yrammuS 要概羽曾部 卓20TakuHASOBE垂直配向P/N接合界面を有する超分子光電変換セルの創製(2016採択)Construction and Evaluation of Supramolecular Photovoltaic Cells Composed of Vertical P/N Junction(Project 2016)31Rep. Grant. Res., Asahi Glass Foundation (2018)テアーゼに対し安定となること，を明らかとした．また，光切断性リンカーをはじめ，複数の新規リンカーを開発した．Since peptides possess specific and potent biological activities, they receive remarkable attention as potential chemical tools and pharmaceuticals. Stimulus-responsive peptides are a class of modified peptides which are able to be activated upon the addition of external stimuli such as light and redox. These peptides would work as not only chemical tools, but also pharmaceuticals with reduced side ef-fects. However, 1) peptides are easily metabolized by proteases and often have short half-lives, 2) pep-tides are not membrane-permeable, so that they cannot affect intracellular target. In order to solve these limitations, stimulus-responsive peptides are developed by incorporating a stimulus-responsive linker to the cyclic peptide. We developed redox-responsive cyclic LSD1 inhibitor peptide, and revealed that 1) the cyclic peptide is activatable under reduced condition, 2) the cyclic peptide is more stable to-ward protease than the linear peptide. Besides, novel stimulus-responsive linkers are developed includ-ing photocleavable linkers.本研究では超分子型の光エネルギー変換系構築をめざし，まず，電子ドナーであるポルフィリンを外層，電子アクセプターであるカーボンナノホーン（CNH)を内層とするCNH内包型ポルフィリンナノロッドの構築を行った．また，このポルフィリン集合体をITO基板上に垂直配向させることにも成功し，湿式光電気化学セルでは可視光領域において良好な光電変換特性が観測された．一方，ペンタセン分子集合体についてはペンタセンアルカンチオールを金ナノ粒子や金ナノロッドに修飾し，比較的高密度の分子集合体を得ることができた．フェムト秒過渡吸収測定（トルエン中）によりペンタセン金ナノ粒子では一光子吸収から二励起子生成を示す多励起子生成（一重項分裂）が高効率（三重項量子収率: ~170％）で観測され，今後の太陽電池構築に向けた重要な結果が得られた．In this study, first, we constrctuted carbon nanohorn (CNH)-encapsulated porphyrin nanorods (supra-molecular assemblies) for efficient solar energy conversion. Then, vertically-oriented formation of these porphyrin nanoassemblies on ITO electrode was successfully observed. In the photoelectrochemical solar cell, efficient photovoltaic properties were observed in the whole visible region. The other topic includes the synthesis and photophysical properties of pentacene-modified gold nanoparticles and nanorods. In pentacene-modified nanoparticles, efficient singlet fission occurred and the quantum yield of triplet excited states attains ~170%. This result is quite promisng for construction of future or-ganic photovolitacs.
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