Gaseous acidity and basicity scales as guides to chemical ionization in reversed-phase liquid chromatography-mass spectrometry with direct liquid introduction.
During direct liquid introduction (DLI) liquid chromatography-mass spectrometry (LC-MS), the detectability of acetone is shown to be predictable, based on consideration of the gas-phase acidities and basicities of solvents methanol and acetonitrile and modifiers formic acid and ammonium formate. Consequently, ion formation in DLI LC-MS resembles gas-phase chemical ionization processes; since the order of acidities is altered in solution, solution ionization must be much less important than gas-phase. Ion populations could be predicted on the basis of gas-phase proton affinities and acidities: acetone could be detected in all solvent mixture by positive ions, but it was not readily detected by negative ions when acid was also present. In solvents without additives it was always detected.
D000097:Acetonitriles / Q000032:analysis; D002853:Chromatography, Liquid / Q000379:methods*; D006863:Hydrogen-Ion Concentration; D013058:Mass Spectrometry; D000432:Methanol; D012997:Solvents
D000097:Acetonitriles; D012997:Solvents; D000432:Methanol; C032159:acetonitrile