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Mass spectrometry (MS) has become an essential analytical method in every sector of science and technology. Because of its unique ability to provide direct molecular structure information on analytes, an extra method is rarely required. This review describes fabrication of a variable-pressure hollow cathode discharge (HCD) ion source for MS in detection, quantification and investigation of gas-phase ion molecule reactions of explosives and related compounds using air as a carrier gas. The HCD ion source has been designed in such a way that by altering the ion source pressures, the system can generate both HCD and conventional GD. This design enables for the selective detection and quantification of explosives at trace to ultra-trace levels. The pressure-dependent HCD ion source has also been used to investigate ion-molecule reactions in the gas phase of explosives and related compounds. The mechanism of ion formation in explosive reactions is also discussed. [ABSTRACT FROM AUTHOR]

In this study, we have developed a variable pressure operating hollow cathode discharge (HCD) ion source to investigate the gas phase ion-molecule reactions of nitroaromatic explosive compounds. The developed HCD ion source coupled MS system has also been validated as an analytical method to analyze explosives at trace levels. The ion source was designed in such a way that the plasma can be generated alternatively at high pressure (~30 Torr), medium pressure (~5 Torr) and low pressure (~1 Torr) regions. The plasma contains a sufficient amount of reactant ions, electrons and excited species, thus the gaseous analyte molecules were efficiently ionized when they passed through the plasma. In the ion-molecule reactions of the nitroaromatic explosives, the discharge products of NO x − (x = 2,3), O 3 and HNO 3 originating from the plasma-excited air were suggested to contribute to the formation of mostly [M − H]-, [M − NO]-, [M+NO 3 –HNO 2 ]- and [M-NO+HNO 3 ]- adduct ions at the higher ion source pressures (~5 and 28 Torr) while the electron rich plasma leads to the formation of molecular ion, M−•, at the lower ion source pressure (~1 Torr). Formation of the hydride-adduct ions of the nitroaromatic compounds reveals the surface-assisted Birch type reduction in the HCD plasma. The variety of spectral patterns in the air-assisted glow discharge would be useful for high through-put detection of TNT and TNT-related explosives. An ambient helium dielectric barrier discharge (DBD) ion source was also used and gave identical mass spectra of the nitroaromatic explosive compounds to those observed by the HCD ion source, but did not give any hydride-adduct ions of the explosive compounds. Ion formation mechanism of these ions is also discussed. Gas phase ion-molecule reactions of nitroaromatic explosive compounds studied by hollow cathode discharge ionization-mass spectrometry. [Display omitted] • Development of variable pressures hollow cathode discharge ion source. • Gas phase ion-molecule reactions of nitroaromatic explosives by mass spectrometry. • High ion source pressure facilitates adduct ion, low pressure provides molecular ion. • Metallic surface leads Birch reduction type reactions that lead hydride-adduct ions. • High through-put detection of TNT and TNT-related explosives. [ABSTRACT FROM AUTHOR]