title: Accuracy and sensitivity of the determination of rate constants of interconversion in achiral and chiral environments by dynamic enantioselective electrophoresis.
abstract: The method for determination of rate constants of interconversion of enantiomers in chiral and achiral environments of a dynamic enantioseparation system was investigated in order to reveal its accuracy, sensitivity and robustness. Two significantly different enantioseparation systems were selected, one with a single (well-defined) chiral selector (CS) and the second with a mixture of CSs, and the rate constants of interconversion for these two systems were compared statistically. While the rate constants of interconversion in the chiral environment were found to be significantly different, the rate constants in achiral environment were confirmed to be statistically the same. The accuracy of the method was independent of experimental conditions. Influence of a CS and temperature on the rate of interconversion were discussed within the scope of determined thermodynamic parameters and statistical evaluation. A certain temperature may exist at which two different types of CSs influence the rate of interconversion equally while the extent of their influence may largely differ at other temperatures.
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Prague, Czech Republic.
authors.forename: Jana
authors.initials: J
authors.lastname: Svobodová
authors.forename: Pavel
authors.initials: P
authors.lastname: Dubský
authors.forename: Eva
authors.initials: E
authors.lastname: Tesařová
authors.forename: Bohuslav
authors.initials: B
authors.lastname: Gas
mesh_terms: D000465:Algorithms; D003505:Cyclodextrins; D004586:Electrophoresis / Q000379:methods*; D007700:Kinetics; D016014:Linear Models; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D003505:Cyclodextrins