Stabilization of anionic adducts in negative ion electrospray mass spectrometry

Attachment of small anions to neutral molecules is an important ionization mechanism in negative ion electrospray mass spectrometry. In this report, the tendency for different anions to remain attached to selected analyte compound classes has been systematically investigated. A rationale for the formation and stability of preferred anionic adducts is proposed in light of thermodynamic considerations. A series of collision-induced dissociation experiments reveals that the gas-phase basicities of the deprotonated analyte molecule (M - H]-) and the anion moiety play important roles in determining the stability of anionic adducts. Adducts of the form M - H]-...H+...anion]- manifest increased stability when the two anions have similar gas-phase basicities. Within certain limitations, the difference in deltaG degrees values for proton combination with M - H]- and with anion]- can be used as a first-order predictor of adduct stability. In addition, stability increases with the rising gas-phase basicities of the two moieties. The specific interaction between a small inorganic anion (bisulfate) and a neutral analyte molecule (alpha-D-glucose) in the form of multiple hydrogen bonding has also been affirmed by computer modeling to contribute to the stability of some anionic adducts. Last, the gas-phase basicity of deprotonated alpha-D-glucose (i.e., the gas-phase acidity of alpha-D-glucose) is determined by a "bracketing method" to be in the range of 1373-1407 kJ/mol.