五氟代锰卟啉模拟酶体系快速混合停流吸收谱  

Rapid-Mixing Stopped-Flow Spectra of Manganese (Pentafluorophenyl) Porphyrin Enzyme-Mimic Systems

作　　者：李臻[1] 夏春谷[1] 尉迟力[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,兰州730000

出　　处：《物理化学学报》1999年第8期714-719,共6页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金资助项目!(29773056)

摘　　要：采用快速混合停流技术，在实际反应条件下，考察了五氟代锰卟啉配合物Ｍｎ＾Ⅲ（ＴＦＰＰ）Ｃｌ与两种单氧给体亚碘酰苯ＰｈＩＯ和过氧苯甲酸ｍ－ＣＰＢＡ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煅烃环氧化过程。The reactions of manganese (pentafluorophenyl) porphrin complex, Mn~Ⅲ(TFPP ) C1 with two oxidants iodosobenzene (PhIO) and m-chloroperoxybenzoic acid(m-CPBA) under ambient con- ditions have been investigated by stopped-flow spectraphotometry. It is shown that high-valent oxo- manganese porphyrin complexes and dimeric μ-oxo manganese(IV) porphrin complex intermediates were produced in the reaction between Mu~Ⅲ (TFPP)C1 and PhIO, and the oxomanganese porphrin complexes almost completely decomposed to the corresponding Mn~Ⅲ（TFPP)C1 species. With m-CPBA as the oxygen donor, only a few short-lived high-valent oxomanganese porpdrin complexes were pro- duced. Epoxidization of 1, 4 - diphenylbutadiene (DPBD) by Mn~Ⅲ(TFPP ) C1 with PhIO and m-CPBA showed that since a stable species was produced in the reaction of Mu~Ⅲ (TFPP)C1 with m-CPBA, so the reactivity of this model system was lower than that with oxidant PhIO.

关 键 词：锰卟啉 P-450 环氧化 模拟酶 催化剂 烯烃 

分 类 号：O643.36[理学—物理化学]