基于圆偏振发光的缺电子受体选择性识别  

Circularly polarized luminescence enables selective recognition of electron-deficient acceptors

作　　者：赵晨阳 冀璐康[1] 欧阳光辉 刘鸣华[1,2] Chenyang Zhao;Lukang Ji;Guanghui Ouyang;Minghua Liu(CAS Key Laboraoyof Coloid Interace and ChemcalThermodynamics,Instiute of Chemry Chinse Academyof Sciences,Bejing 100190 China;Green Catalysis Center and College of Chemistry,Zhengzhou University,Zhengzhou 450001,China)

机构地区：[1]中国科学院化学研究所,中国科学院胶体、界面与化学热力学重点实验室,北京100190 [2]郑州大学化学学院(绿色催化中心),郑州450001

出　　处：《中国科学：化学》2024年第8期1380-1388,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:22322207,92356307)资助项目。

摘　　要：由于集成了激发态信息和手性信息,圆偏振发光可以为荧光探针设计提供新的信息维度,有望在分子识别领域发挥独特作用.在本工作中,我们设计并合成了含有两个芘发光单元的“Y”型芘-谷氨酸乙酯手性分子(PyGlu),利用Py-Glu与缺电子受体的共组装圆偏振发光实现了八氟萘(OFN)的选择性识别.在较低浓度下(1×10^(-5)M),Py-Glu在N,N-二甲基甲酰胺(DMF)和水的混合溶剂中可以自组装成纳米球结构,增加浓度可以诱导纳米球融合成一维纳米纤维,这些纳米结构具有明显的圆二色光谱信号,表明谷氨酸的分子手性通过自组装有效传递到超分子层次.富电子的Py-Glu与十余种卤代芳烃和氰基取代芳烃的共组装结果表明,加入不同受体后Py-Glu组装体的荧光强度呈无规律的增强或减弱,但是只有L-Py-Glu/OFN体系具有明显的圆偏振发光现象,从而为通过圆偏振发光选择性识别缺电子受体提供了一种新方法.Due to the integration of excited state information and chiral information, circularly polarized luminescence can provide an additional information channel for common fluorescent probes, which is expected to play a unique role in the field of molecular recognition. In this work, we designed and synthesized a Y-type pyrene-glutamate chiral molecule(Py-Glu) containing two pyrene chromophores. Selective recognition of octafluoronaphthalene(OFN) among 11 electron-deficient acceptors was realized by using the turn-on circularly polarized luminescence from Py-Glu/acceptor co-assemblies. Py-Glu self-assembled into nanosphere structures at a low concentration(1 × 10^(-5)M in N,Ndimethylformamide(DMF)/water, v/v = 1:9), which could transform into nanofibers upon nanosphere fusion by increasing concentration to 3 × 10^(-4)M. Obvious circular dichroism signals of the nanospheres and nanofibers indicated an effective chirality transfer from molecular to supramolecular level. Co-assembly of electron-rich Py-Glu with a library of electron-deficient halogenated or cyano-substituted aromatic hydrocarbons caused irregularly changed fluorescence intensity, which was difficult to achieve precise molecular recognition. In contrast, L-Py-Glu/OFN system showed the ability of turn-on circularly polarized luminescence(CPL) while other acceptors remained CPL silence,which provided a new method for the selective recognition of electron-deficient acceptors by circularly polarized luminescence.

关 键 词：圆偏振发光 自组装 分子识别 缺电子受体 超分子手性 

分 类 号：O641.3[理学—物理化学] O657.3[理学—化学]