Hydrogen Bonding Sequence Directed Coil-Globule Transition in Water Soluble Thermoresponsive Polymers

Abstract

The origin of the coil-globule transition for water-soluble thermoresponsive polymers frequently used in nanomaterials remains elusive. Using polypropylene oxide as an example we demonstrate by means of atomistic molecular dynamics simulations that temperature-induced increase in the sequence length of monomers that are not hydrogen bonded to water drives the coil-globule transition. Longer chains statistically exhibit longer sequences which serve as nucleation sites for hydrophobic cluster formation, facilitating chain collapse at lower temperature in agreement with experimental data.