两种高分子化锌卟啉络合物与特丁津相互作用的光谱性能研究

将苯基卟啉(PP)功能化的聚甲基丙烯酸缩水甘油酯(PGMA)即PP-PGMA和羟基苯基卟啉(HPP) 功能化的PGMA(HPP-PGMA)分别与锌离子发生络合反应,制得高分子化的苯基锌卟啉ZnPP-PGMA或羟苯基锌卟啉ZnHPP-PGMA。采用¹H-NMR对ZnPP-PGMA和ZnHPP-PGMA的化学结构进行了表征,用紫外-可见光谱法、荧光光谱法研究了其光谱性能。将ZnPP-PGMA或ZnHPP-PGMA与特丁津作用,研究特丁津对其光谱性能的影响。研究结果表明:高分子化的金属卟啉ZnPP-PGMA和ZnHPP-PGMA都具有强的光谱性能,相对于PP-PGMA和HPP-PGMA,其电子吸收光谱Soret吸收带红移,荧光发射峰蓝移。ZnPP-PGMA和ZnHPP-PGMA分别与特丁津作用后,ZnPP-PGMA的紫外光谱发生一定程度的红移,且ZnPP-PGMA和ZnHPP-PGMA发生明显的荧光猝灭现象。随着特丁津浓度的增大,ZnHPP-PGMA发生荧光猝灭的程度增大。

Spectroscopic Properties of Two Kinds of Zn Porphyrin-functionalized Polymer and Their Coordination Products with Terbuthylazine

The benzylporphyrin (PP)-functionalized polyglyceryl methacrylate (PGMA) and the hydroxylbenzylporphyrin (HPP)-functionalized PGMA, i.e. PP-PGMA and HPP-PGMA, were coordinated with Zn²⁺ ion respectively, resulting in the Zn porphyrin-functionalized PGMA, i.e. ZnPP-PGMA and ZnHPP-PGMA. The chemical structures of ZnPP-PGMA and ZnHPP-PGMA were characterized by nuclear magnetic resonance (¹H-NMR) spectroscopy. The spectroscopic properties of ZnPP-PGMA and ZnHPP-PGMA were studied by means of UV-Vis spectroscopy and fluorescence spectroscopy. The axial coordination reaction between two kinds of Zn porphyrin-functionalized PGMA and terbuthylazines was studied by using the fluorescence spectrum titration method. The affective factors for fluorescence character of axial coordination reaction were investigated. The results show that both ZnPP-PGMA and ZnHPP-PGMA have possessed strong spectral characteristics. Comparing with PP-PGMA and HPP-PGMA, the Soret absorption bands of ZnPP-PGMA and ZnHPP-PGMA exhibited obvious red shift, and the blue shift occurred for Q emission bands of them. In addition, both the Soret and Q absorption bands of ZnPP-PGMA exhibited red shift in the electronic absorption spectra. The fluorescence quenching occurred in the product of terbuthylazine. The fluorescence quenching for ZnHPP-PGMA was a little less than ZnPP-PGMA. It is because the hydrogen bonding between ZnHPP-PGMA and terbuthylazine led to the weaker axial coordination. Moreover, the fluorescence quenching of ZnHPP-PGMA was strengthed with the increasing concentration of terbuthylazine.