论文部分内容阅读
构筑了组氨酸钴配合物及其氧合构型、双核氧合构型的模型,通过Guassian 03对上述结构进行构型优化并进行频率计算。利用计算结果对各构型的能量、几何构型及电子构型进行讨论,分析了组氨酸钴的氧合过程及老化机理。根据分析,组氨酸钴氧合主要历程是高自旋的未氧合构型氧合形成单核氧合构型,进一步氧合形成过氧桥桥联的双核氧合产物。双核氧合产物的HOMO轨道主要集中在双氧分子上,反应活性较高,易老化;而单核氧合构型中双氧上未配位的氧原子与氨基上的氢形成氢键,双氧自身能量下降,活性低,构型更稳定,表现出很好的氧合可逆性。
The cobalt histidine complex, its oxygenated configuration and the dinuclear oxygenated configuration model were constructed. The above structure was optimized by Guassian 03 and the frequency was calculated. The energy, geometry and electronic configuration of each configuration were discussed with the calculation results. The oxygenation process and aging mechanism of histidine cobalt were analyzed. According to the analysis, the main course of histidine cobalt oxygenation is the formation of the mononuclear oxygenation structure of the highly-spinned, non-oxygenated oxygenation and further oxygenation to form the dinuclear oxygenation product of the peroxide bridge. The HOMO orbitals of the dinuclear oxygenated products are mainly concentrated on the dioxygen molecules, which have high reactivity and easy aging. However, uncoordinated oxygen atoms on the dioxygen in the mononuclear oxygenation form hydrogen bonds with hydrogen on the amino groups, and bis Oxygen itself decreased energy, low activity, the configuration is more stable, showing good oxygen reversibility.