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Competitive molecular-/ion-recognition responsive characteristics of poly(N-isopropylacrylamide-co-benzo-12-crown-4-acrylamide) copolymers with benzo-12-crown-4 as both guest and host units.

Novel dual molecular- and ion-recognition responsive poly(N-isopropylacrylamide-co-benzo-12-crown-4-acrylamide) (PNB12 C4 ) linear copolymers with benzo-12-crown-4 (B12C4) as both guest and host units are prepared. The copolymers exhibit highly selective sensitivities toward γ-cyclodextrin (γ-CD) and Na(+) . The presence of γ-CD induces the lower critical solution temperature (LCST) of PNB12 C4 copolymer to shift to a higher value due to the formation of 1:1 γ-CD/B12C4 host-guest inclusion complexes, while Na(+) causes a negative shift in LCST due to the formation of 2:1 "sandwich" B12C4/Na(+) host-guest complexes. Regardless of the complexation order, when γ-CD and Na(+) coexist with PNB12 C4 , competitive complexation actions of B12C4 as both guest and host units toward γ-CD and Na(+) finally form equilibrium 2:2:1 γ-CD/B12C4/Na(+) composite complexes, and the final LCST values of PNB12 C4 copolymer reach almost the same level. The results provide valuable guidance for designing and applying PNB12 C4 -based smart materials in various applications.