Radical Generation from the Gas-Phase Activation of Ionized Lipid Ozonides.

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Journal of the American Society for Mass Spectrometry, ISSN: 1879-1123, Vol: 28, Issue: 7, Page: 1345-1358

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Ellis, Shane R; Pham, Huong T; In Het Panhuis, Marc; Trevitt, Adam J; Mitchell, Todd W; Blanksby, Stephen J
Springer Nature
Biochemistry, Genetics and Molecular Biology; Chemistry; Medicine and Health Sciences; Social and Behavioral Sciences
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article description
Reaction products from the ozonolysis of unsaturated lipids at gas-liquid interfaces have the potential to significantly influence the chemical and physical properties of organic aerosols in the atmosphere. In this study, the gas-phase dissociation behavior of lipid secondary ozonides is investigated using ion-trap mass spectrometry. Secondary ozonides were formed by reaction between a thin film of unsaturated lipids (fatty acid methyl esters or phospholipids) with ozone before being transferred to the gas phase as [M + Na] ions by electrospray ionization. Activation of the ionized ozonides was performed by either energetic collisions with helium buffer-gas or laser photolysis, with both processes yielding similar product distributions. Products arising from the decomposition of the ozonides were characterized by their mass-to-charge ratio and subsequent ion-molecule reactions. Product assignments were rationalized as arising from initial homolysis of the ozonide oxygen-oxygen bond with subsequent decomposition of the nascent biradical intermediate. In addition to classic aldehyde and carbonyl oxide-type fragments, carbon-centered radicals were identified with a number of decomposition pathways that indicated facile unimolecular radical migration. These findings reveal that photoactivation of secondary ozonides formed by the reaction of aerosol-bound lipids with tropospheric ozone may initiate radical-mediated chemistry within the particle resulting in surface modification. Graphical Abstract ᅟ.