Importance of gas-phase proton affinities in determining the electrospray ionization response for analytes and solvents.
The effect of gas-phase proton transfer reactions on the mass spectral response of solvents and analytes with known gas-phase proton affinities was evaluated. Methanol, ethanol, propanol and water mixtures were employed to probe the effect of gas-phase proton transfer reactions on the abundance of protonated solvent ions. Ion-molecule reactions were carried out either in an atmospheric pressure electrospray ionization source or in the central quadrupole of a triple-quadrupole mass spectrometer. The introduction of solvent vapor with higher gas-phase proton affinity than the solvent being electrosprayed caused protons to transfer to the gas-phase solvent molecules. In mixed solvents, protonated solvent clusters of the solvent with higher gas-phase proton affinity dominated the resulting mass spectra. The effect of solvent gas-phase proton affinity on analyte response was also investigated, and the analyte response was suppressed or eliminated in solvents with gas-phase proton affinities higher than that of the analyte.
Department of Chemistry, University of New Mexico, Albuquerque 87131-1096, USA.
M H
MH
Amad
N B
NB
Cech
G S
GS
Jackson
C G
CG
Enke
D001274:Atmospheric Pressure; D005740:Gases; D013058:Mass Spectrometry / Q000379:methods*; D011522:Protons; D012997:Solvents
D005740:Gases; D011522:Protons; D012997:Solvents