The use of dicationic ion‐pairing compounds to enhance the ambient detection of surface lipids in positive ionization mode using desorption electrospray ionisation mass spectrometry

Abstract

RATIONALE: Lipids are typically analysed in negative ionisation mode in desorption electrospray ionisation mass spectrometry (DESI-MS), which can result in reduced sensitivity. In this study we examine the use of dicationic compounds as reactive DESI-MS agents to detect a range of lipid standards from the surface in positive ionisation mode. METHODS: Nine dicationic compounds were tested for their ability to detect seven representative lipid species (palmitoleic acid, linoleic acid, phosphatidic acid (34:1), phosphoethanolamine (34:2), phosphatidylglycerol (34:1), phosphatidylserine (36:1), and phosphoinositol (34:2)) with a 2D DESI source on hydrophobic surfaces. Two different solvent systems (methanol/chloroform (1:1) and methanol) were tested with each dicationic compound, with the DESI-MS analysis performed in the positive ionisation mode. RESULTS: Most of the dications tested were able to form stable ion-pairs with the negatively charged lipid species when analysed from the surface with DESI-MS, and were detected readily in positive ionisation electrospray mode as singly charged species. The optimal solvent system was found to be methanol. The dicationic compound [C6(C1Pyrr)2][Br]2 was found to enhance the detection of palmitoleic acid (638%), linoleic acid (304%) and phosphoethanolamine (269%) compared with the negative ionisation mode. CONCLUSIONS: We demonstrate the first successful application of dicationic compounds in DESI-MS for the ambient surface detection of model lipids in positive electrospray ionisation mode. Dicationic compounds could potentially be used as reactive DESI-MS agents to improve the ambient detection of a number of negatively charged analytes.