京都大学 / 新制・課程博士 / 博士(工学) / 甲第23160号 / 工博第4804号 / 新制||工||1751(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 関 修平, 教授 今堀 博, 教授 梶 弘典 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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In this study, tetraphenylthiophenen (TP) with aggregation-induced emission enhancement (AIEE) property is served as terminal and central fluorophores of poly(£^-benzyl-L-glutamate) (PBLG)-based polymers of TP1PBLG and TP2PBLG, respectively, to probe for the relationship between the secondary structure (£\-helix) of polypeptides and the ALEE-operative fluorescence (FL). Intermolecular aggregation of the central TP unit in the di-substituted TP2PBLG is sterically blocked by the large £\-helical PBLG chains, which lead to the reduced AIEE-oriented FL. On the contrast, the terminal TP units in TP1PBLG can easily approach each other to form aggregates with strong FL. Factor (e.g. solvent annealing) controlling the fraction of £\-helix chain also varies the corresponding emission intensity. Conformational difference between TP1PBLG and TP2PBLG evaluated from the infrared and the X-ray (wide- and small-angle) diffraction spectra is also used to verify its influence on the AIEE-operative FL behavior.

In this study, organic and polymeric fluorophores based on 2,4,6-triphenylpyridiene (TPP) structure were found to have the novel aggregation-induced emission enhancement (AIEE) property. For the small-mass fluorophores, TPP and cyano-functionalized TPP (TPP-CN) were prepared from the facile Chichibabin reaction and their AIEE properties were characterized by the emission behavior in solvent/nonsolvent pair. Solid samples of TPP and TPP-CN exhibit enhanced emission with increasing annealing time under solvent vapors, thus, both compounds have the characters of crystallization-induced emission enhancement (CIEE) behavior. For polymeric system, copolymers PTPPF containing alternative TPP and 9,9-dioctylfluorene units were prepared through Suzuki coupling and study on its fluorescence behavior also reveals its AIEE feature. The rigid polymer possesses high emission intensity in its dilute solution state and remains almost unchanged with increasing nonsolvent fraction. The solid sample was found to have a high quantum yield (ФF) of 70 %.