Effects of solvent quality and non-equilibrium conformations on polymer translocation.

Abstract

The conformation and its relaxation of a single polymer depend on solvent quality in a polymer solution: a polymer collapses into a globule in a poor solvent, while the polymer swells in a good solvent. When one translocates a polymer through a narrow pore, a drastic conformational change occurs such that the kinetics of the translocation is expected to depend on the solvent quality. However, the effects of solvent quality on the translocation kinetics have been controversial. In this study, we employ a coarse-grained model for a polymer and perform Langevin dynamics simulations for the driven translocation of a polymer in various types of solvents. We estimate the free energy of polymer translocation using steered molecular dynamics simulations and Jarzynski's equality and find that the free energy barrier for the translocation increases as the solvent quality becomes poorer. The conformational entropy contributes most to the free energy barrier of the translocation in a good solvent, while a balance between entropy and energy matters in a poor solvent. Interestingly, contrary to what is expected from the free energy profile, the translocation kinetics is a non-monotonic function of the solvent quality. We find that for any type of solvent, the polymer conformation stays far away from the equilibrium conformation during translocation due to an external force and tension propagation. However, the degree of tension propagation differs depending on the solvent quality as well as the magnitude of the external force: the tension propagation is more significant in a good solvent than in a poor solvent. We illustrate that such differences in tension propagation and non-equilibrium conformations between good and poor solvents are responsible for the complicated non-monotonic effects of solvent quality on the translocation kinetics.