Department of Chemistry, University of Science and Technology of China, Hefei 230026, PR China.
The Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, PR China.
J Hazard Mater. 2021 Aug 15;416:125789. doi: 10.1016/j.jhazmat.2021.125789. Epub 2021 Apr 6.
Mustard gas has been used as a chemical warfare agent for a century, and is the most likely chemical weapon used in wars or by terrorists. Thus, it is important to develop a facile, rapid and highly selective method for the detection of mustard gas. In this paper, two fluorescent probe molecules, 4-mercaptocoumarins, have been developed for rapid and sensitive detections of SM and its analogues (CEES and NH1) in both solutions and gas phase. The sensing reaction is a nucleophilic addition at three-membered hetercyclic sulfonium/ammonium formed from SM, CEES/NH1 in ethanol. Two fluorescent probes (4-mercaptocoumarins, ArSH) in ethanol deprotonate to form thiophenol anions (ArS) resulting from their low pKa values (3.2-3.4), and the nucleophilic addition of the anion ArS generates the corresponding thioethers, giving a turn-on fluorescence response. The thiophenol anion can fast sense SM, CEES and NH1 (within 1-4 min) with high sensitivity (~nM level) at 60 °C, and high selectivity through adding a tertiary amine, and two probes exhibit excellent chemical and photostability in detection systems. Furthermore, a facile test strip with the sensor was fabricated for the detection of CEES vapor with rapid response (3 min), high sensitivity (9 ppb) and high selectivity.
芥子气作为一种化学战剂已经使用了一个世纪，是战争或恐怖分子最有可能使用的化学武器。因此，开发一种简便、快速和高选择性的检测芥子气的方法非常重要。在本文中，我们设计了两种荧光探针分子 4-巯基香豆素，用于快速和灵敏地检测 SM 及其类似物（CEES 和 NH1）在溶液和气相中的存在。传感反应是由 SM、CEES/NH1 在乙醇中形成的三元杂环硫翁/铵盐的亲核加成。两种荧光探针（4-巯基香豆素，ArSH）由于其低 pKa 值（3.2-3.4）在乙醇中去质子化形成苯硫酚阴离子（ArS），阴离子 ArS 的亲核加成生成相应的硫醚，产生开环荧光响应。苯硫酚阴离子可以在 60°C 下快速感应 SM、CEES 和 NH1（1-4 分钟内），具有高灵敏度（~nM 级），通过加入叔胺具有高选择性，两种探针在检测体系中表现出优异的化学和光稳定性。此外，我们还制备了一种带有传感器的简便测试条，用于检测 CEES 蒸气，具有快速响应（3 分钟）、高灵敏度（9 ppb）和高选择性。
