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Multiple-stage linear ion-trap with high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum.

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 MS(n) 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 MS(n) 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.

SUBMITTER: Hsu FF

PROVIDER: S-EPMC4007172 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Multiple-stage linear ion-trap with high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum.

Hsu Fong-Fu FF Kuhlmann F Matthew FM Turk John J Beverley Stephen M SM

Journal of mass spectrometry : JMS 20140301 3

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 MS(n) on both the ...[more]

PMID: 24619546

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Project description:Linear ion-trap multiple-stage mass spectrometric approach (MS(n)) towards nearly complete structural elucidation of triacylglycerol (TAG) including (1) assignment the fatty acid substituents on the glycerol backbone and (2) location of the double bond(s) on the unsaturated fatty acyl groups is reported. The characterization is established by the findings that MS(2) on the [M + Li](+) ions of TAG yields more abundant ions reflecting losses of the outer fatty acid substituents either as free acids (i.e., [M + Li - R(1)CO(2)H](+) and [M + Li - R(3)CO(2)H](+) ions) or as lithium salts (i.e., [M + Li - R(1)CO(2)Li](+) and [M + Li - R(3)CO(2)Li](+) ions) than the ions reflecting the similar losses of the inner fatty acid substituent (i.e., [M + Li - R(2)CO(2)Li](+) and [M + Li - R(2)CO(2)Li](+) ions). Further dissociation (MS(3) of [M + Li - R(n)CO(2)H](+) (n = 1, 2, or 3) gives rise to the ion series locating the double bonds along the fatty acid chain. These ions arise from charge-remote fragmentations involving beta-cleavage with gamma-H shift, analogous to those seen for the unsaturated long-chain fatty acids characterized as initiated ions. Significant differences in abundances in the ion pairs reflecting the additional losses of the fatty acid moieties, respectively, were also seen in the MS(3) spectra of the [M + Li - R(n)CO(2)H](+) and [M + Li - R(n)CO(2)Li](+) ions, leading to confirmation of the fatty acid substituents on the glycerol backbone. MS(n) on the [M + Na](+) and [M + NH(4)](+) adduct ions also affords location of fatty acid substituents on the glycerol backbone, but not the position of the double bond(s) along the fatty acid chain. Unique ions from internal losses of the glycerol residues were seen in the MS(3) spectra of [M + Alk - R(n)CO(2)H](+) (n = 1, 2, 3) and of [M + Alk - R(n)CO(2)Alk](+) (Alk = Li, Na, NH(4); n = 1, 3). They are signature ions for glycerides and the pathways leading to their formation may involve rearrangements.

Dataset Information

Multiple-stage linear ion-trap with high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum.

Publications

Multiple-stage linear ion-trap with high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum.

Similar Datasets

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