Study of Chemiluminescence Mechanism and Application

本研究通过有机合成的方法对化学发光的机理进行了研究，以解释目前尚不清楚的化学发光机理。我们研究了过氧草酸盐化学发光以及邻苯二甲酰肼化学发光。此外，还研究了荧光二苯乙烯染料在分子传感中的应用，几种含供电子基团的草酸盐引起消除基团与高能中间体之间的分子内相互作用，形成酚类的准分子，这支持了电子相互作用在过氧草酸盐化学发光过程中的重要作用，4-苯乙烯基苯二甲酰肼的化学发光行为与取代基的电子性质密切相关。强供电子基团增加了发射体邻苯二甲酸阴离子的荧光量子产率，导致化学发光增强， ...更多信息 紧张为了发展利用化学发光的分子传感技术，研究了具有强荧光的二苯乙烯基苯类化合物作为反映其周围微环境变化的荧光团的应用。推拉型的二苯乙烯基苯响应于各种质子溶剂，水和醇，被荧光猝灭。荧光猝灭效率与溶剂的pKa值有密切关系，这可能为底物的传感器提供了质子特性。有机氯代和硝基化合物是农药和爆炸物的有害残留物，也会猝灭具有强给电子取代基的强荧光二苯乙烯基苯。苯硼酸和钙离子对二苯乙烯基苯的荧光也有猝灭作用。这种荧光猝灭是由于光诱导电子转移（PET）过程引起的，因此本研究为有机化学发光的发展提供了一些新的方向。少

In this study, the mechanism of chemiluminescence was examined by an organic synthetic method in order to explain those that have been unclear. We investigated peroxyoxalate chemiluminescence as well as phthalhydrazide chemiluminescence. Additionally, application of the fluorescent stilbene dyes was also investigated to use them for molecular sensing.The several oxalates with the electron-donating groups caused the intramolecular interaction between the eliminating groups and the high energy intermediates to form the excimers of the phenols, which supports the important role of the electronic interaction such as a CIEEL process during peroxyoxalate chemiluminescence,The reactions of 4-styrylphthalhydrazides revealed that the chemiluminescence behavior was highly dependent on the electronic nature of the substituents. The strongly electron-donating groups increased the fluorescence quantum yields of the emitters, phthalic acid anions, resulting in enhancement of the chemiluminescence in … More tensities. Control of the chemiluminescence feature by such the effect provides a new finding in the phthalhydrazide chemiluminescence.To develop a molecular sensing using chemiluminescence, the strongly fluorescent distyrylbenzenes were examined for the use as the fluorophores that reflect the change in the microenvironment around them. The pull-push type of distyrylbenzenes responded toward various protic solvents, water and alcohols, to be fluorescence-quenched. The close relation between the fluorescence-quenching efficiency and the pKa values of the solvent was established, which might provide the sensor of the substrates with protic characters.Organic chloro- and nitro compounds that are harmful residues of agricultural chemicals and explosives also quenched the strongly fluorescent distyrylbenzenes with the strongly electron-donating substituents. Phenylboronic acid and calcium ion also quenched the fluorescence of these distyrylbenzenes. Such fluorescence quenching was due to the photo-induced electron transfer (PET) process.Thus, this study provides some new aspects useful to develop the organic chemiluminescence. Less