脂質二分子膜を反応場とする光誘起電子移動反応

概要

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In the vesicle system, a photoinduced electron transfer from sodium ascorbate (AscNa) in the inner phase to methyl viologen (MV2+) in the outer phase was carried out by using pyrene derivatives incorporated into the lipid bilayers as a sensitizer. The initial rate of formation of methyl viologen radical cation (MV+·) was very dependent on the substituent of sensitizers; an efficient electron transfer was achieved in the case of sensitizers having a hydrophilic group connected with the pyrenyl ring by a shorter methylene chain. This observation indicated that the electron transfer was facilitated when the pyrenyl moiety was located at the membrane surface. We examined the dependence of the initial rate of the MV+· formation on light intensity, revealing that the reaction proceeds by the one-photon mechanism. Based on Stern-Volmer constants for the quenching of sensitizer fluorescence by AscNa and MV2+, we presume that the initial process of the reaction is the electron transfer from AscNa in the inner phase to the excited sensitizer incorporated into the membrane. We will discuss the detailed mechanism on the basis of the dependence of the initial rate of the MV+· formation on the AscNa concentration, as well as on the reaction temperature.
基礎有機化学会（基礎有機化学連合討論会）の論文