Premium
Desorption electrospray ionization mass spectrometric analysis of organophosphorus chemical warfare agents using ion mobility and tandem mass spectrometry
Author(s) -
D'Agostino Paul A.,
Chenier Claude L.
Publication year - 2010
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.4547
Subject(s) - chemistry , sarin , chromatography , mass spectrometry , ion mobility spectrometry , electrospray ionization , soman , chemical ionization , analytical chemistry (journal) , ion source , sample preparation , tandem mass spectrometry , ambient ionization , electrospray , ion , ionization , organic chemistry , acetylcholinesterase , enzyme
Abstract Desorption electrospray ionization mass spectrometry (DESI‐MS) has been applied to the direct analysis of sample media for target chemicals, including chemical warfare agents (CWA), without the need for additional sample handling. During the present study, solid‐phase microextraction (SPME) fibers were used to sample the headspace above five organophosphorus CWA, O ‐isopropyl methylphosphonofluoridate (sarin, GB), O ‐pinacolyl methylphosphonofluoridate (soman, GD), O ‐ethyl N,N ‐dimethyl phosphoramidocyanidate (tabun, GA), O ‐cyclohexyl methylphosphonofluoridate (cyclohexyl sarin, GF) and O ‐ethyl S‐2‐diisopropylaminoethyl methyl phosphonothiolate (VX) spiked into glass headspace sampling vials. Following sampling, the SPME fibers were introduced directly into a modified ESI source, enabling rapid and safe DESI of the toxic compounds. A SYNAPT HDMS™ instrument was used to acquire time‐aligned parallel (TAP) fragmentation data, which provided both ion mobility and MS n (n = 2 or 3) data useful for the confirmation of CWA. Unique ion mobility profiles were acquired for each compound and characteristic product ions of the ion mobility separated ions were produced in the Triwave™ transfer collision region. Up to six full scanning MS n spectra, containing the [M + H] + ion and up to seven diagnostic product ions, were acquired for each CWA during SPME fiber analysis. A rapid screening approach, based on the developed methodology, was applied to several typical forensic media, including Dacron sampling swabs spiked with 5 µg of CWA. Background interference was minimal and the spiked CWA were readily identified within one minute on the basis of the acquired ion mobility and mass spectrometric data. Copyright © 2010 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.