Direct detection and quantification of malondialdehyde vapour in humid air using selected ion flow tube mass spectrometry supported by gas chromatography/mass spectrometry.

Rationale It has been proposed that malondialdehyde (MDA) reflects free oxygen-radical lipid peroxidation and can be useful as a biomarker to track this process. For the analysis of MDA molecules in humid air by selected ion flow tube mass spectrometry (SIFT-MS), the rate coefficients and the ion product distributions for the reactions of the SIFT-MS reagent ions with volatile MDA in the presence of water vapour are required. Methods The SIFT technique has been used to determine the rate coefficients and ion product distributions for the reactions of H3O+, NO+ and O2+• with gas-phase MDA. In support of the SIFT-MS analysis of MDA, solid-phase microextraction, SPME, coupled with gas chromatography/mass spectrometry, GC/MS, has been used to confirm the identification of MDA. Results The primary product ions have been identified for the reactions of H3O+, NO+ and O2+• with MDA and the formation of their hydrates formed in humid samples is described. The following combinations of reagent and the analyte ions (given as m/z values) have been adopted for SIFT-MS analyses of MDA in the gas phase: H3O+: 109; NO+: 89, 102; O2+•: 72, 90, 108, 126. The detection and quantification of MDA released by a cell culture by SIFT-MS are demonstrated. Conclusions This detailed study has provided the kinetics data required for the SIFT-MS analysis of MDA in humid air, including exhaled breath and the headspace of liquid-phase biogenic media. The detection and quantification by SIFT-MS of MDA released by a cell culture are demonstrated. Copyright © 2015 John Wiley & Sons, Ltd.