β-Cyclodextrin Host−Guest complexes probed under thermodynamic equilibrium: thermodynamics and AFM force spectroscopy

The rupture forces of individual host−guest complexes between β-cyclodextrin (β-CD) heptathioether monolayers on Au(111) and several surface-confined guests were measured in aqueous medium by single molecule force spectroscopy using an atomic force microscope. Anilyl, toluidyl, tert-butylphenyl, and adamantylthiols (0.2−1%) were immobilized in mixed monolayers with 2-mercaptoethanol on gold-coated AFM tips. For all guests and for all surface coverages, the force−displacement curves measured between the functionalized tips and monolayers of β-CD exhibited single, as well as multiple, pull-off events. The histograms of the pull-off forces showed several maxima at equidistant forces, with force quanta characteristic for each guest of 39 ± 15, 45 ± 15, 89 ± 15, and 102 ± 15 pN, respectively. These force quanta were independent of the loading rate, indicating that, because of the fast complexation/decomplexation kinetics, the rupture forces were probed under thermodynamic equilibrium. The force values followed the same trend as the free binding energy ΔG° measured for model guest compounds in solution or on β-CD monolayers, as determined by microcalorimetry and surface plasmon resonance measurements, respectively. A descriptive model was developed to correlate quantitatively the pull-off force values with the ΔG° of the complexes, based on the evaluation of the energy potential landscape of tip−surface interaction.