Retention of acidic and basic analytes in reversed phase column using fluorinated and novel eluent additives for liquid chromatography-tandem mass spectrometry

J Chromatogr A. 2020 Feb 22;1613:460667. doi: 10.1016/j.chroma.2019.460667. Epub 2019 Nov 1.


This research focuses on retention mechanisms in a LC column with C18 stationary phase when novel eluent additives (HFIP, HFTB and TFE as well as NFTB and perfluoropinacol) are used. The retention factors between novel eluent additives and conventional ones like ammonium acetate and ammonium bicarbonate at different eluent pH values were compared. A simple set of drug-like molecules, widely spread over different logP values, containing protonated and deprotonated acids and bases was selected for this investigation. HFIP, HFTB, NFTB and PP demonstrated strong influence on basic polar analytes in basic medium. These additives drastically increased retention. A decrease in retention was observed for acidic analytes when novel eluent additives were used. Additionally, for the first time, the absolute pH (pHabs) scale was used for expressing the mobile phase pH.

Keywords: Eluent additives; HFIP; HFTB; NFTB; PP; Retention mechanisms.

MeSH terms

  • Acetates / chemistry
  • Acids
  • Bicarbonates / chemistry
  • Chromatography, Liquid*
  • Fluorocarbons / chemistry
  • Hydrogen-Ion Concentration
  • Tandem Mass Spectrometry*


  • Acetates
  • Acids
  • Bicarbonates
  • Fluorocarbons
  • ammonium bicarbonate
  • ammonium acetate