物理化学学报 >> 2010, Vol. 26 >> Issue (10): 2779-2786.doi: 10.3866/PKU.WHXB20101018

量子化学及计算化学 上一篇    下一篇

海萤荧光素衍生物发光反应关键步骤的理论研究

孙颖, 任爱民, 闵春刚, 邹陆一, 任雪峰   

  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 130023
  • 收稿日期:2010-06-07 修回日期:2010-07-17 发布日期:2010-09-27
  • 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(20673045, 20973078), 留学回国人员启动基金(外交司留(2008)890 号)和国家重点基础研究发展计划项目(973)(2002CBN613406) 资助

Theoretical Investigation of the Key Reaction for the Chemiluminescence of Cypridina Luciferin Analogues

SUN Ying, REN Ai-Min, MIN Chun-Gang, ZOU Lu-Yi, REN Xue-Feng   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University,Changchun 130023, P. R. China
  • Received:2010-06-07 Revised:2010-07-17 Published:2010-09-27
  • Contact: REN Ai-Min E-mail:aimin_ren@yahoo.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20673045, 20973078), Start Fund for Returned Overseas People, China ((2008)890), and Major State Basic Research Development Program of China (973) (2002CBN613406).

摘要:

用不同取代基对化学发光物质6-芳基-2-甲基咪唑[1,2-α]吡嗪-3-(7H)酮环(海萤发光的类似物)的芳基位进行取代, 形成系列海萤荧光素类似物MIPa-MIPd; 并采用B3LYP/6 -311+G(d,p)方法, 通过电子抽取能(EEP) 的计算和自然电荷布居分析(NPA), 研究了在气相、二甲亚砜(DMSO) 和二甘醇二甲醚(DG) 中海萤发光的类似物从阴离子变化到自由基过程中取代基的作用. 结果表明: 在这个过程中, 吲哚在DG 中作为取代基(MIPb) 时的EEP 最小, 电荷变化最大, 说明这种取代基有利于反应的进行.

关键词: 密度泛函理论, 海萤荧光素, 化学发光, 电子抽取能, 自然电荷布居分析

Abstract:

A series of 6-aryl-2-methylimidazo[1,2-α]pyrazin-3-(7H)-ketone based derivatives MIPa-MIPd (cypridina luciferin analogues) were investigated using the B3LYP/6-311+G(d,p) method, and we modeled a 6-site replacement by different substituents. The effect of different substitutions on cypridina luciferin analogues in their transition from anions to free radicals was studied by electron extraction potentials (EEP) and natural charge population analysis (NPA) in gas phase, dimethyl sulfoxide (DMSO), and diglyme (DG). The calculated results indicated that MIPb (3-indolyl as the substituent) had a lower EEP and a larger natural charge population change occurred at the MIP moiety in DG when transitioning from the anion to its free radical than in the other solvents. We also showed that 3-indolyl, as a substituent, accelerated the luminescent reaction of MIP.

Key words: Density functional theory, Cypridina luciferin, Chemiluminescence, Electron extraction potential, Natural charge population analysis

MSC2000: 

  • O641