Study of Chemiluminescence Mechanism and Application

在这项研究中，通过有机合成的方法研究了化学发光的机制，以解释那些一直不清楚的事情。我们研究了过氧草酸盐的化学发光和邻苯二甲酰肼的化学发光。此外，还研究了荧光二苯乙烯类染料在分子传感方面的应用。几种带有给电子基的草酸酯类化合物通过消除基团与高能中间体之间的分子内相互作用形成了苯酚类化合物的准分子，这支持了电子相互作用的重要作用，如CIEEL过程在过氧草酸盐类化学发光中的作用，4-苯基邻苯二甲酰肼的反应表明化学发光行为高度依赖于取代基的电子性质。强给电子基增加了邻苯二甲酸阴离子发射体的荧光量子产率，从而增强了…的化学发光更多的张力。通过这种效应控制化学发光特性提供了邻苯二甲酰肼化学发光的新发现。为了开发一种基于化学发光的分子传感，研究了强荧光二苯基苯作为荧光团的作用，以反映其周围微环境的变化。拉推型二苯基苯对各种质子型溶剂、水和醇都有荧光猝灭作用。建立了荧光猝灭效率与溶剂pKa值之间的密切关系，为底物传感器提供了质子性特征。有机氯和硝基化合物是农药和爆炸物的有害残留物，它们也猝灭了具有强给电子性取代基的强荧光二芳基苯。苯基硼酸和钙离子也对这些二苯基苯的荧光有猝灭作用。这种荧光猝灭是由于光诱导电子转移(PET)过程造成的。因此，本研究为有机化学发光的发展提供了一些新的方面。较少

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