Liquid chromatography/tandem mass spectrometric analysis of 7,10-dihydroxyoctadecenoic acid, its isotopomers, and other 7,10-dihydroxy fatty acids formed by Pseudomonas aeruginosa 42A2
2010 (English)In: Rapid Communications in Mass Spectrometry, ISSN 0951-4198, E-ISSN 1097-0231, Vol. 24, no 6, 777-783 p.Article in journal (Refereed) Published
Pseudomonas aeruginosa is an opportunistic pathogen, which oxidizes oleic acid to 7(S),10(S)-dihydroxy-8(E)-octadecenoic acid (7,10-(OH)(2)-18:1) of biological and industrial interest. Electrospray tandem mass spectrometric (MS/MS) analysis of hydroxylated fatty acids usually generates characteristic fragments containing the carboxylate anion and formed by alpha-cleavage at the oxidized carbon. These fragments indicate the positions of the hydroxyl group. In contrast, liquid chromatography (LC)/MS/MS analysis of 7,10-(OH)(2)-18:1 yielded a series of other ions with structural information. To study the fragmentation mechanism, we prepared (2)H- and (18)O-labeled isotopomers. We also performed MS(3) analysis of the major ions, and for comparison we generated the corresponding 7,10-dihydroxy metabolites of 16:1n-7, 18:2n-6, and 20:1n-11 with a protein extract of P. aeruginosa. The MS/MS spectra of 7,10-(OH)(2)-18:1 and its isotopomers, 7,10-(OH)(2)-16:1, and 7,10-(OH)(2)-20:1, contained a series of prominent fragments that all hold the omega end. The 8,9-double bond was not essential for this fragmentation, as 7,10-(OH)(2)-18:0, and its isotopomers, formed essentially the same fragments in the lower mass range. In contrast, 7,10-dihydroxy-8(E),12(Z)-octadecadienoic acid (7,10-(OH)(2)-18:2) fragmented by alpha-cleavage at the oxidized carbons with formation of carboxylate anions. Our results demonstrate that C(16)-C(20) fatty acids with a 7,10-dihydroxy-8(E) functionality undergo charge-driven fragmentation after charge migration to the omega-end, whereas the main ions of 7,10-(HO)(2)-18:2 retain charge at the carboxyl group.
Place, publisher, year, edition, pages
2010. Vol. 24, no 6, 777-783 p.
Charge remote fragmentation, Electrospray ionisation, Isotopomers, Hydroxy fatty acids, MS/MS/MS analysis
Pharmacology and Toxicology
Research subject Biochemical Pharmacology
IdentifiersURN: urn:nbn:se:uu:diva-109711DOI: 10.1002/rcm.4446ISI: 000276111100010PubMedID: 20187080OAI: oai:DiVA.org:uu-109711DiVA: diva2:273612