Enhanced LC-ESI-MS/MS Sensitivity by Cationic Derivatization of Organophosphorus Acids.

The chemical derivatization to enhance the signal intensity and signal-to-noise (S/N) of several organophosphorus (OP) acids in liquid chromatography tandem mass spectrometry (LC-ESI-MS/MS) is illustrated. The OP class of compounds represents the environmental degradants of OP nerve agents and pesticides. N-(2-(bromomethyl)benzyl)-N,N-diethylethanaminium bromide (CAX-B) was utilized to derivatize a panel of eight acids consisting of five alkyl methylphosphonic acids (ethyl-, isopropyl-, isobutyl-, cyclohexyl-, and pinacolyl-methylphosphonic acid) along with three dialkylphosphate analogs (diethyl-, dibutyl-, and diethyl thio-phosphate). The derivatization reaction with CAX-B was conducted in acetonitrile in the presence of potassium carbonate at 70 °C for 1 h. The resulting acid derivatives were analyzed with an LC-Orbitrap-ESI-MS/MS, and their dissociation processes were investigated. It was found that the derivatization procedure increased the limits of identification (LOIs) by one to over two orders of magnitude from the range of 1 to 10 ng/mL for the intact OP-acids to the range of 0.02-0.2 ng/mL for the derivatized acids utilizing an LC-MS(QqQ) in MRM mode, regardless of the sample matrix (hair, concrete, or plant extracts). The interpretation of the corresponding ESI-MS/MS spectra for each type of derivatized sub-OP family revealed the formation of characteristic neutral losses and a characteristic ion for the organophosphorus core. This derivatization is beneficial and useful for screening and identifying target and "unknown" OP acids.

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 new derivatization strategy for the detection and identification of sulfur mustard (HD) via liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) is developed. The method incorporates selective oxidation of the sulfide group by the electrophilic iodine reagent N-iodosuccinimide (NIS) to produce sulfur mustard monoxide (HDSO). The derivatization reaction efficiencies were evaluated with acetonitrile extracts of soil, asphalt, cloth, Formica, and linoleum spiked with HD at concentrations of 50-5000 pg/ml and found to be similar to that with pure acetonitrile. The current derivatization approach is the first to preserve the identity of chloride groups and support HD regulation and evidentiary findings.

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.

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.