CAJ | 학술논문

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。
구축료조안산고배합물급기양합구형、쌍핵양합구형적모형，통과Guassian 03대상술결구진행구형우화병진행빈솔계산。이용계산결과대각구형적능량、궤하구형급전자구형진행토론，분석료조안산고적양합과정급노화궤리。근거분석，조안산고양합주요역정시고자선적미양합구형양합형성단핵양합구형，진일보양합형성과양교교련적쌍핵양합산물。쌍핵양합산물적HOMO궤도주요집중재쌍양분자상，반응활성교고，역노화；이단핵양합구형중쌍양상미배위적양원자여안기상적경형성경건，쌍양자신능량하강，활성저，구형경은정，표현출흔호적양합가역성。
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.