摘要/Abstract

生物体系中，金属酶活化氧气进而参与新陈代谢相关的各种氧化反应，可高效实现有机化合物氧化反应.因此，揭示金属酶的循环机理，对发展清洁高效的催化氧化反应具有重要的指导意义.金属酶的循环过程通常会形成一系列的金属-氧加合物，如金属超氧、过氧、过氧化氢、氧及羟基等物种.由于生物体的酶循环过程十分复杂，所形成的高活性的金属-氧加合物极难捕捉和表征.为此，化学家开展了生物酶的仿生模拟研究，即用化学的方法仿照酶的活性位点构建具有类似配位环境的金属中心，获得人工合成的各种金属-氧加合物，进而了解其结构与活性.本文以近年来单核铁-氧和锰-氧加合物取得重要进展为背景，举例说明金属酶活化氧气所涉及的金属-氧加合物，并重点从结构及活性等方面总结了模拟酶的金属-氧加合物的研究进展.
关键词: 金属-氧加合物, 金属酶, 模拟酶, C—H键活化, 氧气活化
In biological system, metalloenzymes utilize dioxygen for metabolically oxidative transformations, in which organic compounds can be oxidized efficiently. Therefore, it is of great interest to unravel the enzymatic mechanism in the development of clean and efficient catalytic oxidation reactions. In the dioxygen activation by metalloenzymes, a series of metal-oxygen adducts, such as metal-superoxo, -peroxo, -hydroperoxo, -oxo and -hydroxo species, are formed as the active intermediates. In general, these intermeditates are difficult to capture for further characterizations and investigations because of their unstability and the complicated enzymatic systems. Alternatively, the enzyme models, designed and synthesized by mimicking the active center and coordination environment of metalloenzymes, can be easily acquired and manipulated for further structure and reactivity studies. In this review, we briefly illustrate the active sites of metalloenzymes in biology and focus on the recent achievements in mononuclear iron-oxygen and manganese-oxygen adducts in biomimetic studies.
Key words: metal-oxygen adduct, metalloenzymes, enzyme models, C—H bond activation, dioxygen activation


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