Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (10): 2779-2786.doi: 10.3866/PKU.WHXB20101018


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
  • 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).


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