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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry

Background:

  • Ionization and fragmentation are fundamental to mass spectrometry.
  • In-source fragmentation can occur, affecting data quality.
  • A 2005 review established a baseline for understanding internal energy and fragmentation in electrospray ionization (ESI) sources.

Purpose of the Study:

  • To review literature on internal energy and fragmentation in ESI sources since 2005.
  • To introduce new thermometer molecules for quantifying source heating.
  • To compare the 'softness' (internal energy) of various ambient pressure ionization sources.

Main Methods:

  • Literature survey of in-source fragmentation and ionization techniques.
  • Utilizing thermometer molecules to measure source temperatures.
  • Compiling threshold (E₀) and appearance energies (Eapp) for the survival yield method.
  • Comparing different ambient pressure ionization (API) sources based on ion internal energy.

Main Results:

  • Droplet size and desolvation dynamics significantly influence ion internal energy.
  • Methods producing smaller droplets without charging can be gentler than ESI.
  • New dielectric barrier discharge (DBD) sources show comparable low internal energy to ESI.
  • Source interface tuning is critical for controlling ion internal energy and fragmentation.

Conclusions:

  • Controlling in-source ion activation conditions is crucial for standardizing mass spectrometry data.
  • Understanding and managing internal energy transfer is key to ensuring data transferability and reproducibility.
  • Further research is needed to optimize ionization source design and operation for minimal fragmentation.