STUDY ON NOVEL PHOTORESPONSIVE POLYMER MATERIAL

1.在光合成中，meso-四（羧基苯基）卟啉通过与H_2N（CH_2）_nNH_2的缩合反应，通过酰胺键生成二聚体。然后将所得二聚体的剩余羧基用苄基卤化物酯化以提供单乙烯基化合物，其与大量过量的N-乙烯基-2-吡咯烷酮共聚以提供带有卟啉二聚体作为侧基的水溶性聚合物。还合成了在卟啉环中具有中心金属如Mg、Zn、Co（II）、Ni（II）和Cu（II）的可聚合二聚物，并进行共聚以提供水溶性共聚物。考察了共聚物在光氧化还原体系FRA-L-抗坏血酸水溶液中的作用。因此，具有其中两个卟啉或金属卟啉环与最短链连接的侧链二聚体的共聚物作为光氧化还原催化剂是最有效的。具有镁卟啉二聚体侧链的聚合物是最多的 关于我们 所有这些都是有效的，超过了具有侧基单体的那些。除Mg外，Zn对土壤的影响最大，其它金属对土壤的影响不大.偶氮苯的光顺-反异构化及其空间结构的变化被利用。因此，使用亚氨基二乙酸向偶氮苯的3，3’-位提供金属螯合性质。苯乙烯部分也被引入到5-或3-位以提供可聚合单体，其被共聚以提供承载螯合功能作为侧基的苯-或水溶性共聚物。将来自上述具有亚氨基二乙酸部分的偶氮苯的酸酐与二胺进行缩聚，以提供具有分离的羧基并在主链中带有偶氮苯单元的水溶性聚酰胺。这些聚合物的金属离子萃取能力的变化与光的反-顺异构化和依赖于金属的种类，锌是最好的金属调查。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