Desorption Electrospray Ionization Mass Spectrometry (DESI-MS) Analysis of Organophosphorus Chemical Warfare Agents: Rapid Acquisition of Time-Aligned Parallel (TAP) Fragmentation Data

Abstract

Desorption electrospray ionization-mass spectrometric (DESI-MS) analysis has been applied to the direct analysis of chemical warfare agents spiked on a variety of sample media including soils, water, food products and indoor samples that could be collected during a forensic investigation following a chemical incident. Solid phase microextration (SPME) fibers were used in this investigation to sample the headspace above five organophosphorus chemical warfare agents, O-isopropyl methylphosphonofluoridate (sarin, GB), O-pinacolyl methylphosphonofluoridate (soman, GD), O-ethyl N,N-dimethylphosphoramidocyanidate (tabun, GA), O-cyclohexyl methylphosphonofluoridate (cyclohexyl sarin, GF) and O-ethyl S-2- diisopropylaminoethyl methylphosphonothiolate (VX). The exposed SPME fibers were introduced directly into a modified Z-spray electrospray (ESI) source, enabling rapid and safe DESI-MS analysis of the toxic chemical warfare agents. Time-aligned parallel (TAP) fragmentation data, which provides both ion mobility spectrometry (IMS) and tandem mass spectrometry (MSn, where n=2 or 3) data for an individual compound, was acquired for the first time for organophosphorus chemical warfare agents. Unique ion mobility profiles and up to six full scanning MSn spectra, containing the [M+H]+ ion and up to seven diagnostic product ions, were acquired for each chemical warfare agent during DESI-IMS-MSn analysis of the exposed SPME fiber analysis. A rapid screening approach, based on the developed methodology, was applied to several typical forensic media (Dacron sampling swabs, office furniture fabric and cardboard) spiked with 5 mug of chemical warfare agent. Background interference was minimal and the spiked chemical warfare agents were readily identified within a minute on the basis of the acquired ion mobility and mass spectrometric data.

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Document Details

Document Type
Technical Report
Publication Date
Jun 01, 2010
Accession Number
ADA534864

Entities

People

  • Claude L. Chanier
  • Paul A. D'aghostino

Tags

Communities of Interest

  • Biomedical

DTIC Thesaurus Topics

  • Chemical Synthesis
  • Chemical Warfare
  • Chemical Warfare Agents
  • Chemical Weapons
  • Chemistry
  • Electrospray Ionization
  • Ionization
  • Liquid Chromatography
  • Mass Spectra
  • Mass Spectrometers
  • Mass Spectrometry
  • National Security
  • Solid Phases
  • Spectra
  • Spectrometers
  • Spectrometry
  • Spectroscopy

Fields of Study

  • Chemistry

Readers

  • Analytical Chemistry
  • Neurotoxicology