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Adduct Formation in ESI/MS by Mobile Phase Additives.

Anneli Kruve1, Karl Kaupmees2

  • 1Institute of Chemistry, University of Tartu, Ravila 14a, Tartu, 50411, Estonia. anneli.kruve@ut.ee.

Journal of the American Society for Mass Spectrometry
|March 17, 2017
PubMed
Summary

Controlling adduct formation in electrospray ionization mass spectrometry (ESI/MS) is challenging. Mobile phase additives effectively manipulate adduct formation efficiencies, significantly enhancing sensitivity and repeatability for bases.

Keywords:
Ammonium adductsElectrosprayIonization efficiencyMobile phase additivesSodium adducts

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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry

Background:

  • Adduct formation is a key ionization technique in electrospray ionization mass spectrometry (ESI/MS).
  • The mechanisms governing adduct formation are not fully understood, making control difficult.

Purpose of the Study:

  • To investigate the control of adduct formation using mobile phase additives in ESI positive mode.
  • To evaluate the impact of additives on the formation efficiencies of various adducts for 17 oxygen and nitrogen bases.

Main Methods:

  • Electrospray ionization mass spectrometry (ESI/MS) in positive mode.
  • Systematic variation of mobile phase additives for 17 oxygen and nitrogen bases.
  • Quantification of adduct formation efficiencies, including sodium adducts [M + Na]+ and protonated molecules [M + H]+.

Main Results:

  • Mobile phase additives significantly influence adduct formation efficiencies, with potential sensitivity increases up to three orders of magnitude.
  • Sodium adduct formation was more sensitive to mobile phase properties than protonated molecule formation.
  • While highest formation efficiencies were in un-added water/acetonitrile, additives improved repeatability.

Conclusions:

  • Mobile phase additives are powerful tools for manipulating adduct formation in ESI/MS.
  • Additives offer a means to enhance sensitivity and improve the reproducibility of adduct formation.
  • Careful selection of additives is crucial for optimizing ESI/MS experiments.