title: GC separation of enantiomers of alkyl esters of 2-bromo substituted carboxylic acids enantiomers on 6-TBDMS-2,3-di-alkyl- β- and γ-cyclodextrin stationary phases.
abstract: The gas chromatographic separation of enantiomers of 2-Br carboxylic acid derivatives was studied on four different 6-TBDMS-2,3-di-O-alkyl- β- and -γ-CD stationary phases. The differences in thermodynamic data {ΔH and -ΔS} for the 15 structurally related racemates were evaluated. The influence of structure differences in the alkyl substituents covalently attached to the stereogenic carbon atom, as well as in the ester group of the homologous analytes, and the selectivity of modified β- and γ- cyclodextrin derivatives was studied in detail. The cyclodextrin cavity size, as well as elongation of alkyl substituents in positions 2 and 3 of 6-TBDMS-β-CD, also affected their selectivity. The quality of enantiomeric separations is influenced mainly by alkyl chains of the ester group of the molecule and this appears to be independent of the CD stationary phase used. In some cases the separations occur as the result of external adsorption rather than inclusion complexations with the chiral selector. It was found that the temperature dependencies of the selectivity factor were nonlinear.
authors.affiliation: Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Bratislava, Slovak Republic.
authors.forename: Ivan
authors.initials: I
authors.lastname: Spánik
authors.forename: Darina
authors.initials: D
authors.lastname: Kačeriaková
authors.forename: Jan
authors.initials: J
authors.lastname: Krupčík
authors.forename: Daniel Wayne
authors.initials: DW
authors.lastname: Armstrong
mesh_terms: D001966:Bromine / Q000737:chemistry; D002264:Carboxylic Acids / Q000302:isolation & purification*; D002849:Chromatography, Gas; D004952:Esters / Q000302:isolation & purification*; D012833:Siloxanes / Q000737:chemistry*; D013237:Stereoisomerism; D013343:Styrenes / Q000737:chemistry*; D013816:Thermodynamics; D047392:beta-Cyclodextrins / Q000737:chemistry*; D047408:gamma-Cyclodextrins / Q000737:chemistry*
chemical_list: C506477:4-(tert-butyldimethylsiloxy)styrene; D002264:Carboxylic Acids; D004952:Esters; D012833:Siloxanes; D013343:Styrenes; D047392:beta-Cyclodextrins; D047408:gamma-Cyclodextrins; C023792:gamma-cyclodextrin; D001966:Bromine
keywords: 6-TBDMS-2,3-alkyl- β- and γ-cyclodextrins; capillary GC; chiral recognition; enantiomer separation