Structure elucidation

Paterno-Buchi photochemistry for lipid double-bond localization

Couple lipid photochemical derivatization to tandem MS to locate carbon-carbon double bonds.

Angewandte Chemie International Edition · 2014 · 10.1002/anie.201310699

Direct-infusion MSLipidomicsStructure elucidation

What does this strategy enable?

The defining approach converts unsaturated lipids into oxetane reaction products. Collision-induced fragmentation of those products yields diagnostic ions that report double-bond position.

Transferable workflow

Workflow

  1. 1

    Photochemically modify lipid double bonds

    The original implementation irradiates a nanoelectrospray plume containing lipids and acetone with UV light.

  2. 2

    Fragment reaction products

    Acquire tandem mass spectra of the derivatized lipids using collision activation.

  3. 3

    Interpret diagnostic fragments

    Assign candidate double-bond locations from the oxetane-cleavage products.

Evidence of reuse

Published implementations and adaptations

These papers applied, adapted, extended, benchmarked or formalized the Strategy after its originating publication. They are examples of precedent, not a ranking of software choices.

Extension · Proceedings of the National Academy of Sciences · 2016

Identification and quantitation of lipid C=C location isomers: A shotgun lipidomics approach enabled by photochemical reaction

Extends the photochemical method to identification and quantitation in complex lipid mixtures. Tissue comparisons are use cases, not additional Strategies.

doi:10.1073/pnas.1523356113

Strategy profile

Related objectives

Chemical-reactivity profiling

Components

Sample preparation, Data acquisition, Annotation or identification

Scope and considerations

Designed for

  • Locating double bonds in unsaturated lipids.

Important requirements

  • A compatible UV photoreaction and tandem-MS setup.

Considerations

  • This is photochemical derivatization, distinct from gas-phase ozone-induced dissociation.
  • Do not assume that software written for OzID interprets these spectra.

Reusable resources

✓ Published method available

Publication

Ma X, Xia Y. Pinpointing Double Bonds in Lipids by Paternò-Büchi Reactions and Mass Spectrometry. Angewandte Chemie International Edition 53, 2592–2596 (2014).

doi:10.1002/anie.201310699

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