Molecular Rotors for the Detection of Chemical Warfare Agent Simulants

Abstract

The fluorogenic probe o-OH is able to detect and quantify organophosphorus nerve agent mimics in solution and in the vapor phase following immobilization on a solid substrate, making the system a suitable candidate for the field detection of chemical warfare agents. Detection is achieved by the suppression of internal rotation upon phosphorylation of a reactive phenolate, resulting in a large fluorescence "turn-on" response.

Challenges in Fluorescence Detection of Chemical Warfare Agent Vapors Using Solid‐State Films

“…O‐based nucleophiles as chemosensors for solid‐state detection have contained either phenols or oximes. Phosphorylation of phenols does not normally lead to a significant change in the fluorescent properties of the sensing material . However, if phosphorylation is able to alter the molecular rotation of a chromophore, the fluorescence may change .…”

“…Phosphorylation of phenols does not normally lead to a significant change in the fluorescent properties of the sensing material . However, if phosphorylation is able to alter the molecular rotation of a chromophore, the fluorescence may change . For example, when compound 7 is phosphorylated with DCP, it restricts the rotation in 7′ , leading to enhanced fluorescence ( Figure ).…”

“…However, if phosphorylation is able to alter the molecular rotation of a chromophore, the fluorescence may change . For example, when compound 7 is phosphorylated with DCP, it restricts the rotation in 7′ , leading to enhanced fluorescence ( Figure ). Detection using 7 employed a porous silica thin‐layer chromatography (TLC) plate as the substrate in order to evenly mix the sensing material and the organic base [e.g., TEA or 4‐ N , N ‐dimethylaminopyridine (DMAP)] that was required to enhance the phosphorylation rate.…”

“…Despite a large number of sensing materials being developed for the vapor phase detection of nerve agents and simulants, most research articles only present proposed mechanisms with limited evidence on how the sensing works. The reporter compounds, i.e., the product from the reaction between the sensing compound and the analyte such as DCP or DFP are given in some reports, but many are not characterized to a sufficient level to unambiguously confirm the structures . In some cases, the reporter compounds were synthesized from the sensing compound using more reactive reagents, e.g., tosyl chloride and thionyl chloride, but this in itself is not sufficient evidence that the compounds would be formed during the sensing process.…”

Construction of a luminescent sensor based on a lanthanide complex for the highly efficient detection of methyl parathion

“…Therefore, a number of uorescent sensors based on organic uorophores, Au nanoparticles, quantum dots and carbon dots et al have been constructed for the detection of OPs in real samples. [14][15][16][17][18] Barba-Bon and co-workers designed two Eu 3+ and Au 3+ complexes based on commonly used organic uorophore BODIPY. The BODIPY-containing complexes can effectively detect V-type nerve agent surrogates, demeton-S, by a colorimetric and uorescent double-detection assay with high sensitivity and selectivity.…”