Multiple‐stage linear ion‐trap with high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum |
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Authors: | Fong‐Fu Hsu F. Matthew Kuhlmann John Turk Stephen M. Beverley |
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Affiliation: | 1. Mass Spectrometry Resource, Division of Endocrinology, Diabetes, Metabolism and Lipid Research, USA;2. Division of Infectious Diseases, Washington University School of Medicine, MO, USA;3. Department of Molecular Microbiology, Washington University School of Medicine, St. Louis, MO, USA |
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Abstract: | The structures of phosphatidylethanolamine (PE) in Leishmania infantum are unique in that they consist of a rare cyclopropane fatty acid (CFA) containing PE subfamily, including CFA‐containing plasmalogen PE species. In this contribution, we applied multiple‐stage linear ion‐trap combined with high‐resolution mass spectrometry to define the structures of PEs that were desorbed as [M – H]? and [M – H + 2Li]+ ions by ESI, respectively. The structural information arising from MSn on both the molecular species are complimentary, permitting complete determination of PE structures, including the identities of the fatty acid substituents and their location on the glycerol backbone, more importantly, the positions of the double bond(s) and of the cyclopropane chain of the fatty acid chain, directing to the realization of the CFA biosynthesis pathways that were reported previously. We also uncovered the presence of a minor dimethyl‐PE subclass that has not been previously reported in L. infantum. This LIT MSn mass spectrometric approach led to unambiguous identification of PE molecules including many isomers in complex mixture that would otherwise be very difficult to define using other analytical approaches. Copyright © 2014 John Wiley & Sons, Ltd. |
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Keywords: | phosphatidylethanolamine plasmenylethanolamine cyclopropane fatty acids linear ion‐trap mass spectrometry ESI Leishmania infantum Leishmania major |
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