APPI (Supplementary Information)

APPI process

Energetics for Photoionization

PhotoMateTM lamp

Krypton 10.0 eV and 10.6 eV

Ionization Potentials (IP)

Anthracene 7.4 eV*

Fluoranthene 7.8 eV*

Caffeine 8.0 eV*

4-Nitrotoluene 9.5 eV*

2,4,6-Trinitrotoluene 10.59 eV

Dopant Ionization Potentials

Toluene 8.82 eV*

Acetone 9.70 eV*

Solvent Ionization Potentials

Methanol 10.85 eV

Acetonitrile 12.19 eV

Water 12.61 eV


* Ionized by Kr UV photons    


  • The photons from the Kr lamp can only photoionize compounds of lower IP
  • Common HPLC solvents (H2O, CH3OH and CH3CN) are NOT ionized and therefore cannot aid ion formation
  • In this circumstance, only direct photoionization of the analyte can yield characteristic ions such as M+.  (not very efficient)
    • subsequent ion/molecule reactions can form [M+H]+
  • Dopants are used that will be ionized by the Kr lamp