Resonant electron capture mass spectrometry of free fatty acids: examination of ion structures using deuterium-labeled fatty acids and collisional activation

被引:12
作者
Voinov, VG
Van den Heuvel, H
Claeys, M
机构
[1] Univ Instelling Antwerp, Dept Pharmaceut Sci, B-2610 Antwerp, Belgium
[2] Russian Acad Sci, Pacific Inst Bioorgan Chem, Vladivostok 690022, Russia
来源
JOURNAL OF MASS SPECTROMETRY | 2002年 / 37卷 / 03期
关键词
charge-remote fragmentation; collision-induced dissociation; resonant electron capture; fatty acids;
D O I
10.1002/jms.285
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
The structures of [M-H](-) ions generated from free fatty acids in resonant electron capture at energies of 1.2 and 7.2 eV were investigated using deuterium-labeled isotopomers and collision-induced dissociation. The [M-H](radical anion) ions occur in both a carboxylate anion and a carbanion form. While the formation of the carboxylate anion at 1.2 eV involves the loss of a carboxylic hydrogen, that at 7.2 eV involves the loss of a hydrogen from different positions in the aliphatic chain followed by a rearrangement of a carboxylic hydrogen on to the radical site in the chain. The [M-H-H2O](-) ion which is a minor ion in the resonant electron capture spectrum at 7.2 eV is shown to be a precursor for the charge-remote fragment ions corresponding to formal losses of a hydrogen and elements of alkanes. The [M-H-H2O](-) ion corresponding to the second major ion in the resonant electron capture spectrum at 7.2 eV is demonstrated to be consistent with a cyclopentanone anion structure. On the basis of new insights obtained in the present study and taking into account previous results, an updated proposal is presented for the mechanism of charge-remote fragmentation which operates in resonant electron capture of free fatty acids at 7.2 eV. Copyright ( C) 2002 John Wiley Sons, Ltd.
引用
收藏
页码:313 / 321
页数:9
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