Effects of solvent and counterion on ion pairing and observed charge states of diquaternary ammonium salts in electrospray ionization mass spectrometry

Two diquaternary ammonium chloride salts have been used to examine the roles of solvent and counterion in determination of the degree of ion pairing in solution and the resultant charge state distributions in electrospray ionization mass spectrometry (ESI-MS). Three series of solvents, that is, alcohol, polar aprotic, and chlorinated solvents, have been employed to test the influence of solvent polarity and other parameters on the desorption behavior of diquaternary ammonium ions observed in ESI-MS. Solvents of higher polarity were found to yield gas-phase ions of higher charge states, in accordance with their reduced tendency toward ion pairing in solution. Counterion effects were investigated via the following approaches: (1) increase the diquaternary ammonium salt concentration; (2) increase the concentration of an external electrolyte that contained the common counterion Cl^?; (3) replace Cl^? with trifluoroacetate (TFA_c ^?); (4) increase the concentration of an external electrolyte that contained TFAc^?. These experiments indicate that variation of the specific counterion employed alters the degree of influence that the counterion exerts (via ion pairing) on electrospray ionization mass spectra. Increasing amounts of trifluoroacetate ions in a variety of solvent systems invariably led to a progressive shift of the observed ESI-MS charge states of diquaternary ammonium ions toward lower values.