高等学校化学学报

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (11): 2586.

• 研究论文 • 上一篇    下一篇

海萤荧光素类似物发光反应机理的理论研究

孙颖, 任爱民, 李作盛, 闵春刚, 任雪峰, 封继康   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130021
  • 收稿日期:2011-02-15 修回日期:2011-03-25 出版日期:2011-11-10 发布日期:2011-10-14
  • 通讯作者: 任爱民 E-mail:aimin_ren@yahoo.com
  • 基金资助:

    国家自然科学基金(批准号: 20673045, 20973078)、留学回国人员启动基金(批准号: 2008890)和吉林大学研究生创新基金(批准号: 20111031)资助.

Theoretical Investigation of the Reaction Mechanism of Cypridina Luciferin Analogues

SUN Ying, REN Ai-Min*, LI Zuo-Sheng, MIN Chun-Gang, REN Xue-Feng, FENG Ji-Kang   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China
  • Received:2011-02-15 Revised:2011-03-25 Online:2011-11-10 Published:2011-10-14
  • Contact: REN Ai-Min E-mail:aimin_ren@yahoo.com
  • Supported by:

    国家自然科学基金(批准号: 20673045, 20973078)、留学回国人员启动基金(批准号: 2008890)和吉林大学研究生创新基金(批准号: 20111031)资助.

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被引次数

10

摘要： 选取海萤类似物6-芳基-2-甲基咪唑[1,2-α]吡嗪-3(7H)酮环的C6位取代物(命名为MIPa~MIPd)进行理论研究. 采用密度泛涵理论B3LYP方法在气相和二甲亚砜(DMSO)及二甘醇二甲醚(DG)两种溶剂中, 对这些类似物在脱去二氧化碳反应过程中所涉及的2个反应路径的反应活化能和产物激发态的荧光寿命进行了计算, 结果表明, 取代吡嗪酮的过氧化四元环在DMSO溶剂中的反应活化能较低, 给电子基团作为取代基时反应更快. 在DMSO溶剂中, 路径Ⅱ的荧光量子效率比路径Ⅰ的高, 但在DG溶剂中, 路径Ⅰ的荧光效率高于路径Ⅱ的荧光效率.

关键词: 海萤荧光素, 化学发光; , 活化能 , 荧光寿命, 密度泛函理论

Abstract: In order to study the chemiluminescent reaction mechanism of Cypridina luciferin, a series of 6-aryl-2-methyllimidazo[1,2-a]pyrazin-3-(7H)-ketone rings based derivetives(named MIPa—MIPd) was chosen as studied objectives in this work. We employed the DFT//B3LYP/6-31G* method to calculate the activation energy and the fluorescence lifetime(τ) of the products in the reaction from the dioxetanones to amidopyrazines in the gas phase, dimethyl sulfoxide(DMSO), and diglyme(DG). The calculated results indicate that Cypridina luciferin analogues possessing the electron-donating aryl group have lower activation energy(ΔEa) and the solvent has significant effect on activation energy(ΔEa), which is lowest in DMSO. The fluorescence-quantum-yield of path Ⅱ is higher in DMSO than that in path Ⅰ, but it reverses in DG.

Key words: Cypridina luciferin, Chemiluminescence, Activation energy, Fluorescence lifetime, Density functional theory(DFT)

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