组氨酸钴(Ⅱ)氧合过程的理论研究  

Theoretical research of cobalt(Ⅱ)-histidine oxygenation process

作　　者：杨杨[1] 邓雅丽[1] 岳凡[1] 陈华梅[2] 孙都成[2] 王吉德[1,2] 

机构地区：[1]新疆大学,石油天然气及精细化工重点实验室 [2]新疆大学化学化工学院

出　　处：《计算机与应用化学》2013年第6期633-637,共5页Computers and Applied Chemistry

基　　金：国家自然科学基金(20961010;21162027);教育部高等学校博士学科点专项科研基金(20106501120002);重点实验室开放课题基金(XJDX0908-2011-11)

摘　　要：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 structures of cobalt（Ⅱ）-histidine complexes, its oxygenated configuration and dual core oxygenated configuration were built, and optimized by means of the Guassian 03. The energy, the geometrical configuration and the electronic configuration of every structure was discussed through the calculation results and then the oxygenation process and ageing mechanism of cobalt（Ⅱ）-histidine was analysised. According to the analysis, the main oxygenation process of cobalt（Ⅱ）-histidine is high spin unoxygenation configuration oxygenates to form single core oxygenation configuration and then transformed to dual-core oxygenation bridgied by peroxide bridge. The HOMO orbital of dual-core oxygenation product focuses on dioxygen molecules, so the dioxygen has high reactivity and easy to age; but to the mononuclear oxygenation configuration, there are a hydrogen bond between the uncoordinated oxygen atom of dioxygen and the hydrogen atoms on Amino, the energy of dioxygen reduced and its activity is low, therefore the mononuclear oxygenation configuration is more stable which induced it＇s good oxygenation reversibility.

关 键 词：氧载体 组氨酸钴 氧合过程 理论计算 

分 类 号：O614[理学—无机化学]