Steady-State and Transient Behavior of Knotted Chains in Extensional Fields.

ABSTRACT

Recently, there has been a push to understand how molecular topology alters the nonequilibrium dynamics of polymer systems. In this paper, we probe how knotted polymers evolve in planar extensional fields using Brownian dynamics simulations and single-molecule experiments. In the first part of the study, we quantify the extension versus strain-rate curves of polymers and find that knots shift these curves to larger strain-rates. These trends can be quantitatively explained by Rouse-like scaling theories. In the second half of the study, we examine the consequences of knot untying on the time-dependent conformations of polymers in these external fields. We find that knot untying creates significant, transient changes in chain extension. If the topology is complex, the chain undergoes a wide range of time-dependent conformations since knot untying proceeds through many different stages. We provide examples of such untying trajectories over time.