STUDY ON NOVEL PHOTORESPONSIVE POLYMER MATERIAL

1. 为了建立mg -叶绿素a在光合成中的合成模型，将中四（羧基苯基）卟啉与H_2N(CH_2)_nNH_2通过酰胺键反应转化为二聚体。剩下的二聚体羧基与苄基卤化物酯化，得到单乙烯基化合物，单乙烯基化合物与大量的n -乙烯基-2-吡咯烷酮共聚，得到以卟啉二聚体为垂坠物的水溶性聚合物。在卟啉环上合成了含有中心金属如Mg、Zn、Co（II）、Ni（II）和CU（II）的可聚合二聚体，并进行了共聚得到水溶性共聚物。研究了这些共聚物在H_2O中加入到FRA - l -抗坏血酸光氧化还原体系中的效果。因此，具有两个卟啉或金属卟啉环以最短链连接的垂坠二聚体的共聚物是最有效的光氧化还原催化剂。具有悬垂型镁-卟啉二聚体的聚合物比具有悬垂型单体的聚合物更有效。2.除Mg外，其他金属的作用均以Zn有效，其他金属几乎没有作用。利用了偶氮苯的光顺式异构化及其引起的立体结构变化。因此，用亚氨基二乙酸对偶氮苯的3,3'位提供了金属螯合性能。苯乙烯段也被引入到5位或3位，得到可聚合的单体，共聚得到具有螯合功能的苯溶或水溶性共聚物。从上述偶氮苯中分离出的带有亚氨基二乙酸部分的酸酐与二胺缩聚，得到具有分离羧基且主链上有偶氮苯单元的水溶性聚酰胺。这些聚合物的金属离子提取能力随光反式异构化而改变，并与金属种类有关，其中锌的提取能力最好。少

1. In order to get a synthetic model for Mg-chlorophyll a In photo- synthesis, meso-tetra(carboxyphenyl)porphyrin was converted to its dimers via amide linkage by condensation with H_2N(CH_2)_nNH_2. The remaining carboxyl groups of the resulting dimers were then esterified with benzyl halides so as to afford monovinyl compounds, which were copolymerized with a large excess of N-vinyl-2-pyrrolidone to afford water-soluble polymers bearing porphyrin dimer as pendant. Polymerizable dimers bearing central metals such as Mg, Zn, Co(II), Ni(II), and CU(II) in porphyrin rings were also synthesized and copolymerized to provide water-soluble copolymers. The effect of addition of these copolymers to a photo-redox system: FRA - L-Ascorbic acid in H_2O ,was noted. Thus, copolymers with the pendant dimers in which two porphyrin or metalloporphyrin rings were linked with the shortest chains were the most effective as photoredox catalyst. Polymers with pendant magnesium- porphyrin dimers was the most … More effective of all, exceeding those with pendant monomers. As for the effect of metals other than Mg, Zn was effective but other metals were hardly effective.2. The photo trans-cis isomerization and the resulting sterical structure change of azobenzenes were utilized. Thus, the metal-chelating property was provided to 3,3'-positions of azobenezene using iminodiacetic acid. Styrenic moiety was also introduced to either the 5- or 3-position to afford a polymerizable monomer, which was copolymerized to provide either benzene- or water-soluble copolymers bearing chelating function as pendant. Acid anhydrides from the above-mentioned azobenzene with the iminodiacetic acid moiety were subjected to polycondensation with diamine to provide a water soluble polyamide with the isolated carboxyl group and bearing the azobenzene unit in the principal chain. The metal ion-extracting ability of these polymers was changed with photo trans-cis isomerization and dependent on the kind of metal, Zn being the best among metals investigated. Less