HPLC separation of enantiomers of chiral arylpropionic acid derivatives using polysaccharide‐based chiral columns and normal‐phase eluents with emphasis on elution order

Abstract

The separation of enantiomers of ten chiral arylpropionic acid derivatives was studied on six different polysaccharide-based chiral HPLC columns with various normal-phase eluents. Along with the successful separation of analyte enantiomers, the emphasis of this study was on the effect of the chiral selector and mobile phase composition as well as of the separation temperature on the elution order of enantiomers. The interesting phenomena of reversal of enantiomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature and position of the substituent(s) in the phenylcarbamate moiety, the polar modifier of the mobile phase (ethanol or 2-propanol), its content in the mobile phase, and separation temperature were investigated. In addition, an unusual increase in retention with increasing temperature was observed for some arylpropionic acid derivatives.

High-performance liquid chromatographic separation of unusual β3-amino acid enantiomers in different chromatographic modes on Cinchona alkaloid-based zwitterionic chiral stationary phases

“…However, on the ZWIX(−)™ column the behavior of 4, 10 and 16 was unique; k increased but α decreased, whereas increasing temperature. Increasing k and α values with increasing temperature were earlier observed for nonchiral separations (Adlof and List 2004;Wu et al 2004;and Yogo et al 2011) and recently also for separation of the enantiomers of neutral compounds (Matarashvili et al 2013) and zwitterionic compounds (Ilisz et al 2014b, c). It should be noted that this behavior was seen only on ZWIX(−)™ [not on ZWIX(+)™], indicating that the changes in the threedimensional structure and solvation of ZWIX(−)™ with temperature probably contribute to this unusual effect.…”

Investigation of Novel Cinchona Alkaloid-based Zwitterionic Chiral Stationary Phases in Cation- and Zwitterion-Exchange Modes

“…the k1 values increased with increasing temperature. This behavior was earlier registered in nonchiral separations [98][99][100] and for enantiomer separations [37,88] . This phenomenon was observed on ZWIX(-) Since the effect of temperature on the separation was complex, a detailed thermodynamic study may contribute to understand the mechanistic aspects of chiral recognition [97,[101][102][103] .…”

“…interactions, Hbonding and steric effects π-electron donor π-electron acceptor/π-electron donor [30] anion- [31] , cation- [32] zwitterionicexchange [33] ionic interaction polysaccharidebased cellulose [34,35] π-π, dipole-dipole, Hbonding and steric effects amylose [36,37] macrocyclic antibiotic-based macrocyclic glycopeptide [38,39] ionic, H-bonding, hydrophobic, dipoledipole, π-π-interaction, steric effects inclusion complexes modified cyclodextrin [40,41] complexation-, ionic interaction and steric effects crown ethers [42,43] CSPs derived from synthetic polymers polymers including vinyl, aldehyde, isocyanide, and acetylene polymers, condensation polymers including polyamides and polyurethanes, or cross-linked gels [44,45] steric effects molecularly imprinted polymers synthetic antibodies, enzymes, nucleic acid, hormones or glycoproteins [46,47] steric effects…”

Liquid Chromatography Enantioseparations of Halogenated Compounds on Polysaccharide‐Based Chiral Stationary Phases: Role of Halogen Substituents in Molecular Recognition

“…Three chiral halogenodienes iodo-(36), bromo- (37) and chlorosubstituted (38) were enantioseparated by Roussel and colleagues on three polysaccharide-based columns: Chiralpak IA, IB, and IC (250 × 4.6 mm). The atropisomerism of 1,3-butadienes is due to the hindered rotation around the central C 2 -C 3 bond.…”