Ozone-induced dissociation: Elucidation of double bond position within mass-selected lipid ions

被引:294
作者
Thomas, Michael C. [1 ,2 ]
Mitchell, Todd W. [1 ,2 ]
Harman, David G. [1 ,2 ]
Deeley, Jane M. [1 ,2 ]
Nealon, Jessica R. [1 ,2 ]
Blanksby, Stephen J. [1 ,2 ]
机构
[1] Univ Wollongong, Dept Chem, Wollongong, NSW 2522, Australia
[2] Univ Wollongong, Sch Hlth Sci, Wollongong, NSW 2522, Australia
关键词
D O I
10.1021/ac7017684
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Ions formed from lipids during electrospray ionization of crude lipid extracts have been mass-selected within a quadrupole linear ion trap mass spectrometer and allowed to react with ozone vapor. Gas-phase ion-molecule reactions between unsaturated lipid ions and ozone are found to yield two primary product ions for each carbon-carbon double bond within the molecule. The mass-to-charge ratios of these chemically induced fragments are diagnostic of the position of unsaturation within the precursor ion. This novel analytical technique, dubbed ozone-induced dissociation (OzID), can be applied both in series and in parallel with conventional collision-induced dissociation (CID) to provide near-complete structural assignment of unknown lipids within complex mixtures without prior fractionation or derivatization. In this study, OzID is applied to a suite of complex lipid extracts from sources including human lens, bovine kidney, and commercial olive oil, thus demonstrating the technique to be applicable to a broad range of lipid classes including both neutral and acidic glycerophospholipids, sphingomyelins, and triacylglycerols. Gas-phase ozonolysis reactions are also observed with different types of precursor ions including [M + H](+), [M + Li](+), [M + Na](+), and [M H](-): in each case yielding fragmentation data that allow double bond position to be unambiguously assigned. Within the human lens lipid extract, three sphingomyelin regioisomers, namely SM(d18:0/15Z-24:1), SM(d18:0/17Z-24:1), and SM(d18:0/19Z-24:1), and a novel phosphatidylethanolamine alkyl ether, GPEtn(11Z-18:1e/9Z18:1), are identified using a combination of CID and OzID. These discoveries demonstrate that lipid identification based on CID alone belies the natural structural diversity in lipid biochemistry and illustrate the potential of OzID as a complementary approach within automated, high-throughput lipid analysis protocols.
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收藏
页码:303 / 311
页数:9
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