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Ion Mobility Studies on the Negative Ion-Molecule Chemistry of Isoflurane and Enflurane.

In the present work we present an investigation of the negative ion-molecule chemistry of the anaesthetics isoflurane, ISOF, and enflurane, ENF, in an ion mobility spectrometry/mass spectrometry (IMS/MS), in both air and nitrogen. Hexachloroethane (HCE) was introduced in both air and nitrogen to produce Cl(-) as a reactant ion. This study was undertaken owing to uncertainties in the chemical processes, which lead to the cluster ions reported in other work (Eiceman et al. Anal. Chem. 61, 1093-1099, 1). In particular for ISOF the product ion observed was ISOF.Cl(-), and it was suggested that the Cl(-) was formed by dissociative electron attachment (DEA) although there was mention of a chlorine containing contaminant. We show in this study that ISOF and ENF do not produce Cl(-) in an IMS system either by capture of free electrons or reaction with O2(-). This demonstrates that the Cl(-) containing ions, reported in the earlier study, must have been the result of a chlorine containing contaminant as suggested. The failure of ISOF and ENF to undergo DEA was initially surprising given the high calculated electron affinities, but further calculations showed that this was a result of the large positive vertical attachment energies (VAEs). This experimental work has been supported by electronic structure calculations at the B3LYP level, and is consistent with those obtained in a crossed electron-molecular beam two sector field mass spectrometer. An unusual observation is that the monomer complexes of ISOF and ENF with O2(-) are relatively unstable compared with the dimer complexes. Graphical Abstract ᅟ.

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