Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phase

Paine, M. R. L., Kirk, B. B., Ellis-Steinborner, S., & Blanksby, Stephen J. (2009) Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phase. Rapid Communications in Mass Spectrometry, 23(18), pp. 2867-2877.

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2,3-Dimethyl-2,3-dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour-phase detection systems. In this study, the formation and detection of gas-phase [M+H](+), [M+Li](+), [M+NH(4)](+) and [M+Na](+) adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The [M+H](+) ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50 degrees C. In contrast, the [M+Na](+) ion demonstrated increasing ion abundance at source temperatures up to 105 degrees C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision-induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source-formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the [M+Na](+) adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright (C) 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

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ID Code: 70227
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: ion mobility spectrometry, electrospray-ionization, explosives taggant, dmnb
DOI: 10.1002/rcm.4192
ISSN: 0951-4198
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2012 John Wiley & Sons, Ltd.
Deposited On: 13 May 2014 01:14
Last Modified: 19 Jan 2016 05:39

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