Preparation of Redox Active Polymers and Their Application as Mediator Membranes

氧化还原活性聚合物的制备及其作为介体膜的应用

• 批准号: 01550708
• 负责人: IWABUCHI Susumu
• 金额: $ 1.15万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01550708/
• 关键词: Redox Polymers; Mediator Membranes; Ferrocene; Ruthenium Trisbipyridyl; Diquat; Copper Phthalocyanine; Methyl Viologen; Photoredox Properties; スチレン@無水マレイン酸共重合体; ビニルフェロセン; ルテニウムトリスビピリジン; 酸化還元特性

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.

1. 研究了聚乙烯基二茂铁-马来酸酐和聚苯乙烯-马来酸酐衍生膜的电化学性能。发现形式氧化还原电位取决于支持电解质溶液的pH值（pH值2-5），与四甘醇的交联程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应用。研究了以三联吡啶钌和电子受体/继电器diquat衍生的聚合物中光诱导的分子内电子转移和电荷分离。高浓度的电子供体，如三乙醇胺，被发现是抑制反向电子转移所必需的。在这种条件下，发现光还原三联吡啶钌可以进行双元还原。当聚合物膜制备完成后，将其插入到甲基紫素和三乙醇胺溶液中，并进行辐照后，可以通过还原性diquat进行中介作用，从而实现两种基质之间的能量上坡氧化还原反应。研究了紫外光照射下分散在聚合物基质中的四硫酞菁铜的光还原反应。此外，还研究了分散在聚乙烯醇中的CuPcTS光诱导跨膜介导三乙醇胺与紫紫甲基之间的氧化还原反应。研究发现，与三乙基乙醇溶液相比，甲基紫素溶液侧照射的氧化还原反应效率约为三倍。上述发现和溶液中得到的结果表明，处于高激发态的纸杯ts在膜/甲基紫胶溶液界面上通过所谓的氧化机制将电子转移到紫胶甲基上。

项目成果

塚本 健人、 田口 修二、 中平 隆幸、 岩淵 晋、 小嶋 邦晴、 杉浦 猛人: "Photoredox reactions of copper(II) tetrasulphophthalocyanine in polymer matrices under ultraviolet irradiation" Polymer Communications. 31. 108-111 (1990)

Kento Tsukamoto、Shuji Taguchi、Takayuki Nakahira、Susumu Iwabuchi、Kuniharu Kojima、Taketo Sugiura：“紫外线照射下聚合物基质中四磺基酞菁铜 (II) 的光氧化还原反应”Polymer Communications。

T. Nakahira, Y. Maejima, Y. Kouda, and S. Iwabuchi: "Preparation and pH-dependent redox properties of crosslinked poly (vinylferrocene co-maleic anhydride)"

T. Nakahira、Y. Maejima、Y. Kouda 和 S. Iwabuchi：“交联聚（乙烯基二茂铁共马来酸酐）的制备和 pH 依赖性氧化还原特性”

中平 隆幸,前嶋 佳人,幸田 豊,岩淵 晋: "Preparation and photoinduced redox properties of polymers having ruthenium trisbipyridyl and diquat moieties" Makromol.Chem.

Takayuki Nakahira、Yoshito Maejima、Yutaka Koda、Susumu Iwabuchi：“具有三联吡啶基钌和敌草快部分的聚合物的制备和光诱导氧化还原性能”Makromol.Chem。

中平隆幸,近藤和彦,伊藤静枝,進藤晃,岩淵晋: "Preparation of cross-linked poly(vinylferrocene-co-maleic anhydride)membranes and pH dependence of their redox potentials" Makromolkulare Chemie,Rapid Communications.

Takayuki Nakahira、Kazuhiko Kondo、Shizue Ito、Akira Shindo、Susumu Iwabuchi：“交联聚（乙烯基二茂铁-马来酸酐）膜的制备及其氧化还原电位的 pH 依赖性”Makromolkulare Chemie，Rapid Communications。

塚本 健人,田口 修二,中平 隆幸,岩淵 晋,小嶋 邦晴,杉浦 猛人: "Photoredox reactions of copper(II) tetrasulphophthalocyanine in polymer matrices under ultraviolet irradiation" Polymer Communications. 31. 108-111 (1990)

Kento Tsukamoto、Shuji Taguchi、Takayuki Nakahira、Susumu Iwabuchi、Kuniharu Kojima、Taketo Sugiura：“紫外线照射下聚合物基质中四磺基酞菁铜 (II) 的光氧化还原反应”Polymer Communications。