Molecular insights on Poly(N-isoproylacrylamide) coil-to-globule transition induced by pressure

Abstract

Poly-N-isopropylacrylamide (PNIPAM) phase diagram is explored in a wide range of temperature and pressure using extensive all-atom molecular dynamics simulations. By exploiting a simple model of an atactic linear polymer chain, we provide novel insights into PNIPAM coil-to-globule transition addressing the roles played by both temperature and pressure. We find that a coil-to-globule transition exists up to large pressures, undergoing an intriguing reentrant behavior of the lower critical solution temperature with increasing pressure in agreement with experimental observations. Furthermore, we report the existence of a new kind of globular state at high pressures, again confirming experimental results: this is characterized by a more structured hydration shell, that is closer to PNIPAM hydrophobic domains, with respect to the atmospheric pressure counterpart. Our results clearly show that temperature and pressure induce PNIPAM coil-to-globule transition through different molecular mechanisms, opening the way for a systematic use of both thermodynamic parameters to tune the location of the transition and the properties of the associated swollen/collapsed states.

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• Phenol release from pNIPAM hydrogels: Scaling Molecular Dynamics simulations with Dynamical Density Functional Theory
• Modulating internal transition kinetics in responsive macromolecules by collective crowding