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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，光发射是从羰基化合物的激发态产生的，所述羰基化合物通过不稳定中间体的热分解形成，所述不稳定中间体分别例如在前者中的二氧杂环丁烷和在后者中的二氧杂环丁烷酮。羰基化合物的热分解产生激发态的机理尚不清楚，因为协同方式导致三重态，其仅产生弱发射。Schuster提出的CIEEL机理包含了分子内电子转移，但最近发现这一观点并不能解释某些实验事实。主要研究结果如下：进行了二氧杂环丁烷酮的氧化反应，确定了二氧杂环丁烷酮的结构。合成了罗非碱（2，4，5-三苯基咪唑）的各种衍生物，发现了具有很高量子产率（0.8）的结构条件，并提出了分子内电子转移的参与。发现具有富电子烯属结构的化合物，例如双异喹啉鎓盐的还原物质与分子氧和/或超氧化物反应。对于新制备的3-芳基二氧杂环丁烷，在室温下分解，给出发射，的芳基基团的二氧杂环丁烷环的构象被证明有很强的影响的发射强度和稳定性的二氧杂环丁烷。