Locked ortho- and para-Core Chromophores of Green Fluorescent Protein; Dramatic Emission Enhancement via Structural Constraint
Locked ortho- and para-Core Chromophores of Green Fluorescent Protein; Dramatic Emission Enhancement via Structural Constraint
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DOI：
10.1021/ja5062856
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发表时间：
2014-08-20
影响因子：
15
通讯作者：
Chou, Pi-Tai
中科院分区：
文献类型：
--
作者：
Hsu, Yen-Hao;Chen, Yi-An;Chou, Pi-Tai
我们报告的设计策略和合成的结构锁定的GFP核心发色团p-LHBDI，其邻位衍生物，o-LHBDI，和H2 BDI具有对位和邻位羟基基团，使固有的旋转运动的标题化合物已部分限制。o-LHBDI具有双重锁定构型，即，七元环氢键和五元环C（4-5-10-13-14）环化，由此发生激发态分子内质子转移，产生创纪录的高互变异构体发射产率（甲苯中为0.18）和放大的自发发射的产生。与未锁分子相比，p-LHBDI和H_2BDI在水溶液中以阴离子形式存在时，其发光产率也有了显著的提高，并从化学和光谱学角度讨论了它们的结构与发光的关系.在固体中，o-LHBDI具有H-聚集体状的分子堆积，具有窄带宽的发光，并已成功地应用于制备黄色有机发光二极管（λ（max）= 568 nm，eta（ext）1.9%），其发光半峰全宽窄至70 nm。
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 (lambda(max) = 568 nm, eta(ext) 1.9%) with an emission full width at half-maximum as narrow as 70 nm.