Fundamental Research on Chemi-and Bioluminescence for High-Efficiency Light Emission

高效发光的化学和生物发光基础研究

基本信息

批准号：
06303003
负责人：
MAEDA Koko
金额：
$ 2.69万
依托单位：
Ochanomizu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

In the chemiluminescence and bioluminescence, the light emission is brought out from an excited state of carbonyl compounds formed by thermal decomposition of unstable intermediates, such as dioxetanes in the former and dioxetanones in the latter, respectively. The mechanism of the thermal decomposition to give an excited state of carbonyl compounds is still unclear, because the concerted way leads to a triplet state which gives only weak emission. Schuster reported CIEEL mechanism which contains intramolecular electron transfer, but recently the idea was found not to explain some experimental facts.In this research the oxygenation mechanism of chemi-and bio-luminescent compounds and thermal decomposition mechanism of dioxetanes were investigated. The results obtained are as follows : The oxygenation of imidazopyrazinone which is a main part of luciferins was carried out, and the structure of the dioxetanone was determined. Various derivatives of lophine (2,4,5-triphenylimidazol) were prepared and a structural condition which has very high quantum yield (0.8) was found, and involvement of the intramolecular electron transfer was suggested. Compounds which have electron rich olefinic structure, for example the reduced species of biisoquinolinium salts were found to react with molecular oxygen and/or superoxide. For newly prepared 3-aryl dioxetanes which decompose at room temperature to give emission, the conformation of the aryl group to the dioxetane ring was shown to have strong effect on the emission intensity and on the stability of the dioxetanes.

在化学发光和生物发光中，光发射是由不稳定中间体热分解形成的羰基化合物的激发态引起的，例如分别为前者的二氧杂环丁烷和后者的二氧杂环丁酮。热分解产生羰基化合物激发态的机制仍不清楚，因为协同方式导致仅产生微弱发射的三重态。 Schuster报道了包含分子内电子转移的CIEEL机制，但最近发现这个想法不能解释一些实验事实。本研究研究了化学和生物发光化合物的氧化机制以及二氧杂环丁烷的热分解机制。所得结果如下：对荧光素的主要部分咪唑并吡嗪酮进行了氧化反应，并确定了二氧杂环丁酮的结构。制备了洛芬（2,4,5-三苯基咪唑）的各种衍生物，并发现了具有非常高量子产率（0.8）的结构条件，并暗示涉及分子内电子转移。具有富电子烯属结构的化合物，例如二异喹啉鎓盐的还原物质，被发现与分子氧和/或超氧化物反应。对于新制备的在室温下分解产生发光的3-芳基二氧杂环丁烷，芳基在二氧杂环丁烷环上的构象对发光强度和二氧杂环丁烷的稳定性有很大影响。