pro.)Cl with PhIO indicates that Mn Ⅲ(Pro.)Cl is more effective and stable than Fe Ⅲ(Pro.)Cl.

关 键 词：锰卟啉 环氧化 细胞色素P450 催化剂 模拟酶 

分 类 号：O643.36[理学—物理化学]