10.1021/ac051326z.s001
Chagit Denekamp
Chagit
Denekamp
Alexander Tsoglin
Alexander
Tsoglin
Development of Mass Spectrometric Method for
Analysis of Cyclic Nitramine Explosives DTIW and
HNIW
American Chemical Society
2005
isowurzitane structure
fragmentation pathway
HNIW Mass
DCI
Cyclic Nitramine Explosives DTIW
MS 2 experiments
Mass Spectrometric Method
pressure chemical ionization techniques
MH
ESI
CO
CF
HNIW fragmentation pathways
Several anion adducts
LC
fragmentation pathways
DFT calculations
Several anions
2005-12-01 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Development_of_Mass_Spectrometric_Method_for_Analysis_of_Cyclic_Nitramine_Explosives_DTIW_and_HNIW/3253738
Mass spectrometric (MS) methods are used for the
analysis of two novel nitramine explosivesî—¸hexanitrohexaazaisowurzitane (HNIW) and 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurzitane (DTIW). The methods include electrospray (ESI) and atmospheric pressure chemical ionization techniques for liquid chromatography/MS
(LC/MS), chemical ionization for direct introduction
(DCI), and gas chromatography/MS (CI-GC/MS). It is
found that HNIW (438 Da) is detectable using both
positive and negative modes of DCI and in the negative
mode ESI-MS. Several anions were found to complex with
HNIW, e.g., CF<sub>3</sub>CO<sub>2</sub><sup>-</sup>, Cl<sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>, NO<sub>3</sub><sup>-</sup>, and NO<sub>2</sub><sup>-</sup>. On
the other hand, DTIW could only be detected using
positive DCI and CI-GC/MS, where an MH<sup>+</sup> ion (<i>m</i>/<i>z</i>
263) was formed. The fragmentation pathways of the two
nitramines were further studied by MS<sup>2</sup> experiments.
Apparently, the main fragmentation pathway of the MH<sup>+</sup>
ion of DTIW involves the loss of nitrous acid. Several
anion adducts of HNIW that were studied dissociate to
afford neutral HNIW and the added anions. However, Cl<sup>-</sup>,
Br<sup>-</sup>, I<sup>-</sup>, and NO<sub>2</sub><sup>-</sup> afford a series of fragments that
resulted from the dissociation of the isowurzitane structure. For these anions, limit of detection was also found.
To understand some of the HNIW fragmentation pathways, DFT calculations were used.