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Capillary atmospheric pressure chemical ionization using liquid point electrodes.

Sonja Klee1, Marco Thinius, Klaus J Brockmann

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Summary

This study introduces a new atmospheric pressure chemical ionization (APCI) source that uses a liquid effluent instead of a metal electrode. This novel APCI source provides stable operation and minimizes analyte ion fragmentation for enhanced mass spectrometry analysis.

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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry
  • Chemical Physics

Background:

  • Conventional atmospheric pressure chemical ionization (APCI) sources using point-to-plane DC discharges often face electrode degradation.
  • This degradation can lead to unwanted oxidation and fragmentation of analyte ions during mass spectrometry analysis.

Purpose of the Study:

  • To develop a novel APCI source that overcomes the limitations of traditional metal point electrodes.
  • To enhance the stability and reduce ion fragmentation in APCI mass spectrometry.

Main Methods:

  • Replaced the metal electrode with a liquid effluent from a fused-silica capillary, analogous to Taylor cone formation.
  • Utilized a nano-flow liquid delivery system (1-800 μL/h) with water or water/formic acid.
  • Directly coupled the source to mass spectrometers (e.g., Bruker Daltonics, Agilent).

Main Results:

  • Achieved controlled and highly stable source operation by continuously supplying reagent gas (H2O).
  • Observed analyte protonation as the primary ionization pathway with extremely low primary analyte fragmentation.
  • Demonstrated stable performance over extended operation periods.

Conclusions:

  • Developed a novel APCI source for hyphenating nano-flow liquid chromatography and gas chromatography with mass spectrometry.
  • The proposed electrochemical reaction mechanism explains the formation of protonated analyte molecules with minimal fragmentation.
  • The system offers exceptional stability and exclusive generation of protonated molecules.