Fluorescent sensors for organophosphorus nerve agent mimics.
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.
Dale
Trevor J
TJ
The Skaggs Institute for Chemical Biology and the Department of Chemistry, The Scripps Research Institute, MB-26, 10550 North Torrey Pines Road, La Jolla, California, 92037, USA.
Rebek
Julius
J
D000438:Alcohols / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D002619:Chemical Warfare Agents / Q000032:analysis*; D002800:Cholinesterase Inhibitors / Q000032:analysis; D005456:Fluorescent Dyes / Q000138:chemical synthesis / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000032:analysis*; D011721:Pyrenes / Q000138:chemical synthesis / Q000737:chemistry*; D011934:Reagent Strips; D013050:Spectrometry, Fluorescence
D000438:Alcohols; D000588:Amines; D002619:Chemical Warfare Agents; D002800:Cholinesterase Inhibitors; D005456:Fluorescent Dyes; D009943:Organophosphorus Compounds; D011721:Pyrenes; D011934:Reagent Strips