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Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives

Journal Article


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Abstract


  • RATIONALE

    Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required.

    METHODS

    Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M + Na]+ ions that can be mass-selected and subjected to laser irradiation (λ = 266 nm) on a modified linear ion-trap mass spectrometer.

    RESULTS

    Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carbon–carbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M + Na – I]•+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carbon–carbon bond dissociation without scrambling of molecular information.

    CONCLUSIONS

    Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box.

Publication Date


  • 2013

Citation


  • Pham, H. T., Trevitt, A. J., Mitchell, T. W. & Blanksby, S. J. (2013). Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives. Rapid Communications in Mass Spectrometry, 27 (7), 805-815.

Scopus Eid


  • 2-s2.0-84875199852

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1524&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/512

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 805

End Page


  • 815

Volume


  • 27

Issue


  • 7

Place Of Publication


  • United Kingdom

Abstract


  • RATIONALE

    Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required.

    METHODS

    Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M + Na]+ ions that can be mass-selected and subjected to laser irradiation (λ = 266 nm) on a modified linear ion-trap mass spectrometer.

    RESULTS

    Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carbon–carbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M + Na – I]•+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carbon–carbon bond dissociation without scrambling of molecular information.

    CONCLUSIONS

    Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box.

Publication Date


  • 2013

Citation


  • Pham, H. T., Trevitt, A. J., Mitchell, T. W. & Blanksby, S. J. (2013). Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives. Rapid Communications in Mass Spectrometry, 27 (7), 805-815.

Scopus Eid


  • 2-s2.0-84875199852

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1524&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/512

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 805

End Page


  • 815

Volume


  • 27

Issue


  • 7

Place Of Publication


  • United Kingdom