水体系中含卟啉基团的两亲高分子的自组装行为和性质的研究

Study of Self-Assemble and Properties of Amphiphilic Polymer Containing Porphyrin Units in Aqueous Media

在文中合成了两种不同的卟啉单体5-(4-acryloyloxyphenyl)-10,15,20-tris(4-carboxylphenyl)porphyrinate zinc(II)(ZnAOTCPP)和5-(4-acrylo-yloxyphenyl)-10,15,20-tris(4-methoxycarboxylphenyl)porphyrinate zinc(II)(ZnMeAOTCPP),它们分别与丙烯酰胺(Acrylamide,AM)聚合得到含有卟啉基团的两亲高分子.与对应的单体相比,含有三羧酸卟啉基团的高分子在水中形成了一个新的紫外吸收峰和一个新的荧光发射峰,而含有三羧酸甲酯卟啉基团的高分子除此之外在更长波的方向上还另外出现了一个新的紫外吸收峰和一个新的荧光发射峰.随着高分子水溶液浓度的提高,高分子中卟啉基团的光谱性质的变化趋势显示高分子在水中的自组装行为可以分为分子间缔合和分子内缔合的两种情况.此外,实验结果显示含有三羧酸甲酯卟啉基团的高分子相对于含有三羧酸卟啉基团的高分子更加有利于卟啉缔合物的形成.

Two porphyrin monomers 5- （4-acryloyloxyphenyl） -10,15,20-tris （4-carboxylphenyl） porphyrinate zinc （Ⅱ） （ZnAOTCPP） and 5-（4-acryloyloxyphenyl）-10, 15, 20-tris （ 4- methoxycarboxylphenyl） porphyrinate zinc （Ⅱ） （ZnMeAOTCPP） were synthesized, and their corresponding amphiphilic polymers with acrylamide （AM） were prepared. Compared with corresponding porphyrin monomer, the polymer containing tricarboxyl-porphyrin units displayed a new absorption band and a new fluorescence emission band in water, while the one containing trimethoxycarboxyl-porphyrin units exhibited an additional new absorption band and fluorescence emission band at even longer wavelength region. The variations of spectroscopic properties of porphyrin units in polymers with increasing concentrations of polymers in aqueous media indicated that the self-assemble behavior of polymers had intermolecular association and intramolecular association two stages. Moreover, the polymer containing trimethoxycarboxyl- porphyrin units showed larger ability in the formation of porphyrin association complexes than the one containing tricarboxyl-porphyrin units.