Springer Online Journal Archives 1860-2000
Chemistry and Pharmacology
Abstract The complexation process between gentian violet (CV+) and four different cyclodextrins (α-, β-, γ-, and HP-β-CDs) has been investigated under different reaction conditions (pH, solvent, and temperature) by electronic absorption and 1H NMR (NOE and NOESY) spectroscopies. All the binding constants were determined by the direct spectroscopic method. The ΔH and ΔS complexation values have been evaluated and discussed according to the diverse factors that affect the chemical interactions in these systems. A simple association takes place between the secondary hydroxyl or the hydroxypropyl groups of α and HP-β-cycloamyloses, respectively, with the amine group of the gentian violet, while the binding between CV+ and β- or γ-CDs corresponds to a real inclusion. Also, a CV22+ dimmeric species within the γ-CD cavity was detected in aqueous solution, while two molecules of α-CD react with one molecule of gentian violet in DMSO at 294 K. In all the reaction media the β-CD forms 1 : 1 complexes, but in the buffered aqueous solution at pH 7.5 the inclusion is deeper than in the other solvents. It is important to point out that the solvophobic effect is the most important binding factor in the complexation of the CV+ with the α- and HP-β-CDs, while the complexes with β-, and γ-cyclodextrins are mainly stabilized by van der Waals interactions between the guest and the host cavity. In all cases, the inclusion orientation is probably determined by the ion-dipole interactions between gentian violet and the solvent.
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