Gas-phase fragmentation analysis of nitro-fatty acids

GUSTAVO BONACCI, ELIANA K. ASCIUTTO, STEVEN R. WOODCOCK, SONIA R. SALVATORE,BRUCE A. FREEMAN, FRANCISCO J. SCHOPFER

ELSEVIER SCIENCE INC

Año: 2011 vol. 22 p. 1 - 1

itro-fatty acids are electrophilic signaling mediators formed in increased amounts during inflammation by nitric oxide and nitrite-dependent redox reactions. A more rigorous characterization of endogenously-generated species requires additional understanding of their gas-phase induced fragmentation. Thus, collision induced dissociation (CID) of nitroalkane and nitroalkene groups in fatty acids were studied in the negative ion mode to provide mass spectrometric tools for their structural characterization. Fragmentation of nitroalkanes occurred mainly through loss of the NO2- anion or neutral loss of HNO2. The CID of nitroalkenes proceeds via a more complex cyclization, followed by fragmentation to nitrile and aldehyde products. Gas-phase fragmentation of nitroalkene functional groups with additional gamma or delta unsaturation occurred through a multiple step cyclization reaction process, leading to 5 and 6 member ring heterocyclic products and carbon chain fragmentation. Cyclization