丙氨酸钴配合物氧合性能的实验和理论研究（英文）  

A joint experimental and DFT study on oxygenation properties of alanine cobalt complexes

作　　者：周柯 岳凡[1] 陈华梅[1] 周乐 王吉德[1] ZHOU Ke;YUE Fan;CHEN Huamei;ZHOU Le;WANG Jide(Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education ＆ Xinjiang Uygur Autonomous Region, College of Chemistry and Chemical Engineering of Xinjiang University, Urumqi 830046, Xinjiang Uygur Autonomous Region, China;State Key Laboratory of Solidification Processing, Northwestern Polyteehnical University, Xi＇an 710072, Shaanxi, China)

机构地区：[1]新疆大学石油天然气精细化工教育部和自治区共建重点实验室,新疆乌鲁木齐830046 [2]西北工业大学凝固技术国家重点实验室,陕西西安710072

出　　处：《计算机与应用化学》2018年第3期251-258,共8页Computers and Applied Chemistry

基　　金：National Natural Science Foundation of China(No.21162027,21261022)

摘　　要：本文主要研究了两种氧载体Ala–Co（Ⅱ）和Ala–Co（Ⅱ）–Py氧合性质的差异。实验结果表明Ala–Co（Ⅱ）–Py比Ala–Co（Ⅱ）有更好的氧合性能。利用量子化学密度泛函理论的B3LYP方法,在6-31G（d）水平上,对其几何构型、电子结构、前线轨道进行了研究。理论计算表明Ala–Co（Ⅱ）–Py氧合过程中金属Co（Ⅱ）到O2的π＊轨道电子转移增强,氧合后构型稳定,表现出很好的氧合可逆性。因此,在这类模型研究中,认为Co（Ⅱ）与轴向碱基Py配位后,Co离子可与双氧更好的键合。The different oxygenation properties of the two oxygen carriers（Ala（alanine）–Co（Ⅱ） and Ala–Co（Ⅱ）–Py（pyridine）） were studied in this paper. Experimental results show that Ala–Co（Ⅱ）–Py exhibits better oxygenation performance than that of Ala–Co（Ⅱ）. Density functional theory（DFT） was used to study the changes of geometry structures, electrons structures, and frontier molecular orbitals during oxygenation process, at the B3LYP/6-31G（d） mixed basis set. Theoretical calculations suggest that the electron cloud density of Co（Ⅱ） has a strong electron transfer to π＊ orbital of O2 in Ala–Co（Ⅱ）–Py oxygenation process. After oxygenation, the configuration of Ala–Co（Ⅱ）–Py shows good oxygenation reversibility. Therefore, the coordination of Co（Ⅱ） with axial bases Py ligand promotes the ability of Co（Ⅱ） to bind with O2 in this kind of model study.

关 键 词：氧合性能 钴配合物 实验 量子化学密度泛函理论 丙氨酸 Co(Ⅱ) B3LYP方法 几何构型 

分 类 号：O6[理学—化学] O61