Fluoroalcohols as novel buffer components for basic buffer solutions for liquid chromatography electrospray ionization mass spectrometry: Retention mechanisms

Two fluoroalcohols – 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (HFTB) – were evaluated as volatile buffer acids in basic mobile phases for LC–ESI-MS determination of acidic and basic compounds. HFIP and HFTB as acidic buffer components offer interesting possibilities to adjust retention behavior of different analytes and expand the currently rather limited range of ESI-compatible buffer systems for basic mobile phases. Comparing with commonly used basic buffer components the fluoroalcohols did not suppress the ionization of the analytes, for several analytes ionization enhancement was observed. RP chromatographic retention mechanisms were evaluated and compared to traditional buffer system. All trends in retention of the acidic and basic analytes can be interpreted by the following model: the neutral fluoroalcohols are quite strongly retained by the stationary phase whereas their anions are less retained, thus their amount on the stationary phase is dependent on mobile phase pH; the anions of the fluoroalcohols form ion pairs in the mobile phase with the basic analytes; the fluoroalcohols on the stationary phase surface compete with acidic analytes thereby hindering their retention; the fluoroalcohols on the stationary phase bind basic analytes thereby favoring their retention.

► HFIP and HFTB result in complex RP retention behavior of analytes.
► The retention of basic analytes is enhanced due to ion pairing ability.
► The retention of acidic analytes is decreased, due to the repulsion.
► This work shows ability to expand range of ESI buffer systems.