侧链键合锰卟啉的线型聚甲基丙烯酸缩水甘油酯的制备及其谱学性质

Preparation and Spectroscopic Properties of Line-Type Poly(glyceryl methacrylate) Bonding Manganoporphyrin on Side Chain

采用Adler法合成了Meso-四(对羟基苯基)卟啉(THPP),在均相体系中使聚甲基丙烯酸缩水甘油酯(PGMA)与THPP发生开环反应,得到侧链键合有羟基苯基卟啉的线型PGMA(HPP-PGMA);进一步使HPP-PGMA与锰离子发生配合作用,得到侧链键合有锰卟啉(MnP)的线型PGMA(MnP-PGMA),测定了HPP-PGMA的1HNMR谱,表征了其化学结构;测定了HPP-PGMA与MnP-PGMA的UV-Vis光谱及荧光发射光谱,考察了其光物理行为.实验结果表明,通过THPP外环上羟基与PGMA侧基环氧键的开环成醚反应,可以顺利地将羟基苯基卟啉及其锰配合物键合在PGMA的侧链上.HPP-PGMA具有THPP的特征电子吸收光谱与荧光发射光谱,且随着THPP键合度的增加,光谱的强度增强.MnP-PGMA具有小分子锰卟啉的特征电子吸收光谱与荧光特征,其Soret吸收带发生显著红移(红移58nm),Q吸收带的数量减为3个吸收峰;实验发现,MnP-PGMA与小分子锰卟啉类似,在Q发射带没有荧光发射.

The special chemical structures and properties of porphyrins make them have wide applications in many fields, such as biomimetic catalysis, electrocatalysis, chemical and biological sensors, solar energy conversion, and so on. If polymeric materials are functionalized with porphyrins, a new class of functional polymeric materials will be obtained, and it will have potential applications in advanced science and technology fields. In this paper, a valuable and significant exploration in the immobilization of porphyrins onto polymeric materials or the functionalization of polymers with porphyrins was studied based on poly （ glyceryl methacrylate） （PGMA）. Meso-tetra （4-hydroxylphenyl） porphyrin （THPP） was synthesized by adopting Adler＇ s method. The bonding reaction between PGMA and THPP was carried out in a homogeneous system, （hydroxylphenyl） porphyrin was bonded on the side chains of PGMA, and porphyrin-bonding PGMA was obtained （denoted as HPP-PGMA）. Further, the coordination reaction between HPP-PGMA and MnCl2 was performed and manganese porphyrin-bonding PGMA was gained （denoted as MnP-PGMA）. The structure of HPP-PGMA was characterized with 1H NMR spectrum. The electronic absorption and fluorescence emission spectra of HPP-PGMA and MnP-PGMA were determined and their photophysical behavior was examined. The experimental results show that（hydroxylphenyl） porphyrin and its manganese complex can be favorably bonded on the side chains of PGMA via the ring-openibg reaction between epoxy bonds on the side chains of PGMA and the hydroxyl groups of THPP, and line-type HPP-PGMA and MnP-PGMA were prepared successfully. HPP-PGMA possesses the characteristic electronic absorption spectrum and fluorescence emission of porphyrins, and MnP-PGMA have the characteristic electron absorption spectrum and fluorescence emission of original manganese porphyrins.