Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids
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  • 作者:Xiaorong Liang (1)
    Jian Liu (1)
    Yves LeBlanc (2)
    Tom Covey (2)
    A. Celeste Ptak (3)
    J. Thomas Brenna (3)
    Scott A. McLuckey (1)
  • 刊名:Journal of The American Society for Mass Spectrometry
  • 出版年:2007
  • 出版时间:October 2007
  • 年:2007
  • 卷:18
  • 期:10
  • 页码:1783-1788
  • 全文大小:2322KB
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  • 作者单位:Xiaorong Liang (1)
    Jian Liu (1)
    Yves LeBlanc (2)
    Tom Covey (2)
    A. Celeste Ptak (3)
    J. Thomas Brenna (3)
    Scott A. McLuckey (1)

    1. Department of Chemistry, Purdue University, 1393 Brown Laboratories, 47907-2084, West Lafayette, IN, USA
    2. MDS SCIEX, Concord, Ontario, Canada
    3. Division of Nutritional Sciences, Cornell University, Ithaca, New York, USA
文摘
The ability to generate gaseous doubly charged cations of glycerophosphocholine (GPC) lipids via electrospray ionization has made possible the evaluation of electron-transfer dissociation (ETD) for their structural characterization. Doubly sodiated GPC cations have been reacted with azobenzene radical anions in a linear ion trap mass spectrometer. The ion/ion reactions proceed through sodium transfer, electron-transfer, and complex formation. Electron-transfer reactions are shown to give rise to cleavage at each ester linkage with the subsequent loss of a neutral quaternary nitrogen moiety. Electron-transfer without dissociation produces [M+2Na]+· radical cations, which undergo collision-induced dissociation (CID) to give products that arise from bond cleavage of each fatty acid chain. The CID of the complex ions yields products similar to those produced directly from the electron-transfer reactions of doubly sodiated GPC, although with different relative abundances. These findings indicate that the analysis of GPC lipids by ETD in conjunction with CID can provide some structural information, such as the number of carbons, degree of unsaturation for each fatty acid substituent, and the positions of the fatty acid substituents; some information about the location of the double bonds may be present in low intensity CID product ions.

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