The solvent composition induced reentrant behavior of poly(N-isopropylacrylamide) (PNIPAM) chains grafted on a SiO2 surface in water-methanol mixtures was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D) at 20 °C. The frequency and energy dissipation responses showed that the grafted PNIPAM chains sharply collapse when the methanol content (xm) reaches 17 mol %. In the range 17-50 mol %, the grafted chains remain in a collapsed state. Further increase of the methanol content leads to an abrupt reswel領(lǐng) of the collapsed chains at xm > 50 mol %. The sharp reentrant swel領(lǐng)-to-collapse-to-swel領(lǐng) transition was attributed to the water-methanol complexation instead of the preferential adsorption effect. Our results also suggest that the water-methanol complexation is not induced by hydrophobic interaction but by hydrogen bonding.
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