A Novel Thermoresponsive Hydrogel with Ion-Recognition Property through Supramolecular Host−Guest Complexation

Abstract

A novel thermoresponsive hydrogel with ion-recognition property was prepared via free-radical cross-linking copolymerization of N-isopropylacrylamide (NIPAM) with benzo-18-crown-6-acrylamide (BCAm) as host receptor. Both chemical structures and stimuli-sensitive properties of the prepared poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) P(NIPAM-co-BCAm) hydrogel were characterized. The smart hydrogel could respond to both temperature and ion stimuli. When the crown ether units captured Ba²⁺ and formed stable BCAm/Ba²⁺ host−guest complexes, the lower critical solution temperature (LCST) of the hydrogel increased due to the repulsion among charged BCAm/Ba²⁺ complex groups and osmotic pressure within the hydrogel. Whereas crown ethers captured Cs⁺, the LCST shifted to a lower temperature because of the formation of 2:1 sandwich complexes. Unexpectedly, the LCST of the cross-linked P(NIPAM-co-BCAm) hydrogel in K⁺ solution did not shift to a higher temperature, which was definitely different from the previously reported linear P(NIPAM-co-BCAm) copolymer in K⁺ solution. The results of this work provide valuable information for development of dual thermo- and ion-responsive hydrogels which have potential applications in drug controlled-release systems or biomedical fields.