Xinjiang Key Laboratory of Explosives Safety Science, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830000, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
Anal Chem. 2022 Aug 23;94(33):11679-11687. doi: 10.1021/acs.analchem.2c02407. Epub 2022 Aug 10.
Inhibition of twisting intramolecular charge transfer (TICT) is one of the most attractive methods for fluorescence-on analysis, whereas it remains enigmatic whether the fluorescence in a TICT-based probe could be thoroughly lightened. Here, for maximizing the fluorescence-on signal of the TICT-based probe, we develop a model by employing chemical reaction to directly cleave the linkage between the rotational electron donor and acceptor with a predisposed fluorescent signal close to zero. To validate this assumption, a nonfluorescent probe with barrierless rotation is successfully achieved by grafting acryloyl with -C═C- recognition sites onto coumarin, and 7-hydroxycoumarin with bright blue fluorescence could be released within 3 s upon probing KMnO with an amount as low as 0.95 nM and 6.6 pg. We believe that the present strategy could not only deepen the insights of photochemistry but also facilitate the development of a theranostic drug delivery system, energy conversion, pollution control, and health risk reduction.
抑制扭转分子内电荷转移（TICT）是荧光开启分析最具吸引力的方法之一，然而，TICT 探针中的荧光是否能够被彻底点亮仍然是一个谜。在这里，为了最大化 TICT 探针的荧光开启信号，我们通过化学反应开发了一种模型，直接切断旋转电子给体和受体之间的连接，同时预先设计了接近零的荧光信号。为了验证这一假设，我们成功地通过将丙烯酰基与 -C═C- 识别位点接枝到香豆素上来制备无阻碍旋转的非荧光探针，并且在探测 KMnO 时，只需 0.95 nM 和 6.6 pg 的量，探针中就可以在 3 秒内释放出具有明亮蓝光荧光的 7-羟基香豆素。我们相信，目前的策略不仅可以加深对光化学的认识，还可以促进治疗诊断药物输送系统、能量转换、污染控制和降低健康风险的发展。
