Thermodynamics of the Complexation of the p-Sulfonatocalix[4]arene with Simple Model Guests in Water: a Microcalorimetric Study

The formation of supramolecular complexes in water involves interactions of various types which are not always easy to identify, especially when complicated species are involved. A complete thermodynamic characterization of the binding process, which includes the enthalpies and entropies of complexation, is obviously one of the key elements in identifying the stabilizing factors and in understanding how the host and guest assemble. In order to thermodynamically characterize typical interactions of various types, we have thus undertaken a microcalorimetric study of the complexation of p-sulfonatocalixarenes with simple guests bearing different functional groups. Association constants, free energies, enthalpies and entropies for the complexation of the p-sulfonatocalix[4]arene with normal alcohols, alkylammonium, carboxylate and guanidinium ions in water, at pH 7.5 and 298.15 K, are reported. The properties for the binding of lysine and arginine, which bear similar functional groups, are also given. The comparison of the thermodynamic behaviour of these different guests allows the driving factors to be identified. This may constitute a starting point for the understanding of the recognition of more complicated guests.