Towards the Rational Design of Ionic Liquid Matrices for Secondary Ion Mass Spectrometry: Role of the Anion

The role of the ionic liquid (IL) anion structure on analyte signal enhancements has been systematically investigated in secondary ion mass spectrometry (SIMS) using a variety of samples, including lipids, sterols, polymers, and peptides. Twenty-four ILs were synthesized. The 12 matrix acids were cinnamic acid derivatives. Two bases were employed: 1-methylimidazole and tripropylamine. Three matrices, methylimmidazolium o-coumarate, tripropylammonium o-coumarate, and tripropylammonium 3,4,5-trimethoxycinnamate, were “universal” matrices enhancing all analytes tested. The pK_a of the matrix acid does not appear to have a strong effect on analyte ion intensities. Rather, it is observed that a single hydroxyl group on the anion aromatic ring leads to significantly increased molecular ion intensities. No analyte signal enhancements were observed for –CH₃, –CF₃ and –OCH₃ groups present on the aromatic ring. The position of the –OH group on the aromatic ring also alters molecular ion intensity enhancements. As well as the chemical identity and position of substituents, the number of moieties on the aromatic ring may affect the analyte signal enhancements observed. These observations suggest that the activation of the IL anion aromatic ring is important for optimizing analyte signal intensities. The implications for SIMS imaging of complex structures, such as biological samples, are discussed.