Determining the stoichiometry and binding constants of inclusion complexes formed between aromatic compounds and β-cyclodextrin by solid-phase microextraction coupled to high-performance liquid chromatography

The complexation of native beta-cyclodextrin (CD) and seven aromatic compounds, namely, phenetole, toluene, m-xylene. naphthalene, biphenyl, fluorene and phenanthrene, has been studied for first time utilizing a solid-phase microextraction (SPME)-high-performance liquid chromatography (HPLC) method. The stoichiometries of the analyte: beta-CD complexes were found to be either 1:1 or 1:2. The formation of 1:2 complexes was confirmed for naphthalene, biphenyl. fluorene, and phenanthrene only when utilizing relatively high concentrations of beta-CD (up to 6.6 mM). The 1:2 stoichiometries were confirmed using the classical modified Benesi-Hildebrand (BH) method. The calculated binding constants for 1: 1 stoichiometries (K-1) using the SPME method varied from 115.3 M-1 for toluene to 3510 M-1 for phenanthrene whereas the corresponding values to the 1:2 stoichiometries (K-3) varied from 7.30 x 10(5) M-2 for biphenyl to 9.03 x 10(6) M-2 for naphthalene. (C) 2009 Elsevier B.V. All rights reserved.