Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids.
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.
Liang
Xiaorong
X
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA.
Liu
Jian
J
LeBlanc
Yves
Y
Covey
Tom
T
Ptak
A Celeste
AC
Brenna
J Thomas
JT
McLuckey
Scott A
SA
D004579:Electron Transport; D005990:Glycerol / Q000737:chemistry*; D005994:Glycerophosphates; D008055:Lipids / Q000737:chemistry*; D010767:Phosphorylcholine / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
D005994:Glycerophosphates; D008055:Lipids; D010767:Phosphorylcholine; D012964:Sodium; D005990:Glycerol
Anal Chem. 2007 Apr 15;79(8):3206-13
17367115
J Am Chem Soc. 2005 Sep 14;127(36):12627-39
16144411
Chem Rev. 2001 Feb;101(2):479-526
11712255
Proc Natl Acad Sci U S A. 2002 Feb 19;99(4):1774-9
11842225
J Am Soc Mass Spectrom. 1998 May;9(5):516-26
9879366
J Am Soc Mass Spectrom. 2005 Dec;16(12):2052-6
16253515
J Am Soc Mass Spectrom. 2003 Oct;14(10):1130-47
14530094
Proc Natl Acad Sci U S A. 2005 Jul 5;102(27):9463-8
15983376
J Am Chem Soc. 2002 Jan 30;124(4):672-8
11804498
Mass Spectrom Rev. 2003 Jan-Feb;22(1):57-77
12768604
Proc Natl Acad Sci U S A. 2004 Jun 29;101(26):9528-33
15210983
J Am Soc Mass Spectrom. 2007 Mar;18(3):466-78
17141526
Anal Chem. 2001 Jan 1;73(1):19-22
11195502
J Am Soc Mass Spectrom. 2003 Mar;14(3):253-61
12648932
Anal Chem. 2000 Feb 1;72(3):563-73
10695143
J Am Soc Mass Spectrom. 2007 Mar;18(3):479-92
17141525
Prostaglandins Other Lipid Mediat. 2005 Sep;77(1-4):131-40
16099398
Science. 1989 Oct 6;246(4926):64-71
2675315
Anal Chem. 2005 Mar 15;77(6):1831-9
15762593
Annu Rev Nutr. 1994;14:269-96
7946521
Anal Chem. 2006 May 1;78(9):3208-12
16643016
Anal Biochem. 1996 Jul 1;238(2):117-28
8660600
Rapid Commun Mass Spectrom. 2003;17(10):1056-64
12720286
Nature. 2005 Dec 1;438(7068):612-21
16319881