Rapid conformational fluctuations in a model of methylcellulose

Abstract

Methylcellulose is a thermoresponsive polymer that undergoes a morphological transition at elevated temperature, forming uniform diameter fibrils. However, the gelation mechanism is still unclear, in particular, at higher polymer concentrations. We use Langevin dynamics simulations to investigate a coarse-grained model for methylcellulose that produces collapsed ringlike structures in dilute solution with a radius close to the fibrils observed in experiments. We show that the competition between the dihedral potential and self-attraction causes these collapsed states to undergo a rapid conformational change, which helps the chain to avoid kinetic traps by permitting a transition between collapsed states. If the dihedral potential is removed, the chains do not escape from their collapsed configuration, whereas at high dihedral potentials, the chains cannot stabilize the collapsed state. We provide systematic data on the effect of the dihedral potential in a model of methylcellulose, and discuss the implication of these previously overlooked rapid conformational fluctuations on the spontaneous formation of high-aspect-ratio fibrils.