Abstract
Collision-induced dissociation (CID) of the [M + H]+ of glycerophospholipids typically results in abundant fragment ions that are related to the polar head group or loss of the polar head group. An exception to this general rule occurs for glycerophosphoethanolamines (GPEtn), which are a class of phospholipids that can have an acyl, 1-O-alkyl, or 1-O-alk-1′-enyl group as a substituent at the sn-1 position. The CID of the [M + H]+ of diacyl-GPEtn typically results in the expected loss of the phosphoethanolamine head group (141 Da). Therefore, constant neutral loss of 141 Da has been used as a diagnostic tool for the determination of GPEtn species in complex lipid mixtures. One disadvantage in using constant neutral loss of 141 Da in order to determine GPEtn content in lipid mixtures is that plasmalogen GPEtn does not undergo neutral loss of phosphoethanolamine to the same extent as diacyl-GPEtn. The current studies have used positive ion mode electrospray tandem mass spectrometry to study the collision-induced dissociation of various GPEtn plasmalogens present in the phospholipid membranes of human neutrophils. The CID of the [M + H]+ of plasmalogen GPEtn resulted in two prominent fragment ions; one that was characteristic of the sn-1 position and one that was characteristic of the sn-2 position. These two ions were used to detect specific molecular species of GPEtn containing esterified arachidonate (precursors of m/z 361) present in the human neutrophil.
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References
Funk, C. D. Prostaglandins and Leukotrienes: Advances in Eicosanoid Biology. Science 2001, 294, 1871–1875.
Honda, Z.; Ishii, S.; Shimizu, T. Platelet-Activating Factor Receptor. J. Biochem. 2002, 131, 773–779.
Taylor, C. W. Controlling Calcium Entry. Cell 2002, 111, 767–769.
Simons, K.; Ikonen, E. Functional Rafts in Cell Membranes. Nature 1997, 387, 569–572.
Berliner, J. A.; Heinecke, J. W. The Role of Oxidized Lipoproteins in Atherogenesis. Free Rad. Biol. Med. 1996, 20, 707–727.
Athar, M. Oxidative Stress and Experimental Carcinogenesis. Indian J. Exp. Biol. 2002, 40, 656–667.
Montine, T. J.; Neely, M. D.; Quinn, J. F.; Beal, M. F.; Markesberry, W. R.; Roberts, L. J., II; Morrow, J. D. Lipid Peroxidation in Aging Brain and Alzheimer’s Disease. Free Rad. Biol. Med. 2002, 33, 620–626.
Pulfer, M.; Murphy, R. C. Electrospray Mass Spectrometry of Phospholipids. Mass Spectrom. Rev. 2003, 22, 332–364.
Cole, M. J.; Enke, C. G. Direct Determination of Phospholipid Structures in Microorganisms by Fast Atom Bombardment Triple Quadrupole Mass Spectrometry. Anal. Chem. 1991, 63, 1032–1038.
Kayganich, K. A.; Murphy, R. C. Fast Atom Bombardment Tandem Mass Spectrometric Identification of Diacyl, Alkylacyl, and Alk-1-Enylacyl Molecular Species of Glycerophosphoethanolamine in Human Polymorphonuclear Leukocytes. Anal. Chem. 1992, 64, 2965–2971.
Haslett, C.; Guthrie, L. A.; Kopaniak, M.; Johnston, R. B., Jr.; Henson, P. M. Modulation of Multiple Neutrophil Functions by Preparative Methods or Trace Concentrations of Bacterial Lipopolysaccharide. Am. J. Pathol. 1985, 119, 101–110.
Bligh, E. G.; Dyer, W. J. A Rapid Method of Total Lipid Extraction and Purification. Can. J. Biochem. Physiol. 1959, 37, 911–917.
Murphy, E. J.; Anderson, D. K.; Horrocks, L. A. Phospholipid and Phospholipid Fatty Acid Composition of Mixed Murine Spinal Cord Neuronal Cultures. J. Neurosci. Res. 1993, 34, 472–477.
MacDonald, J. I.; Sprecher, H. Distribution of Arachidonic Acid in Choline- and Ethanolamine-Containing Phosphoglycerides in Subfractionated Human Neutrophils. J. Biol. Chem. 1989, 264, 17718–17726.
Kerwin, J. L.; Wiens, A. M.; Ericsson, L. H. Identification of Fatty Acids by Electrospray Mass Spectrometry and Tandem Mass Spectrometry. J. Mass Spectrom. 1996, 31, 184–192.
Chilton, F. H.; Murphy, R. C. Remodeling of Arachidonate-Containing Phosphoglycerides with the Human Neutrophil. J. Biol. Chem. 1986, 261, 7771–7777.
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Published online September 11, 2004
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Berry, K.A.Z., Murphy, R.C. Electrospray ionization tandem mass spectrometry of glycerophosphoethanolamine plasmalogen phospholipids. J Am Soc Mass Spectrom 15, 1499–1508 (2004). https://doi.org/10.1016/j.jasms.2004.07.009
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DOI: https://doi.org/10.1016/j.jasms.2004.07.009