Sun Xiaolong, Reuther James F, Phillips Scott T, Anslyn Eric V
Department of Chemistry, The University of Texas at Austin, Austin, TX, 78712, USA.
Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA.
Chemistry. 2017 Mar 17;23(16):3903-3909. doi: 10.1002/chem.201604474. Epub 2017 Feb 15.
The G-class nerve agents, which include sarin, soman, and cyclosarin, react readily with nucleophilic reagents to produce fluoride. Thus, a chemosensing protocol has been designed for these agents that pairs the nucleophilic reactivity of oximates for generating fluoride with an autoinductive target amplification reaction to amplify the quantity of fluoride for facile colorimetric and fluorescent optical quantification. The chemosensing protocol was demonstrated by using the nerve agent surrogate diisopropyl fluorophosphate (DFP) and benzaldoxime as the nucleophile. Autoinductive fluoride amplification responds to fluoride released from DFP by amplifying the fluoride concentration and a yellow reporter molecule. The reporter is a conjugated oligomer with a nominal repeating unit that originates from 4-aminobenzaldehyde. Exposure of the amplified fluoride to a fluoride-specific ratiometric fluorescent reporter provides a fluorescent readout, in which three fluorophores are generated per fluoride. Both colorimetric and fluorescent readouts enable quantitative assays with low micromolar limits of detection for fluoride resulting from DFP. More importantly, this work demonstrates the successful merging of multiple complex reactions for achieving selective, sensitive, and quantitative chemosensing.
包括沙林、梭曼和环沙林在内的G类神经毒剂很容易与亲核试剂反应生成氟化物。因此，针对这些毒剂设计了一种化学传感方案，该方案将肟化物生成氟化物的亲核反应性与自诱导目标放大反应相结合，以放大氟化物的量，便于进行比色和荧光光学定量。使用神经毒剂模拟物氟磷酸二异丙酯（DFP）和苯甲醛肟作为亲核试剂对该化学传感方案进行了验证。自诱导氟化物放大通过放大氟化物浓度和一种黄色报告分子来响应DFP释放的氟化物。该报告分子是一种具有标称重复单元的共轭低聚物，其标称重复单元源自4-氨基苯甲醛。将放大后的氟化物暴露于氟化物特异性比率荧光报告分子可提供荧光读数，其中每个氟化物会产生三种荧光团。比色和荧光读数均能实现对DFP产生的氟化物进行低微摩尔检测限的定量测定。更重要的是，这项工作展示了多种复杂反应成功融合以实现选择性、灵敏和定量化学传感。
