Preparation of Redox Active Polymers and Their Application as Mediator Membranes

1.研究了聚（乙烯基二茂铁-alt-马来酸酐）和聚（苯乙烯-alt-马来酸酐）经二茂铁基甲醇衍生后的膜的电化学性能。发现形式氧化还原电位依赖于支持电解质溶液的pH（pH 2-5）、与四甘醇的交联程度以及膜中二茂铁的含量，表明它们在受控膜介导中的潜在用途。光诱导的分子内电子转移和电荷分离进行了研究与钌trisbipyridine和电子受体/中继，敌草快衍生的聚合物。高浓度的电子供体，e。G.三乙醇胺被发现是抑制反向电子转移所必需的。在这种条件下，发现diquat光还原钌trisbipyridine还原进行。当制备聚合物膜，插入甲基紫精和三乙醇胺溶液之间，并照射时，建议通过还原敌草快进行调解，以影响两种基质之间的能量上坡氧化还原反应.研究了四硫代酞菁铜（CuPcTS）在紫外光照射下的光还原反应。分散在聚乙烯醇中的CuPcTS也被检查用于三乙醇胺和甲基紫精之间的氧化还原反应的光诱导跨膜介导。从甲基紫精溶液一侧照射，氧化还原反应的效率约为100%。与从三乙醇溶液侧照射相比，高三倍。上述发现，连同在溶液中获得的结果，表明，CuPcTS在较高的激发态转移电子甲基紫精在膜/甲基紫精溶液界面的所谓的氧化机制。

1. The electrochemical properties of membranes made of poly (vinylferrocene-alt-maleic anhydride) and poly (styrene-alt-maleic andhydride) derivatized with ferrocenylmethanol were investigated. The formal redox potentials were found to be dependent upon the pH of the supporting electrolyte solution ph 2-5), the degree of crosslinking with tetraethylene glycol, and the ferrocene content in the membrane, demonstrating their potential use in controlled membrane mediation.2. Photoinduced intramolecular electron transfer and charge separation were examined in polymers derivatized with ruthenium trisbipyridyl and an electron acceptor/relay, diquat. A high concentration of an electron donor, e. g. triethanolamine, was found to be necessary to suppress back electron transfer. Under such conditions diquat reduction by photoreduced ruthenium trisbipyridyl was found to proceed. When the polymer membrane was prepared, inserted between methyl viologen and triethanolamine solutions, and irradiated, mediation via reduced diquat was suggested to occur to effect energetically uphill redox reaction between the two substrates.3. Photoreduction of copper (II) tetrasulphophthalocyanine (CuPcTS) dispersed in polymer matrices was investigated under ultraviolet irradiation. CuPcTS dispersed in poly (vinyl alcohol) was also examined for photoinduced cross-membrane mediation of redox reaction between triethanolamine and methyl viologen. Irradiation from the side of methyl viologen solution was found to give an efficiency of the redox reaction ca. three times higher, as compared with irradiation from the side of triethanol solution. The above finding, together with the results obtained in solution, suggests that CuPcTS in a higher excited state transfers electron to methyl viologen in a so-called oxidative mechanism at the membrane/methyl viologen solution interface.