Supramolecular Photoreactor

超分子光反应器

• 批准号: 05804035
• 负责人: SHIMOMURA Masatsugu
• 金额: $ 1.09万
• 依托单位: Hokkaido 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: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05804035/
• 关键词: Viologen; Bilayr Membrane; Charge Transfer Complex; Photoinduced Electrotransfer; Electrochemical Mediation; Enzyme reaction; NADH; LB Film; IB膜; Langmuir-Blodgett膜; 人工光合成; 超分子化学; 電荷分離

This project focused a biomimetic approach of artificial photosynthesis based on two-dimensional supramolecular assemblies. Charge transfer (CT) complexes are often used as a charge separation device in an artificial photosynthesis and photo conductive materials. Two-dimensional supramolecular assemblies.e.g. bilayr membranes and Langmuir-Blodgett films, are suitable candidates for designing CT complexes. Based on "pseudo crystal engineering" of bilayr membranes, we succeeded tailoring an intermolecular CT complex between a hydrophobic biphenyl moiety and a hydrophilic viologen head in an aqueous bilayr membrane.The hydrophilic viologen head and the hydrophobic aromatic segment of the adjacent molecule was expected to be closely packed in the tilted molecular orientation.A broad absorption band at 460nm attributed to a CT complex was observed in the aqueous bilayr solution of C12BphC5V2+, whereas a water solution of C8BphC10V2+ had no absorption in visible region. A long lived viologen radicals was also found on visible light irradiation of the CT complex. Langmuir-Blodgett films of C12BphC5V2+ prepared by the polyion complex technique on ITO electrodes clearly showed reversible redox reaction of the Viologen group and the LB film effectively mediated electrons from the electrode to a redox flavin enzyme, diaphorase. Photochemical reduction of diaphorase and NAD by the photochemically generated viologen radical was investigated.

本项目重点研究了一种基于二维超分子组装的人工光合作用仿生方法。电荷转移(CT)络合物经常被用作人工光合作用和光导材料中的电荷分离装置。二维超分子组装。双层膜和Langmuir-Blodgett膜是设计CT复合体的合适候选材料。基于双分子膜的“伪晶体工程学”，我们成功地在双分子膜中剪裁了疏水联苯部分和亲水紫精分子头之间的分子间CT络合物。亲水紫精头部和相邻分子的疏水芳香族链段有望在倾斜的分子取向上紧密堆积在一起。在C12BphC5V2+的双分子水溶液中，观察到460 nm的宽吸收带，而C8BphC10V2+的水溶液在可见光区没有吸收。在CT络合物的可见光照射下，还发现了一种长寿命的紫精自由基。用多离子络合技术在ITO电极上制备的C12BphC5V2+的Langmuir-Blodgett膜清楚地显示了紫精基团的可逆氧化还原反应，而LB膜有效地将电子从电极传递到氧化还原黄素酶黄递酶。研究了紫精自由基对黄递酶和NAD的光化学还原作用。

项目成果

M.Shimomura: "Crystal Engineering based on two-dimensional molecular assemblies.Relation between chemical structure and molecular orientation in cast bilayer films" Langmuir. 11(印刷中). (1995)

M.Shimomura：“基于二维分子组装的晶体工程。流延双层薄膜中的化学结构和分子取向之间的关系”Langmuir 11（出版中）。

M.Shimomura: "Tailored charge transfer complex based on two-dimensional molecularassemblies" Supramolecular Science. 1. 33-38 (1994)

M.Shimomura：“基于二维分子组装体的定制电荷转移复合物”超分子科学。

M.Shimomura: "Tailored charge transfer complex based on two-dimensional molecular assemblies" Supramoleclar Science. 1. 33-38 (1994)

M.Shimomura：“基于二维分子组装体的定制电荷转移复合物”超分子科学。

M.Shimomura: "Crystal Engineering based on two-dimensional molecular assemblies.Relation between chemical structure and molecular orientation in cast bilayer films" Langmuir. 11(in press). (1995)

M.Shimomura：“基于二维分子组装的晶体工程。流延双层薄膜中化学结构和分子取向之间的关系”Langmuir。

M.Shimomura, S.Aiba, S.Oguma, M.Oguchi, M.Matsute, H.Shimada, R.Kajiwara, H.Emori, K.Yoshihara, K.Okuyama, T.Miyashita, A.Watanabe, M.Matsuda: "Tailored charge transfer complex based on two-dimensional molecular assemblies" Supramolecular Science. 1. 33-3

M.Shimomura、S.Aiba、S.Oguma、M.Oguchi、M.Matsute、H.Shimada、R.Kajiwara、H.Emori、K.Yoshihara、K.Okuyama、T.Miyashita、A.Watanabe、M.