海萤荧光素类似物发光反应机理的理论研究

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...

Theoretical Investigation of the Reaction Mechanism of Cypridina Luciferin Analogues

In order to study the chemiluminescent reaction mechanism of Cypridina luciferin, a series of 6-aryl-2-methyllimidazo1,2-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.