Symmetry breaking during the formation of beta-cyclodextrin-imidazole inclusion compounds: capillary electrophoresis study.
A mathematical model was developed for the estimation of binding constants by capillary electrophoresis. The effective electrophoretic mobility in a solute mixture is dependent on the cyclodextrin concentration in the background electrolyte (BGE) as well as the stoichiometry and the binding constant of the guest-cyclodextrin complex. As well, a determination of the degree of complexation, nc (the percent of complexed guest) could be carried out. The model was applied to a series of imidazole derivatives. Thermodynamic data for the solute complexation mechanism were calculated. Different van't Hoff plot shapes of the degree of complexation were observed with different BGE pH values, indicating a change in the solute complexation mechanism. Enthalpy-entropy compensation revealed that the solute complexation mechanism was independent of the imidazole derivative molecular structure, the same at pH = 4.5, 5.0, 5.5, 6.0, and 6.5 but changed at pH = 7.0 and 7.5. Topological defects formed during a symmetry-breaking transition could be responsible for the modification of the structure of the cyclodextrin cavity and explained the nc variations in relation to pH and temperature.
Guillaume
Y C
YC
Laboratoire de Chimie Analytique, Faculté de Médecine et de Pharmacie, Besançon, France.
Peyrin
E
E
D000465:Algorithms; D003505:Cyclodextrins / Q000737:chemistry*; D019075:Electrophoresis, Capillary; D007093:Imidazoles / Q000737:chemistry*; D008962:Models, Theoretical; D012997:Solvents; D047392:beta-Cyclodextrins
D003505:Cyclodextrins; D007093:Imidazoles; D012997:Solvents; D047392:beta-Cyclodextrins; C031215:betadex