Nitramine Anion Fragmentation: A Mass Spectrometric and Ab Initio Study

Nitramine Anion Fragmentation: A Mass Spectrometric and Ab Initio Study

The fragment ion formation characteristics of the radical anions generated from hexahydro-1,3,5-trinitrotriazine (RDX) and its three nitroso metabolites were studied using GC/MS with negative chemical ionization (NCI) to understand the fragmentation mechanisms responsible for the formation of the mo...

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Bibliographic Details
Published in:Journal of the American Society for Mass Spectrometry Vol. 18; no. 5; pp. 835 - 841
Main Authors: Florián, Jan, Gao, Lan, Zhukhovskyy, Vladimir, MacMillan, Denise K., Chiarelli, M. Paul
Format: Journal Article
Language:English
Published: New York, NY Elsevier Inc 01-05-2007
Elsevier Science
Springer Nature B.V
Subjects:
Analytical chemistry
Anions
Applied sciences
Atrazine
Chemical bonds
Chemical industry and chemicals
Chemistry
Chromatographic methods and physical methods associated with chromatography
Exact sciences and technology
Fragmentation
Gas chromatographic methods
Industrial chemicals
Ionization
Ions
Mass spectra
Mass spectrometry
Mass spectroscopy
Mathematical analysis
Metabolites
Nitrogen
Organic chemistry
Powders, propellants, explosives
RDX
Reactivity and mechanisms
Spectrometry
Nitramines
Chemical analysis
Ab initio method
Coupled method
Reaction path
Theoretical study
Fragmentation pattern
Energy diagram
Free energy
Chemical ionization
Gas chromatography
Hexogen
Density functional method
Explosives
Thermodynamic properties
Mass spectrometry
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Summary:The fragment ion formation characteristics of the radical anions generated from hexahydro-1,3,5-trinitrotriazine (RDX) and its three nitroso metabolites were studied using GC/MS with negative chemical ionization (NCI) to understand the fragmentation mechanisms responsible for the formation of the most abundant ions observed in their NCI mass spectra. Ab initio and density functional theory calculations were used to calculate relative free energies for different fragment ion structures suggested by the m/z values of the most abundant ions observed in the NCI mass spectra. The NCI mass spectra of the four nitramines are dominated by ions formed by the cleavage of nitrogen–nitrogen and carbon–nitrogen bonds in the atrazine ring. The most abundant anions in the NCI mass spectra of these nitramines have the general formulas C 2H 4N 3O ( m/z 86) and C 2H 4N 3O 2 ( m/z 102). The analyses of isotope-labeled standards indicate that these two ions are formed by neutral losses that include two exocylic nitrogens and one atrazine ring nitrogen. Our calculations and observations of the nitramine mass spectra suggest that the m/z 86 and m/z 102 ions are formed from either the (M NO) − or (M NO 2) − fragment anions by a single fragmentation reaction producing neutral losses of CH 2N 2O or CH 2N 2O 2 rather than a set of sequential reactions involving neutral losses of HNO 2 or HNO and HCN.
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ISSN:1044-0305
1879-1123
DOI:10.1016/j.jasms.2007.01.009