QM/MM Investigations on the Bioluminescent Decomposition of Coelenterazine Dioxetanone in Obelin  

作　　者：YUE Ling 

机构地区：[1]Key Laboratory for Non-equilibrium Synthesis and Modulation of Condenaed Matter, Ministry of Education, School of Sciences, Xi 'an Jiaotong University, Xi "an 710049, P. R. China

出　　处：《Chemical Research in Chinese Universities》2018年第5期758-766,共9页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（No.21503156） and the China Postdoctoral Science Foundation（No.2015M572544）.

摘　　要：The bioluminescent mechoafism of colenterazine dioxetanone（CZD） in the photoprotein of Obelia（obelin） was investigated by the combined quantum and molecular mechanics（QM/MM） method at TD-DFT level, which involved the real protein environment in decomposition of 1,2-dioxetanones. The anionic decomposition of CZD in （CZD＋H2O）- model can go through a charge transfer（CT） catalyzed asynchronous-concerted process, which can be elucidated by the gradual reversible CT initiated luminescence（GRCTIL） mechanism. The neutral CZD in （CZDH＋H2O） decomposes through an uncatalyzed non-CT biradical process. The anionic decomposition catalyzed by CT, in which the S0/S1 surface ＂double crossing＂ hence has ability to provide high quantum yield of singlet chemiexcitation is thus more possible in bioluminescence of photoprotein.The bioluminescent mechoafism of colenterazine dioxetanone（CZD） in the photoprotein of Obelia（obelin） was investigated by the combined quantum and molecular mechanics（QM/MM） method at TD-DFT level, which involved the real protein environment in decomposition of 1,2-dioxetanones. The anionic decomposition of CZD in （CZD＋H2O）- model can go through a charge transfer（CT） catalyzed asynchronous-concerted process, which can be elucidated by the gradual reversible CT initiated luminescence（GRCTIL） mechanism. The neutral CZD in （CZDH＋H2O） decomposes through an uncatalyzed non-CT biradical process. The anionic decomposition catalyzed by CT, in which the S0/S1 surface ＂double crossing＂ hence has ability to provide high quantum yield of singlet chemiexcitation is thus more possible in bioluminescence of photoprotein.

关 键 词：1 2-Dioxetanone BIOLUMINESCENCE COELENTERAZINE PHOTOPROTEIN Quantum and molecular mechanics 

分 类 号：O641[理学—物理化学] TQ320.52[理学—化学]