Locked ortho- and para-Core Chromophores of Green Fluorescent Protein; Dramatic Emission Enhancement via Structural Constraint

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• 作者：Yen-Hao Hsu ; Yi-An Chen ; Huan-Wei Tseng ; Zhiyun Zhang ; Jiun-Yi Shen ; Wei-Ti Chuang ; Tzu-Chieh Lin ; Chun-Shu Lee ; Wen-Yi Hung ; Bor-Cherng Hong ; Shih-Hung Liu ; Pi-Tai Chou
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 20, 2014
• 年：2014
• 卷：136
• 期：33
• 页码：11805-11812
• 全文大小：442K
• ISSN：1520-5126

文摘

We report the design strategy and synthesis of a structurally locked GFP core chromophore p-LHBDI, its ortho-derivative, o-LHBDI, and H2BDI possessing both para- and ortho-hydroxyl groups such that the inherent rotational motion of the titled compounds has been partially restricted. o-LHBDI possesses a doubly locked configuration, i.e., the seven-membered ring hydrogen bond and five-membered ring C(4-5-10-13-14) cyclization, from which the excited-state intramolecular proton transfer takes place, rendering a record high tautomer emission yield (0.18 in toluene) and the generation of amplified spontaneous emission. Compared with their unlocked counterparts, a substantial increase in the emission yield is also observed for p-LHBDI and H2BDI in anionic forms in water, and accordingly the structure versus luminescence relationship is fully discussed based on their chemistry and spectroscopy aspect. In solid, o-LHBDI exhibits an H-aggregate-like molecular packing, offers narrow-bandwidth emission, and has been successfully applied to fabricate a yellow organic light emitting diodes (位_max = 568 nm, 畏_ext = 1.9%) with an emission full width at half-maximum as narrow as 70 nm.