Macromolecules, Vol.42, No.4, 1321-1330, 2009
Temperature- and Tension-Induced Coil-Globule Transition of Poly(N-isopropylacrylamide) Chains in Water and Mixed Solvent of Water/Methanol
The concept of cooperative dehydration, defined as the simultaneous dissociation of the water Molecules bound in correlated sequences to a polymer chain, has been applied to study the collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating in aqueous solutions. We examined the applicability of this concept in three situations: (i) PNIPAM in water (in the absence of added force), (ii) PNIPAM in water Subjected to a tension applied to the chain ends, and (iii) PNIPAM in a mixed solvent of water and a second water-miscible solvent. The transition becomes sharper as the cooperativity parameter of hydration increases. The tension-elongation curve of a hydrated chain at various temperatures, calculated following an approach similar to the classical theory of coil - helix transition, presents a flat plateau corresponding to the tension for which collapsed segments reel out of the globules. The reeled-out segments are hydrated immediately upon exposure to water. The calculations suggest a possible shift to higher temperatures of the cloud points of aqueous PNIPAM solutions under shear flow. The reentrant coil-globule-coil transition in mixed solvent of water and methanol is studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer methanol.