A chromogenic and ratiometric fluorogenic probe for rapid detection of a nerve agent simulant DCP based on a hybrid hydroxynaphthalene–hemicyanine dye

Abstract

A new cyanine dye (CYD) based on hybrid hydroxynaphthalene-hemicyanine has been synthesized and characterized. The chromogenic and ratiometric fluorogenic probe (CYD) enables a fast and highly sensitive response to an OP nerve agent mimic diethyl chlorophosphate (DCP) through tandem phosphorylation and intramolecular cyclization reaction within 1 min and with the detection limit as low as 18.86 nM. To our knowledge this is the first report of a hydroxyl assisted bathochromic shift in a selective chemodosimeter for DCP exhibiting a ratiometric response. TDDFT calculations were performed in order to demonstrate the electronic properties of the probe and the cyclized product. Moreover, the utility of the probe CYD for the detection of DCP in live cells, in the gas phase and in a spiked soil sample has also been demonstrated.

Simple and Efficient Chromophoric-Fluorogenic Probes for Diethylchlorophosphate Vapor

“…As a comparison, we summarized the properties of these two probes and other representative chromophoric/fluorogenic probes for DCP reported in the past two years (Table S1). ,,− References − investigated in depth the application of DCP sensing materials in solutions. However, gas-phase sensing research was not involved too much.…”

Organoiridium(III) Complexes as Luminescence Color Switching Probes for Selective Detection of Nerve Agent Simulant in Solution and Vapor Phase

“…Researchers are utilizing less poisonous nerve agent mimics (Chart ) in laboratories as model compounds to evade direct contact. Diethyl chlorophosphate (DCP) serves as a harmless simulant of sarin (GB) with comparable reactivity and low toxicity. , The existing nerve agent mimic probes are mainly based on small organic molecules, such as pyrene, fluorescein, , coumarin, , cyanine/hemicyanine, , rhodamine, − pyronin, BODIPY, − naphthalimide, − and squaraine fluorogenic/chromogenic system (Figure ). Most of them used (i) direct phosphorylation reaction by oximes, ,, alcohols, and amines, , (ii) phosphorylation and rapid n -alkylation using acid groups, carbonyl, and intramolecular cyclization, ,,,,,− and (iii) phosphorylation and successive protonation of pyridine and quinoline ,, groups for nerve agent detection.…”

Chromo-Fluorogenic Detection of Soman and Its Simulant by Thiourea-Based Rhodamine Probe

“…Nevertheless, these protocols usually have some drawbacks, such as operation complexity, non-portability, difficulties in real-time monitoring, etc. As alternatives to these procedures, some new approaches have been explored involving molecularly imprinted polymers [12], nanoparticles [13], and chromo-fluorogenic probes [14,15,16,17,18,19,20,21,22]. Above all, chromo-fluorogenic probes have recently gained increasing interest due to their cost-effectiveness, simplicity, and “naked-eye” detection [23,24].…”

“…A typical chromo-fluorogenic probe is usually formed by two moieties: (1) a chromo-fluorogenic reporter group, which translates the binding event into the change of color and fluorescence, mainly containing rhodamine [22], fluorescein [15], boron dipyrromethene (BODIPY) [16,17], azo [14,20], and cyanine dye [18]; (2) a selective reactive group, which provides a reactive binding site for nucleophilic attack, mainly containing hydroxyl [15,25], oxime [19], and amino groups [26]. Recently, thiourea has been proved to be capable of reacting with nerve agents through hydrogen-bond interaction between N-H protons of thiourea and phosphonate oxygen or hydrolyzed products [27,28].…”