Thin-Layer Chromatography/Desorption Atmospheric Pressure Photoionization Orbitrap Mass Spectrometry of Lipids.

Desorption atmospheric pressure photoionization (DAPPI) allows surface analysis in the open atmosphere and is thus an appropriate method for the direct coupling of thin-layer chromatography (TLC) and mass spectrometry (MS). Here, the capability of DAPPI-MS for ionizing and detecting lipids, namely, cholesterol, triacylglycerols, 1,2-diol diesters, wax esters, cholesteryl esters, and hydrocarbons, from TLC and high-performance thin-layer chromatography (HPTLC) plates in MS and MS2 modes was tested. Limits of detection for lipid standards separated using normal-phase (NP)-TLC and NP-HPTLC were established. TLC/DAPPI-MS was applied for lipids of vernix caseosa, a white creamy proteolipid biofilm that progressively coats the fetus during the last trimester of the pregnancy, and plant oils including caraway, parsley, safflower, and jojoba oils. Various lipids were identified by means of high resolution/accurate mass measurement of Orbitrap and comparison of the retardation factors with standards. Lipid class separation was carried out on the NP-HPTLC plates, whereas individual triacylglycerol and wax ester species were separated on the reversed-phase HPTLC plates. DAPPI-MS was found to be a simple, rapid, and efficient approach for detecting lipids separated by TLC.