基于萤火虫发光原理的新型化学发光体系及其机理研究

Chemiluminescence has been intensively investigated over the past decades due to its broad application in many areas of science. However, limited diversity restricts the development of the chemiluminescence materials. One of important methods to develop a new class of chemiluminescence is simulation of the firefly luminescence. Unfortunately, the key structure characteristics of luciferin in firefly luminescence is still unknown. In this proposal, a series of xanthene derivatives will be developed as new chemiluminescence molecules inspired by the structural characteristics of luciferin and our previous researches. Firstly, the mechanism of xanthene derivatives will be investigated, and the key structural characteristics of luciferin in degradation of luminescence will be summarized. And then the effect of electron donating/withdrawing substituents, conjugacy, and the bond energy of C-X on the properties of the chemiluminescence of xanthene derivatives will be investigated in different oxygen concentrations, pH, solution, temperature etc. And finally, the application of the chemiluminescence of xanthene derivatives in oxygen sensor and pH indicator will be explored. The accomplishment of this project will inspire and accelerate the further development of the mechanism of firefly luminescence and molecular bionics.

化学发光材料已经开始应用于科学技术的各个领域，但种类较少等因素一直制约着这类材料的发展。认识与模拟萤火虫发光机理是拓展化学发光材料种类的重要方法之一，然而哪些结构特征是模拟萤光素发光的关键因素一直是未知的。本项目将依据萤火虫体内的萤光素烯醇降解发光机理以及申请人的前期工作基础，重点开发出一类新型的具有呫吨骨架的化学发光体系。首先深入研究呫吨类分子烯醇降解化学发光的机理，提炼出萤光素烯醇降解发光的关键结构特征；然后系统研究取代基吸/推电子效应、共轭性、C-X键能、氧气、pH、溶剂、温度等内在或者外界的因素对呫吨类分子发光性质的影响；最后探索呫吨类化学发光分子在氧传感，pH试剂等探针领域中的应用。本项目的顺利完成无论对萤火虫发光机理研究还是仿生(特别是分子角度的机理仿生）研究均具有重要意义。

基于萤火虫发光机理，开发新型的化学发光材料是拓展该类材料在生物检测、探针等领域应用的重要方法和方式之一。萤火虫发光的底物萤光素已经被发光的研究和利用，然而哪些结构特征是模拟萤光素发光的关键因素一直是未知的。在本基金资助下，首次证明了烯醇降解发光的机理为二氧四元环的生产以及分子间电子交换，揭示了烯醇降解化学发光所需的结构特征包括易离去的基团和高荧光量子效率的结构，系统地分析了化学发光的内在影响因素（取代基的吸/推电子效应、共轭效应等）和外在影响因素（氧气、pH、溶剂、温度等）。基于此，开发出不同发光颜色和发光效率的新型化学发光材料，为该类材料在探针、生物检测和治疗等领域的应用奠定材料和理论基础。在该基金资助下，本项目基于质子耦合电子转移机理，开发出一系列全新的双稳态电致变色材料，并探讨了其在电子价签等领域的应用。