This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. Mechanisms for phospholipid fragmentation during electrospray ionization mass spectrometry with collision-induced dissociation: The introduction of electrospray ionization mass spectrometry (ESI-MS) to analyze intact complex lipids has advanced the research in this field to a new level. The superb sensitivity and ease of continuous sample introduction with ESI, coupled with tandem mass spectrometry, provide opportunities to explore the structures and fragmentation processes of complex lipids in greater detail. In this chapter, we describe the current state of knowledge about the mechanisms involved in the formation of various product ions following collisional activation of the [M + H]+, [M + Alk]+, and [M - H + 2Alk]+ (if applicable) adduct ions generated by ESI in the positive-ion mode, as well as the [M -H]-, [M - 2H]2- and [M - 2H + Alk]- (if applicable) ions in the negative-ion mode. Mechanisms of fragmentation of common glycerophospholipids, including glycerophosphocholine, glycerophosphoethanolamine, glycerophosphoserine, glycerophosphatidic acid, glycerophosphoinositol, glycerophosphoglycerol, and cardiolipin, as well as sphingolipids including sphingomyelin, glycosphingolipids and sulfatides are described. The fragmentation mechanisms of ceramide and triacylglycerols are also included. Ceramides and TAG cannot be referred to in the glycerophospholipid class.
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