A Novel, Smart Microsphere with K⁺-Induced Shrinking and Aggregating Properties Based on a Responsive Host–Guest System

A novel type of smart microspheres with K(+)-induced shrinking and aggregating properties is designed and developed on the basis of a K(+)-recognition host-guest system. The microspheres are composed of cross-linked poly(N-isopropylacrylamide-co-acryloylamidobenzo-15-crown-5) (P(NIPAM-co-AAB15C5)) networks. Due to the formation of stable 2:1 "sandwich-type" host-guest complexes between 15-crown-5 units and K(+) ions, the P(NIPAM-co-AAB15C5) microspheres significantly exhibit isothermally and synchronously K(+)-induced shrinking and aggregating properties at a low K(+) concentration, while other cations (e.g., Na(+), H(+), NH4(+), Mg(2+), or Ca(2+)) cannot trigger such response behaviors. Effects of chemical compositions of microspheres on the K(+)-induced shrinking and aggregating behaviors are investigated systematically. The K(+)-induced aggregating sensitivity of the P(NIPAM-co-AAB15C5) microspheres can be enhanced by increasing the content of crown ether units in the polymeric networks; however, it is nearly not influenced by varying the monomer and cross-linker concentrations in the microsphere preparation. State diagrams of the dispersed-to-aggregated transformation of P(NIPAM-co-AAB15C5) microspheres in aqueous solutions as a function of temperature and K(+) concentration are constructed, which provide valuable information for tuning the dispersed/aggregated states of microspheres by varying environmental K(+) concentration and temperature. The microspheres with synchronously K(+)-induced shrinking and aggregating properties proposed in this study provide a brand-new model for designing novel targeted drug delivery systems.