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过渡金属离子在各种化学及生物氧化中扮演着极为重要的作用,现有的研究表明参与催化氧化的关键活性物种已不再局限于金属氧物种(Mn+O),金属氢氧物种(Mn+—OH)与金属过氧物种(Mn+—OOH)均被发现能够参与各种氧化反应。有些有机化合物也能直接催化有机物的氧化反应,同时,相似的有机物如NADH和辅酶Q一直在生物代谢中发挥着重要作用。但是,现有的研究结果还难以清楚解释生物体系中各种氧化酶在不同的氧化反应中选择特定活性物种的内在原因。因此,了解这些活性物种之间的氧化性能异同性将非常有助于了解酶对它们的选择,进而理解酶的催化氧化机理,为药物设计提供理论基础,同时也有助于设计新的氧化催化剂。本文对在各种均相催化氧化及生物氧化反应中出现的主要活性中间体种类、各中间体的反应性能、反应机理进行了总结,并就现有的实验数据对过渡金属氧物种与氢氧物种的氧化性能相似性及相异性进行了初步评述。
Transition metal ions play a very important role in various chemical and biological oxidation. The existing research shows that the key active species involved in catalytic oxidation are no longer confined to the metal oxygen species (Mn + O), metal and oxygen species (Mn + -OH) and metal peroxides (Mn + -OOH) were found to be able to participate in various oxidation reactions. Some organic compounds can also directly catalyze the oxidation of organic compounds. Meanwhile, similar organic compounds such as NADH and coenzyme Q have been playing an important role in biological metabolism. However, the existing research results also can not clearly explain the inherent reason why various oxidases in biological systems select specific active species in different oxidation reactions. Therefore, understanding the similarities and differences of the oxidative properties between these active species will greatly help us to understand the enzyme’s selection and further understand the catalytic oxidation mechanism of the enzyme. This will provide a theoretical basis for drug design and help to design a new oxidation catalyst. In this paper, the types of active intermediates, the reaction performance and the reaction mechanism of various intermediates appeared in various homogeneous catalytic oxidation and biological oxidation reactions were summarized. And the existing experimental data for the transition metal oxygen species and hydroxyl The similarities and dissimilarities of the oxidative properties of species were preliminarily reviewed.