A topologically driven glass in ring polymers.

The static and dynamic properties of ring polymers in concentrated solutions remains one of the last deep unsolved questions in polymer physics. At the same time, the nature of the glass transition in polymeric systems is also not well understood. In this work, we study a novel glass transition in systems made of circular polymers by exploiting the topological constraints that are conjectured to populate concentrated solutions of rings. We show that such rings strongly interpenetrate through one another, generating an extensive network of topological interactions that dramatically affects their dynamics. We show that a kinetically arrested state can be induced by randomly pinning a small fraction of the rings. This occurs well above the classical glass transition temperature at which microscopic mobility is lost. Our work both demonstrates the existence of long-lived inter-ring penetrations and realizes a novel, topologically induced, glass transition.

Slow Dynamics of Ring Polymer Melts by Asymmetric Interaction of Threading Configuration: Monte Carlo Study of a Dynamically Constrained Lattice Model.

Abnormally slower diffusional processes than its internal structure relaxation have been observed in ring polymeric melt systems recently. A key structural feature in ring polymer melts is topological constraints which allow rings to assume a threading configuration in the melt phase. In this work, we constructed a lattice model under the assumption of asymmetric diffusivity between two threading rings, and investigated a link between the structural correlation and its dynamic behavior via Monte Carlo simulations. We discovered that the hierarchical threading configurations render the whole system to exhibit abnormally slow dynamics. By analyzing statistical distributions of timescales of threading configurations, we found that the decoupling between internal structure relaxation and diffusion is crucial to understand the threading effects on the dynamics of a ring melt. In particular, in the limit of small but threaded rings, scaling exponents of the diffusion coefficient D and timescale τ diff with respect to the degree of polymerization N agree well with that of the annealed tree model as well as our mean-field analysis. As N increases, however, the ring diffusion abruptly slows down to the glassy behavior, which is supported by a breakdown of the Stokes⁻Einstein relation.

Ring Polymers: Threadings, Knot Electrophoresis and Topological Glasses.

Elucidating the physics of a concentrated suspension of ring polymers, or of an ensemble of ring polymers in a complex environment, is an important outstanding question in polymer physics. Many of the characteristic features of these systems arise due to topological interactions between polymers, or between the polymers and the environment, and it is often challenging to describe this quantitatively. Here we review recent research which suggests that a key role is played by inter-ring threadings (or penetrations), which become more abundant as the ring size increases. As we discuss, the physical consequences of such threadings are far-reaching: for instance, they lead to a topologically-driven glassy behaviour of ring polymer melts under pinning perturbations, while they can also account for the shape of experimentally observed patterns in two-dimensional gel electrophoresis of DNA knots.