“Covalent-Assembly”-Based Fluorescent Probe for Detection of a Nerve-Agent Mimic (DCP) via Lossen Rearrangement

Abstract

The highly selective and sensitive fluorescence "light-up" probe, 5′-(dimethylamino)-2′-formyl-N-hydroxy-[1,1′-biphenyl]-2-carboxamide(PTS), has been fabricated for the nerve-agent mimic diethyl chlorophosphate (DCP). The probe is designed by combining two novel strategies of "covalent assembly" and Lossen rearrangement. Formation of a phosphoryl intermediate from DCP and a hydroxamic acid group in PTS yields an isocyanate that quickly undergoes Lossen rearrangement to produce an aniline that condenses intramolecularly to a fluorescent phenanthridine system. PTS shows superior properties to probe DCP, such as rapid response (within 100 s), low detection limit (10.4 nM), specificity, and excellent linearity (R 2 = 0.9993) in the range from 2 to 16 μM. More importantly, its application of detecting DCP vapor has also been achieved with satisfying results.

Small-molecule fluorescent probes based on covalent assembly strategy for chemoselective bioimaging

“…Because of their strong electrophilic ability, these nerveagents can easily interact with the central nervous enzyme acetylcholinesterase, destroying nerve impulse conduction and resulting in acute toxicity. [78][79][80][81][82][83][84][85][86][87] Fig. 12 (A In 2014, Yang et al developed a novel probe, NA1, to detect sarin via a Vilsmeier-Haack reaction employing the covalent assembly strategy (Fig.…”

“…14A ). 87 The hydroxamic acid group in probe NA3 was combined with DCP, and the newly formed phosphoryl intermediate was rapidly rearranged to provide the corresponding isocyanate, which tended to further react with water to release an NH 2 group. This probe had many advantages, such as low detection limit (10.4 nM), sensitive response (100 s), and outstanding linearity ( R 2 = 0.9993) in the range of 2 to 16 μM.…”

Hydrazone‐Based Supramolecular Organogel for Selective Chromogenic Detection of Organophosphorus Nerve Agent Mimic

“…They are able to irreversibly attach to the free serine amino acid of the acetylcholinesterase enzyme leading to inhibition of its enzymatic function. The consequential excessive aggregation of acetylcholine in the synapse neuronal junctions of the nervous system results in instant symptoms, such as hyperventilation, hindered muscle relaxation or loss of human life [6–11] . Detection of those nerve agents has been accomplished by several techniques, such as photonic crystals, electrochemical tools, ion mobility spectroscopy, microcantilevers, optical fibers and biosensors [12–18] .…”

“…The consequential excessive aggregation of acetylcholine in the synapse neuronal junctions of the nervous system results in instant symptoms, such as hyperventilation, hindered muscle relaxation or loss of human life. [6][7][8][9][10][11] Detection of those nerve agents has been accomplished by several techniques, such as photonic crystals, electrochemical tools, ion mobility spectroscopy, microcantilevers, optical fibers and biosensors. [12][13][14][15][16][17][18] However, most of those techniques demonstrated some limitations, such as high cost, low portability or the necessity of trained personnel.…”

Luminescent Europium(III) “Turn-On” Sensor for G-Series Chemical Warfare Simulants: A Mechanistic Investigation

“…Therefore, the need for a reliable sensing and surveillance system to monitor and combat the resurgence threat of the most notorious OP-CWA is crucial. Several molecular sensing approaches to detect nerve agents have been reported based on organic fluorophores, laser-induced breakdown spectroscopy (LIBS), optical-fiber arrays, GC-MS, AAS, or enzymatic assays. − …”