Application of Photoinduced Electron Transfer Reaction Across the Water-Organic Interface

光致电子转移反应在水-有机界面上的应用

• 批准号: 01550628
• 负责人: NAKAMURA Hiroshi
• 金额: $ 1.22万
• 依托单位: Kyushu 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-01550628/
• 关键词: Photoinduced Electron Transfer; Micelles; Synthetic Bilayer; External Magnetic Field Effect; Biphotonic Ionization; Electron Spin Echo; 逆ミセル; ラジカル対; 界面反応; 光誘起電子移動反応; ポルフィリン; ビオロ-ゲン; 磁場効果

1. Photoinduced electron transfers from porphyrin (at the interface) to various type of viologen (as an acceptor) were investigated by the use of molecular assemblies such as a synthetic bilayer which provided a water-organic interface. In case of reactions at a positively charged bilayer, the yield of photoreduced viologen increased in the application of External Magnetic Field, when negatively charged viologen was used as an electron acceptor. This suggested that the radical pair kept a certain distance in the reaction time, and an electron spin-spin interaction remained. On the other hand, the positively charged viologen rapidly left away from the surface of the bilayer after the electron transfer, and a magnetic field effect was not observed.2. The photoinduced electron transfer from the amphiphilic porphyrin to the water soluble viologen in the AOT reversed micelles was investigated with External Magnetic Field Effect. The result clearly showed that the AOT micro-water pool gave a special microenvironment such as a "Cage" in the radical reactions and that the pseudo-linked system was observed.3. The biphotonic ionization of amphiphilic donor compound on the surface of AOT reversed micelles was also studied. The ionization efficiency was controlled by the size of the water pool. The Electron Spin Echo study also showed that the geometry of the donor position on the water-organic interface was controlled by the microenvironment of the micelles such as water pool size.

1. 利用分子组件（如提供水-有机界面的合成双分子层）研究了卟啉（在界面处）到各种类型的紫素（作为受体）的光致电子转移。在带正电的双分子层上进行反应时，当带负电的双分子层用作电子受体时，在外加磁场的作用下，光还原紫素的产率增加。这说明自由基对在反应时间内保持了一定的距离，电子自旋-自旋相互作用仍然存在。另一方面，带正电的紫胶在电子转移后迅速离开双分子层表面，没有观察到磁场效应。利用外磁场效应研究了两亲性卟啉在AOT反胶束中向水溶性紫胶的光致电子转移。结果清楚地表明，AOT微水池在自由基反应中形成了“笼”状的特殊微环境，并观察到伪连接体系。研究了两亲性给体化合物在AOT反相胶束表面的双光子电离。电离效率受池池大小的控制。电子自旋回波研究还表明，水-有机界面上施主位置的几何形状受水池大小等胶束微环境的控制。

项目成果

Akihiro Uehata: "Magnetic Field Effects on the Decay Rates of Photogenerated Geminate Radical Pairs in Reversed Micelles." The Journal of Physical Chemistry. 93. 8197-8203 (1989)

Akihiro Uehata：“磁场对反胶束中光生双自由基对衰变率的影响。”

Hiroshi NAKAMURA: "Photoionization of Phenothiazine and Carbazole Alkyl Trimethylammonium Bromide in Frozen AOT Reversed Micellar Solutions Studied by Electron Spin Echo Modulation and Electron Spin Resonance." The Journal of Physical Chemistry. 95. 1480-

Hiroshi NAKAMURA：“通过电子自旋回波调制和电子自旋共振研究冷冻 AOT 反胶束溶液中吩噻嗪和咔唑烷基三甲基溴化铵的光电离。”

Akira MITSUI: "Counterion Effects on the Photoinduced Electron Transfer Reaction and the Reverse Process in PorphyrinーViologen Linked Compounds." Chemistry Letters. 1445-1448 (1989)

Akira MITSUI：“抗衡离子对卟啉-紫精连接化合物中光诱导电子转移反应和逆过程的影响”，1445-1448（1989）。

Hide SAITO: "Stability and Exchange Properties of Throughーring Cyclodextrin Complexes.Effects of Chain Length in Polymethylene bis[1ーpyridinium] as Guest Molecules." Chemistry Letters. 535-538 (1990)

Hide SAITO：“贯通环糊精复合物的稳定性和交换特性。作为客体分子的聚亚甲​​基双[1-吡啶鎓]链长的影响。”535-538 (1990)

Akira Mitsui: "Counterion Effects on the Photoinduced Electron-Transfer and the Reverse Process in Porphyr in-Viologen Linked Compounds" Chemistry Letters. 1445-1448 (1989)

Akira Mitsui：“抗衡离子对光诱导电子转移的影响以及卟啉内紫罗碱连接化合物的逆过程”化学快报。