Identification of G‐nerve agents at picogram levels from complex organic samples containing hydrocarbon interferences by aqueous extraction, followed by derivatization and liquid chromatography‐mass spectrometry analysis

Abstract

The chromatograms obtained from the gas chromatography-electron ionization mass spectrometric (GC-EI-MS) analysis of extracts containing G-nerve agents in the presence of diesel, gasoline, etc., are dominated by hydrocarbon backgrounds that "mask" the G-nerve agents, leading to severe difficulties in identification. This paper presents a practical solution for this challenge by transferring the G-nerve agents from the organic phase into the aqueous phase using liquid-liquid extraction (LLE), followed by derivatization with 2-[(dimethylamino)methyl]phenol (2-DMAMP), allowing ultrasensitive LC-ESI-MS/MS analysis of the G-derivatives. The proposed approach enables rapid identification of trace amounts of G-nerve agents with limits of identification (LOIs) at the pg/mL scale.

A novel approach for the detection and identification of sulfur mustard using liquid chromatography–electrospray ionization–tandem mass spectrometry based on its selective oxidation to sulfur mustard monoxide with N‐iodosuccinimide

“…A simple derivatization reaction for the detection and identification of G-nerve agents (GB, GD, GF, and GA) by LC-ESI-MS/MS or by direct ESI-MS/MS was previously developed. [24][25][26][27][28][29] Hence, we were highly motivated to develop a chemical derivatization reaction for the detection and identification of HD by LC-ESI-MS/MS.…”

“…HD is hardly soluble in water, and when dissolved, it dissociates rapidly and is not well ionized by ESI; therefore, its direct analysis by LC‐MS is challenging. A simple derivatization reaction for the detection and identification of G‐nerve agents (GB, GD, GF, and GA) by LC‐ESI‐MS/MS or by direct ESI‐MS/MS was previously developed 24–29 . Hence, we were highly motivated to develop a chemical derivatization reaction for the detection and identification of HD by LC‐ESI‐MS/MS.…”

Oxidative derivatization of V‐type nerve agents as a tool for their structural elucidation by liquid chromatography/tandem mass spectrometry

“…Structural elucidation of V‐type nerve agents by chemical derivatization is an alternative approach; however, to date, no report has been found in the literature 3 . Chemical derivatization that allows sensitivity enhancement for G‐type nerve agents in various matrices was reported by Weissberg et al, 12–14 Blanca et al, 15 Madmon and Weissberg, 16 and Mach et al 17 employing 2‐[(dimethylamino)methyl]phenol (2‐DMAMP). In recent years, we have demonstrated how derivatization can be employed not only for sensitivity enhancement, but also for the structural elucidation of several illicit drugs, pharmaceuticals and other related compounds 18–22 .…”

Chromogenic Detection of the Organophosphorus Nerve Agent Simulant DCP Mediated by Rhodium(II,II) Paddlewheel Complexes

“…A myriad of approaches exist for OPNA detection . Some of the most sensitive and selective of these include instrument-based methods such as mass spectrometry, fluorescence spectroscopy, biosensors, and electrochemical sensors . Unfortunately, they have drawbacks such as limited portability, operational complexity, and higher expense than other options.…”