Formic Acid as a Dopant for Atmospheric Pressure Chemical Ionization for Negative Polarity of Ion Mobility Spectrometry and Mass Spectrometry.

Formic acid (FA) is introduced as a potent dopant for atmospheric pressure chemical ionization (APCI) for ion mobility spectrometry (IMS) and mass spectrometry (MS). The mechanism of chemical ionization with the FA dopant was studied in the negative polarity using a corona discharge (CD)-IMS-MS technique in air. Standard reactant ions of the negative polarity present in air are O 2 - ·(CO 2 ) n ·(H 2 O) m (m = 0, 1 and n = 1, 2) clusters. Introduction of the FA dopant resulted in the production of HCOO - ·FA reactant ions. The effect of the FA dopant on the APCI of different classes of compounds was investigated, including plant hormones, pesticides, acidic drugs, and explosives. FA dopant APCI resulted in deprotonation and/or adduct ion formation, [M - H] - and [M + HCOO] - , respectively. Supporting density functional theory (DFT) calculations showed that the ionization mechanism depended on the gas-phase acidity of the compounds. FA dopant APCI led to the improvement of detection sensitivity, suppression of fragmentation, and changes in the ion mobilities of the analyte ions for analytes with suitable molecular structures and gas acidity.