Histidine Proton Shuttle-Initiated Switchable Inversion of Circularly Polarized Luminescence,ACS Applied Materials & Interfaces

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Histidine Proton Shuttle-Initiated Switchable Inversion of Circularly Polarized Luminescence
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-04-01 , DOI: 10.1021/acsami.0c02080
Dian Niu _{1,

2} , Lukang Ji ₃ , Guanghui Ouyang ₁ , Minghua Liu _{1,

2,

4}

Affiliation

Switchable inversion of the sign of circularly polarized luminescence (CPL) in chiral supramolecular systems has gained remarkable interest because of its role in understanding the chirality-switching phenomena in biological systems and developing smart chiral luminescent materials. Herein, inspired by the histidine proton shuttle in natural enzymes, we synthesized a histidine π-gel (PyC₃H) and realized reversible inversion of supramolecular chirality and CPL by receiving and then transferring a proton. It was found that in the course of histidine protonation by adding an external proton source, the transcription of intrinsic molecular chirality of PyC₃H to the supramolecular level biased, achieving dynamic control over the PyC₃H gel with left-handed CPL inversed into the right-handed one. The mechanism study revealed that the supramolecular chirality and CPL inversion are mainly affected by the cooperation adjustment of hydrogen bonds and π–π stacking upon histidine protonation and deprotonation, which causes the re-orientations of pyrene chromophores. This work sets up an alternative effective method to fabricate tunable CPL-active materials while using the same chiral small molecules, which provides a new insight into developing bio-inspired switchable supramolecular materials.

中文翻译：

组氨酸质子穿梭引发的圆偏振发光的可转换反转。

手性超分子系统中圆偏振发光（CPL）的符号的可逆转换已经引起了人们的极大兴趣，因为它在理解生物系统中的手性转换现象和开发智能手性发光材料方面具有重要作用。在此，受天然酶中组氨酸质子穿梭的启发，我们合成了组氨酸π-凝胶（PyC ₃ H），并通过接收然后转移质子实现了超分子手性和CPL的可逆转化。发现在通过添加外部质子源进行组氨酸质子化的过程中，PyC ₃ H的内在分子手性向超分子水平的转录有偏差，从而实现了对PyC _3的动态控制。具有左手CPL的H凝胶倒转为右手CPL。机理研究表明，超分子手性和CPL反转主要受组氨酸质子化和去质子化时氢键和π-π堆积的协同调节的影响，这导致causes发色团的重新取向。这项工作建立了使用相同的手性小分子制造可调谐CPL活性材料的另一种有效方法，这为开发生物启发的可转换超分子材料提供了新的见识。

更新日期：2020-04-01

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