Fluorescent sensors for organophosphorus nerve agent mimics
Fluorescent sensors for organophosphorus nerve agent mimics
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DOI：
10.1021/ja057449i
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发表时间：
2006-04-12
影响因子：
15
通讯作者：
Rebek, J
中科院分区：
文献类型：
--
作者：
Dale, TJ;Rebek, J
我们提出了一个小分子传感器，提供了一个光学响应的存在下，有机磷（OP）的神经毒剂模拟。该设计包含三个关键特征：伯醇、紧邻醇的叔胺和用作光学读出的荧光基团。在传感器的静止状态下，碱性胺的孤对电子通过光诱导电子转移（PET）猝灭附近荧光团的荧光。暴露于OP神经毒剂模拟物会触发伯醇的磷酸化，随后迅速发生分子内取代反应，因为胺取代了产生的磷酸盐。通过该环化反应产生的季铵盐不再具有孤对电子，并且当荧光团的非辐射PET猝灭途径关闭时观察到荧光读数。
We present a small molecule sensor that provides an optical response to the presence of an organophosphorus (OP)-containing nerve agent mimic. The design contains three key features: a primary alcohol, a tertiary amine in close proximity to the alcohol, and a fluorescent group used as the optical readout. In the sensor's rest state, the lone pair of electrons of the basic amine quenches the fluorescence of the nearby fluorophore through photoinduced electron transfer (PET). Exposure to an OP nerve agent mimic triggers phosphorylation of the primary alcohol followed rapidly by an intramolecular substitution reaction as the amine displaces the created phosphate. The quaternized ammonium salt produced by this cyclization reaction no longer possesses a lone pair of electrons, and a fluorescence readout is observed as the nonradiative PET quenching pathway of the fluorophore is shut down.