Abstract:
© 2019 The Royal Society of Chemistry. Hydration history was found to control the inclusion capacity of α-cyclodextrin (aCD) for volatile organic guests, so that its level may be switched from zero to the stoichiometric value and back by the variation of aCD hydration/dehydration order and direction. Such variation of the inclusion capacity is caused by the balance of two water roles: the activation of guest inclusion and guest/water competition. These observed concurrent roles and the cooperativity of guest inclusion and hydration make possible the smart tuning of the guest inclusion by the subtle change of preparation procedure. Depending on the hydration history, aCD was shown to form hydrates with the same water contents but different packing types and different kinetics of dehydration, which correlates with their different inclusion capacities for organic guests. This correlation reveals how the "high-energy" and "low-energy" water works in the guest inclusion by aCD, which may be relevant for other cyclodextrins and hydrophilic receptors of biomimetic and biological natures. The results can help to rationalize the technologies of producing various inclusion compounds of cyclodextrins.