Preparation of Redox Active Polymers and Their Application as Mediator Membranes

1.研究了二茂铁甲醇衍生的聚(乙烯基二茂铁-α-马来酸酐)膜和聚(苯乙烯-α-马来酸酐)膜的电化学性质。形式氧化还原电位取决于支持电解质溶液的pH值，与四甘醇的交联度，以及膜中二茂铁的含量，这表明它们在受控膜介质中的潜在用途。研究了用三联吡啶和电子受体/继电器diquat衍生的聚合物的光致分子内电子转移和电荷分离。发现需要高浓度的电子供体，例如三乙醇胺，以抑制反向电子转移。在此条件下，光还原Ru-3-联吡啶还原敌草胺的反应得以进行。当聚合物膜被制备，插入甲基紫精和三乙醇胺溶液，并被照射时，建议通过还原敌草枯进行调解，以实现两种底物之间的能量上行氧化还原反应。研究了四磺酸铜(CuPcTS)分散在聚合物基质中的紫外光还原反应。还考察了分散在聚乙烯醇中的CuPcTS对三乙醇胺和甲基紫精之间的光诱导跨膜氧化还原反应的影响。甲基紫精溶液侧照射的氧化还原反应效率比三乙醇溶液侧照射高约3倍。上述发现，结合溶液中的结果，表明处于较高激发态的CuPcTS在膜/甲基紫精溶液界面上以所谓的氧化机制将电子转移到甲基紫精。

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.