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AES is a powerful analytical technique, especially effective when used with plasma sources, producing abundant spectra in characteristic emission lines. The Inductively Coupled Plasma (ICP), in particular, yields superior quantitative analytical data due to its high stability, low noise, low background, and minimal interferences under optimal experimental conditions. However, newer air-operated microwave sources are emerging as promising alternatives that could be more cost-effective than...
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How Soft Is Secondary Electrospray Ionization?

Jérôme Kaeslin1, Cedric Wüthrich1, Stamatios Giannoukos1

  • 1Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland.

Journal of the American Society for Mass Spectrometry
|September 16, 2022
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Summary

Secondary electrospray ionization (SESI) mass spectrometry is a soft ionization technique. However, standard instrument settings are harsh; soft tuning is essential for optimal performance in metabolomics and breath analysis.

Keywords:
annotationin-source fragmentationsecondary electrospray ionizationsoft ionizationthermometer ions

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Area of Science:

  • Analytical Chemistry
  • Physical Chemistry

Background:

  • Secondary electrospray ionization (SESI) mass spectrometry (MS) is a direct infusion technique used for untargeted metabolomics, particularly in online breath analysis.
  • SESI is considered a soft ionization method, crucial for minimizing in-source fragments and simplifying compound annotation.

Purpose of the Study:

  • To investigate the internal energy distribution of ions produced by SESI.
  • To evaluate SESI's softness compared to electrospray ionization (ESI) and assess the impact of instrument settings.

Main Methods:

  • Utilized benzylammonium ions as thermometer ions with known bond dissociation enthalpies.
  • Employed in-source collision-induced dissociation (CID) experiments.

Main Results:

  • Demonstrated that SESI is softer than ESI.
  • Revealed that standard MS instrument settings in SESI are often too harsh for optimal soft ionization.
  • Provided evidence for analyte solvation under soft SESI conditions, supporting the ligand switching mechanism.

Conclusions:

  • SESI qualifies as a soft ionization technique, but requires proper instrument tuning to leverage its full potential.
  • Optimized SESI conditions are critical for accurate metabolomics and breath analysis.
  • Findings support the ligand switching mechanism in SESI.