title: Coupling Activity-Based Detection, Target Amplification, Colorimetric and Fluorometric Signal Amplification, for Quantitative Chemosensing of Fluoride Generated from Nerve Agents.
abstract: 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.
authors.affiliation: Department of Chemistry, The University of Texas at Austin, Austin, TX, 78712, USA.
authors.forename: Xiaolong
authors.identifier: http://orcid.org/0000-0003-4003-6924
authors.initials: X
authors.lastname: Sun
authors.affiliation: Department of Chemistry, The University of Texas at Austin, Austin, TX, 78712, USA.
authors.forename: James F
authors.initials: JF
authors.lastname: Reuther
authors.affiliation: Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA.
authors.forename: Scott T
authors.initials: ST
authors.lastname: Phillips
authors.affiliation: Department of Chemistry, The University of Texas at Austin, Austin, TX, 78712, USA.
authors.forename: Eric V
authors.initials: EV
authors.lastname: Anslyn
mesh_terms: D003124:Colorimetry / Q000379:methods*; D005456:Fluorescent Dyes / Q000737:chemistry; D005459:Fluorides / Q000032:analysis*; D007531:Isoflurophate / Q000032:analysis*; D000067397:Nerve Agents / Q000032:analysis*; D009943:Organophosphorus Compounds / Q000032:analysis; D010091:Oximes / Q000737:chemistry; D010710:Phosphates / Q000032:analysis; D012524:Sarin / Q000032:analysis; D012999:Soman / Q000032:analysis; D013050:Spectrometry, Fluorescence / Q000379:methods*
chemical_list: D005456:Fluorescent Dyes; D000067397:Nerve Agents; D009943:Organophosphorus Compounds; D010091:Oximes; D010710:Phosphates; D007531:Isoflurophate; C012980:fluorophosphate; D012999:Soman; D012524:Sarin; D005459:Fluorides; C053914:cyclohexyl methylphosphonofluoridate
keywords: colorimetry; fluorescence; fluorides; nerve agents; sensors