title: Gas-phase reactions for selective detection of the explosives TNT and RDX.
abstract: Highly selective gas-phase reactions with ethyl vinyl ether (EVE) of major electron (EI) and chemical ionization (CI) fragment ions of the explosives TNT and RDX have been uncovered. The fragment ion of m/z 210 from TNT undergoes [4(+)+ 2] cycloaddition with EVE to form an oxo-iminium ion of m/z 282, which dissociates by acetaldehyde loss after a [1,5-H] shift to form a quinolynium ion of m/z 238. The fragment ion of m/z 149 from RDX reacts with EVE by a formal vinylation reaction, that is, the elusive cyclic adduct loses ethanol to yield a nitro-iminium ion of m/z 175, which reacts further with EVE to form a second cyclic product ion of m/z 247. Calculations and MS/MS experiments support the proposed structures. These highly characteristic reactions of diagnostic EI and CI fragment ions improve selectivity for TNT and RDX detection.
authors.affiliation: Institute of Chemistry, State University of Campinas, UNICAMP, SP, Brazil.
authors.forename: Eduardo C
authors.initials: EC
authors.lastname: Meurer
authors.forename: Hao
authors.initials: H
authors.lastname: Chen
authors.forename: Leah
authors.initials: L
authors.lastname: Riter
authors.forename: Ismael
authors.initials: I
authors.lastname: Cotte-Rodriguez
authors.forename: Marcos N
authors.initials: MN
authors.lastname: Eberlin
authors.forename: R Graham
authors.initials: RG
authors.lastname: Cooks