IDENTIFICATION OF RADICAL ADDUCTS FORMED IN THE REACTIONS OF UNSATURATED FATTY-ACIDS WITH SOYBEAN LIPOXYGENASE USING CONTINUOUS-FLOW FAST-ATOM-BOMBARDMENT WITH TANDEM MASS-SPECTROMETRY
H. Iwahashi et al., IDENTIFICATION OF RADICAL ADDUCTS FORMED IN THE REACTIONS OF UNSATURATED FATTY-ACIDS WITH SOYBEAN LIPOXYGENASE USING CONTINUOUS-FLOW FAST-ATOM-BOMBARDMENT WITH TANDEM MASS-SPECTROMETRY, Free radical research, 25(3), 1996, pp. 255-274
Structures of alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) r
adical adducts formed in the reactions of soybean lipoxygenase with li
noleic acid, linolenic acid, and arachidonic acid were determined usin
g continuous flow fast atom bombardment (CF-FAB) combined with tandem
mass spectrometry. The radical adducts of these lipoxygenase-dependent
reactions were: n-octanoic acid radical, 12,13-dihydroxylinoleic acid
radical, 12,13-epoxylinoleic acid radical, and n-pentyl radical from
linoleic acid; n-octanoic acid radical, ethyl radical, and cis/trans a
nd/or positional isomers (1- and S-pentenyl) of pentenyl radical from
linolenic acid; and 14,15-epoxyarachidonic acid radical and n-pentyl r
adical from arachidonic acid. Of these radical adducts, the n-octanoic
acid radical from linoleic and linolenic acid, the ethyl radical from
linolenic acid, and the 12,13-dihydroxylinoleic acid radical are iden
tified for the first time in the reactions of soybean lipoxygenase. Th
us the CF-FAB combined with tandem mass spectrometry employed here, by
which both radical adducts and their fragment ions can be detected, i
s shown to be a powerful tool in the structural identification of free
radicals.