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Fragmentation Pathways of 2,3-dimethyl-2,3-dinitrobutane Cations in the Gas Phase

Journal Article


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Abstract


  • 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+NH4](+) 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.

UOW Authors


  •   Ellis-Steinborner, Simon (external author)
  •   Paine, Martin (external author)
  •   Kirk, Benjamin B. (external author)
  •   Blanksby, Stephen J. (external author)

Publication Date


  • 2009

Citation


  • Paine, M., Kirk, B. B., Ellis-Steinborner, S. & Blanksby, S. (2009). Fragmentation Pathways of 2,3-dimethyl-2,3-dinitrobutane Cations in the Gas Phase. Rapid Communications in Mass Spectrometry, 23 (18), 2867-2877.

Scopus Eid


  • 2-s2.0-69849097512

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1319&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/285

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 2867

End Page


  • 2877

Volume


  • 23

Issue


  • 18

Abstract


  • 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+NH4](+) 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.

UOW Authors


  •   Ellis-Steinborner, Simon (external author)
  •   Paine, Martin (external author)
  •   Kirk, Benjamin B. (external author)
  •   Blanksby, Stephen J. (external author)

Publication Date


  • 2009

Citation


  • Paine, M., Kirk, B. B., Ellis-Steinborner, S. & Blanksby, S. (2009). Fragmentation Pathways of 2,3-dimethyl-2,3-dinitrobutane Cations in the Gas Phase. Rapid Communications in Mass Spectrometry, 23 (18), 2867-2877.

Scopus Eid


  • 2-s2.0-69849097512

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1319&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/285

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 2867

End Page


  • 2877

Volume


  • 23

Issue


  • 18