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Visible and Reversible Restrict of Molecular Configuration by Copper Ion and Pyrophosphate.
ACS Sensors ( IF 8.2 ) Pub Date : 2020-07-10 , DOI: 10.1021/acssensors.0c00619
Yongxin Chang 1, 2 , Haijuan Qin 3 , Xue Wang 2 , Xiaopei Li 2 , Minmin Li 2 , Hang Yang 2 , Kuoxi Xu 1 , Guangyan Qing 2, 4
Affiliation  

Molecular configuration strongly impacts on its functions; however, due to complicated and diverse configuration as well as easy and rapid conversion among various configurations, research of molecular configuration is extremely difficult. If the free rotation of a molecule could be “slowed down” or even “frozen” by an external stimulus, such as ultralow temperature, then one configuration of the molecule could be captured and characterized relatively easily. Here, we show that the rotation of a hemicyanine-labeled 2-(2′-hydroxyphenyl)-4-methyloxazole (H-HPMO) molecule could be specifically and reversibly restricted by sequential additions of copper ion (Cu2+) and pyrophosphate (P2O74–), reflecting as remarkable fluorescence quenching and recovery, which could be directly observed by naked eyes. Binding affinity tests and cryogenic 1H NMR indicate that Cu2+ forms intensive coordinate bonds with phenolic hydroxyl, oxazole, and methoxyl groups of HPMO, which strongly restricts the free rotations of these groups and blocks charge transfer. This study provides a precise, rapid, visible, reversible, and low-cost method to monitor the molecular configuration, indicating the broad application prospects of near-infrared fluorescent sensors in configuration analysis, biosensing, and drug–substrate complexation.

中文翻译:

铜离子和焦磷酸盐对分子构型的可见和可逆限制。

分子构型强烈影响其功能。但是,由于构型复杂多样,并且在各种构型之间容易且快速地转换,因此对分子构型的研究非常困难。如果分子的自由旋转可以通过外部刺激(例如超低温)“减慢”或什至“冻结”,那么该分子的一种构型可以相对容易地被捕获和表征。在这里,我们表明,通过顺序添加铜离子(Cu 2+)和焦磷酸盐(半磷酸),可以将半花青素标记的2-(2'-羟基苯基)-4-甲基恶唑(H-HPMO)分子的旋转特异性地和可逆地限制。P 2 O 7 4–),反映出显着的荧光猝灭和恢复,可以通过肉眼直接观察到。结合亲和力测试和低温1 H NMR表明,Cu 2+与HPMO的酚羟基,恶唑和甲氧基形成强烈的配位键,从而强烈限制了这些基团的自由旋转并阻止了电荷转移。这项研究提供了一种精确,快速,可见,可逆且低成本的方法来监测分子构型,从而表明了近红外荧光传感器在构型分析,生物传感和药物-底物络合中的广阔应用前景。
更新日期:2020-08-28
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