Fluoroalkylamines: Novel, Highly Volatile, Fast-Equilibrating, and Electrospray Ionization–Mass Spectrometry Signal-Enhancing Cationic Ion-Interaction Reagents

[Image: see text] A new class of cationic ion-interaction reagents for reversed-phase chromatography is introduced in the present work. Compounds belonging to a homologous series of linear fluoroalkyl chains including trifluoroethylamine (TFEAm), pentafluoropropylamine (PFPAm), heptafluorobutylamine (HFBAm), and nonafluoropentylamine (NFPAm) were tested and compared with ammonia and triethylamine (TEA) for the separation of selected organic acids of general interest such as the herbicides glyphosate, ethephon, and fosamine and arsenic metabolites methylarsonic acid and dimethylarsinic acid as well as other compounds. Depending on the carbon and fluorine atom number, the fluoroalkylamines were shown to be effective cationic ion-interaction reagents, significantly enhancing the retention of organic acids on a C18 reversed-phase column. Contrary to the general behavior of ion-interaction reagents (a broader term than ion-pairing reagent), significant (up to 5-fold) and consistent enhancement in the electrospray ionization mass spectrometry signal (ESI-MS) was observed relative to ammonia and triethylamine. Overall, among the tested series HFBAm was found to offer the best overall properties among the tested series as it provided a good compromise between column equilibration time (ca. 25 column volumes) and retention behavior (up to a 10-fold increase in the retention factor of acids relative to ammonia) while providing the same general advantages found for the fluoroalkylamines such as fast washout times from the ESIMS system (ca. 30 min) and a 3–5-fold signal enhancement. The fluoroalkylamines are a new class of cationic ion-interaction reagents with clear advantages over the currently employed alkylamines and may revive the general interest in ion-interaction chromatography.