On the effect of basic and acidic additives on the separation of the enantiomers of some basic drugs with polysaccharide-based chiral selectors and polar organic mobile phases

J Chromatogr A. 2013 Nov 22:1317:167-74. doi: 10.1016/j.chroma.2013.08.029. Epub 2013 Aug 13.

Abstract

This article reports the systematic study of the effect of basic and acidic additives on HPLC separation of enantiomers of some basic chiral drugs on polysaccharide-based chiral columns under polar organic mobile-phase conditions. In contrary to generally accepted opinion that the basic additives improve the separation of enantiomers of basic compounds, the multiple scenarios were observed including the increase, decrease, disappearance and appearance of separation, as well as the reversal of the enantiomer elution order of studied basic compounds induced by the acidic additives. These effects were observed on most of the studied 6 chiral columns in 2-propanol and acetonitrile as mobile phases and diethylamine as a basic additive. As acidic additives formic acid was used systematically and acetic acid and trifluoroacetic acid were applied for comparative purposes. This study illustrates that the minor acidic additives to the mobile phase can be used as for the adjustment of separation selectivity and the enantiomer elution order of basic compounds, as well as for study of chiral recognition mechanisms with polysaccharide-based chiral stationary phases.

Keywords: Basic chiral drugs; Chiral HPLC; Enantioseparations; Polysaccharide-based chiral stationary phases; The role of minor additives.

MeSH terms

  • Acetates / chemistry
  • Acetonitriles / chemistry
  • Amylose / analogs & derivatives
  • Amylose / chemistry*
  • Cellulose / analogs & derivatives
  • Cellulose / chemistry*
  • Chromatography, High Pressure Liquid / instrumentation*
  • Hydrogen-Ion Concentration
  • Pharmaceutical Preparations / chemistry*
  • Pharmaceutical Preparations / isolation & purification*
  • Stereoisomerism

Substances

  • Acetates
  • Acetonitriles
  • Pharmaceutical Preparations
  • Cellulose
  • Amylose
  • acetonitrile