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Simultaneous Characterization of Lipid sn-Positional and Double-Bond Positional Isomers using On-Demand Electrochemical Mass Spectrometry

We
present an on-demand electrochemical mass spectrometry workflow for lipid
structural characterization with the capability of identifying double-bond and sn-positional
isomers. Two voltage-controlled
electrochemical reactions, interfacial electro-epoxidation and anodic corrosion
of a cobalt electrode, are cascaded in this strategy. The epoxidized products and
Co-adducted ions of lipids are fragmented in tandem MS to generate structure
characteristic fragments that indicate double-bond and sn-positions. The
unique feature of this workflow lies in the sequential localization of double
bonds, elucidation of sn-positions,
and collection of native lipid information in a single system and simply by tuning
ESI voltages. This feature, as well as low sample consumption, no need for
extra apparatus, and quantitative analysis, should allow wide applications in the
lipidomic field.