Polymer hydrogels are known to be efficient absorbents of various aqueous solutions. Along with the hydrophilicity of the polymer network, the presence of specific functional groups is required for the absorption of respective solutes. Alternatively, a selective uptake can be realized without any specific attraction of solutes to the network, which is shown in this paper. By combining experimental and simulation approaches, we demonstrated that thermoresponsive poly(N-isopropylacrylamide) gels and microgels in compositionally strongly asymmetric water/1-octanol mixtures selectively uptake the minor (1-octanol) component. Initially swollen in water, the gels substitute water by the organic solvent upon the addition of its small fraction into aqueous solution. In turn, for microgels, it was shown that the single particles could absorb the amount of the organic liquid more than two times higher than their mass while preserving the colloidal stability. At the same time, the accumulation of 1-octanol in the networks "switches off" the temperature response. The mesoscopic computer simulations revealed a physical reason and molecular picture of the phenomenon. Absorption of the minor component by the gels is caused by the decrease in water/1-octanol interfacial tension due to the formation of the dense polymer layer at the interface. The simulations allowed tracking the evolution of the size and the internal structure of the single microgels with changing 1-octanol concentration.
Keywords: hydrogel; immiscible liquids; microgel; selective absorption; soft matter; thermoresponsive polymer.