Characterization of acyl chain position in unsaturated phosphatidylcholines using differential mobility-mass spectrometry |
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Authors: | Alan T Maccarone Jackson Duldig Todd W Mitchell Stephen J Blanksby Eva Duchoslav J Larry Campbell |
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Institution: | *School of Chemistry University of Wollongong, New South Wales 2522, Australia;†School of Medicine, University of Wollongong, New South Wales 2522, Australia;§Central Analytical Research Facility, Queensland University of Technology, Queensland 4000, Australia;**AB SCIEX, Concord, Ontario L4K 4V8, Canada |
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Abstract: | Glycerophospholipids (GPs) that differ in the relative position of the two fatty acyl chains on the glycerol backbone (i.e., sn-positional isomers) can have distinct physicochemical properties. The unambiguous assignment of acyl chain position to an individual GP represents a significant analytical challenge. Here we describe a workflow where phosphatidylcholines (PCs) are subjected to ESI for characterization by a combination of differential mobility spectrometry and MS (DMS-MS). When infused as a mixture, ions formed from silver adduction of each phospholipid isomer {e.g., PC (16:0/18:1) + Ag]+ and PC (18:1/16:0) + Ag]+} are transmitted through the DMS device at discrete compensation voltages. Varying their relative amounts allows facile and unambiguous assignment of the sn-positions of the fatty acyl chains for each isomer. Integration of the well-resolved ion populations provides a rapid method (< 3 min) for relative quantification of these lipid isomers. The DMS-MS results show excellent agreement with established, but time-consuming, enzymatic approaches and also provide superior accuracy to methods that rely on MS alone. The advantages of this DMS-MS method in identification and quantification of GP isomer populations is demonstrated by direct analysis of complex biological extracts without any prior fractionation. |
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Keywords: | lipid isomers sn-positional isomers mass spectrometry differential mobility spectrometry |
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