Effect of varying counterions on the sensitivity of electrohydrodynamic and fast atom bombardment mass spectrometry

  • Johnny D. Reynolds
  • Kelsey D. Cook


The abundance of ion pairs (CA+) relative to that of doubly charged ions (C2+) in electrohydrodynamic (EH) mass spectra of a series of anions with a common dication in glycerol was found to increase in the order acetate < nitrite < chloride < bromide ≈ nitrate < iodide < perchlorate. Correlation with enthalpies of hydration for the anions suggests that this trend reflects the solution chemistry of ion association. These spectra also reveal that solvation rather than interactions with the extracting field is more important in determining the overall EH mass spectrometric sensitivity to doubly charged ions. Therefore, the use of anions that promote more extensive ion pairing enhances the overall sensitivity to multiply charged ions that otherwise interact strongly with the solvent, but reduces sensitivity to singly charged ions. These observations hold in fast atom bombardment mass spectrometry, surviving the invasive effects of the primary beam.


Fast Atom Bombardment Diquat Fast Atom Bombardment Mass Spectrometry Ammonium Iodide Fast Atom Bombardment Ionization 
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Copyright information

© American Society for Mass Spectrometry 1990

Authors and Affiliations

  • Johnny D. Reynolds
    • 1
  • Kelsey D. Cook
    • 1
  1. 1.Department of ChemistryUniversity of TennesseeKnoxville

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