The fragmentation pathways of protonated Amiton in the gas phase: towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry

摘要

Amiton (O,O-diethyl-S-[2-(diethylamino)ethyl] phosphorothiolate), otherwise known as VG, is listed in Schedule 2 of the Chemical Weapons Convention (CWC) and has a structure closely related to VX (O-ethyl-S-(2-diisopropylamino)ethyl methylphosphonothiolate). Fragmentation of protonated VG in the gas phase was performed using an electrospray ionisation ion trap mass spectrometer (ESI-ITMS) and revealed several characteristic product ions. Quantum chemical calculations provide the most probable structures for these ions as well as the likely unimolecular mechanisms by which they are formed. The decomposition pathways predicted by computation are consistent with deuterium labeling studies. The combination of experimental and theoretical data suggests that the fragmentation pathways of VG and analogous organophosphorus nerve agents, such as VX and Russian VX, are predictable and as such ESI tandem mass spectrometry is a powerful tool for the verification of unknown compounds listed in the CWC.