Solvophobic effect of 1-alkyl-3-methylimidazolium chloride on the thermodynamic of complexation between β-cyclodextrin and dodecylpyridinium cation.

Abstract
Preferential solvation participate in various supramolecular self-assembly processes, whose thermodynamic properties can be modulated by the addition of ionic liquids (ILs). However, the effects of these liquids on the thermodynamics of the host-guest complexation process remain unexplored. In this study, the thermodynamic properties of the complexation between 1-dodecylpyridinium cations (C12Py+) and β-cyclodextrin (βCD) species in aqueous solutions with different concentrations of 1-alkyl-3-methylimidazolium halides (CnmimX) were investigated by isothermal titration calorimetry. In water, C12Py+ and βCD form a 1:1 inclusion complex, which is enthalpically ( −9.2 ± 0.1 kJ mol−1) and entropically ( 16.1 ± 0.2 kJ mol−1) favorable. However, in IL aqueous solutions, all the βCD―C12Py+ thermodynamic parameters of the complexation change and this IL effect is dependent on the carbon chain length of Cnmim+ cations. ILs with shorter alkyl chains (Cnmim+, n ≤ 4) decreases the system entropy, while ILs with longer alkyl chains (Cnmim+, n ≥ 6) reduce the enthalpy values. These effects are attributed to i) preferential solvation of surfactant tails by ILs; ii) ability of the ILs to modify the 3D water structure and iii) inclusion of IL molecules into the inner cavities of βCD.
Description
Keywords
Inclusion complex, Ionic liquids, Isothermal titration calorimetry, 1-Dodecylpyridinium chloride
Citation
AGUDELO, A. J. P. et al. Solvophobic effect of 1-alkyl-3-methylimidazolium chloride on the thermodynamic of complexation between β-cyclodextrin and dodecylpyridinium cation. Colloids and Surfaces A-Physicochemical and Engineering Aspects, v. 582, p. 123850, dez. 2019. Disponível em: <https://www.sciencedirect.com/science/article/pii/S0927775719308386>. Acesso em: 10 fev. 2020.