Random walks and polygons are used to model polymers. In this paper we consider the extension of writhe, self-linking number and linking number to open chains. We then study the average writhe, self-linking and linking number of random walks and polygons over the space of configurations as a function of their length. We show that the mean squared linking number, the mean squared writhe and the mean squared self-linking number of oriented uniform random walks or polygons of length n, in a convex confined space, are of the form O(n 2 ). Moreover, for a fixed simple closed curve in a convex confined space, we prove that the mean absolute value of the linking number between this curve and a uniform random walk or polygon of n edges is of the form O( √ n). Our numerical studies confirm those results. They also indicate that the mean absolute linking number between any two oriented uniform random walks or polygons, of n edges each, is of the form O(n). Equilateral random walks and polygons are used to model polymers in θ-conditions. We use numerical simulations to investigate how the self-linking and linking number of equilateral random walks scale with their length.

In this manuscript, we introduce a method to measure entanglement of curves in 3-space that extends the notion of knot and link polynomials to open curves. We define the bracket polynomial of curves in 3-space and show that it has real coefficients and is a continuous function of the curve coordinates. This is used to define the Jones polynomial in a way that it is applicable to both open and closed curves in 3-space. For open curves, the Jones polynomial has real coefficients and it is a continuous function of the curve coordinates and as the endpoints of the curve tend to coincide, the Jones polynomial of the open curve tends to that of the resulting knot. For closed curves, it is a topological invariant, as the classical Jones polynomial. We show how these measures attain a simpler expression for polygonal curves and provide a finite form for their computation in the case of polygonal curves of 3 and 4 edges.

No abstract

We propose a method to estimate N(e), the entanglement length, that incorporates both local and global topological characteristics of chains in a melt under equilibrium conditions. This estimate uses the writhe of the chains, the writhe of the primitive paths, and the number of kinks in the chains in a melt. An advantage of this method is that it works for both linear and ring chains, works under all periodic boundary conditions, does not require knowing the contour length of the primitive paths, and does not rely on a smooth set of data. We apply this method to linear finitely extendable nonlinear elastic chains and we observe that our estimates are consistent with those from other studies.

We employ a primitive path (PP) algorithm and the Gauss linking integral to study the degree of entanglement and knotting characteristics of linear polymer model chains in a melt under the action of a constant pulling force applied to selected chain ends. Our results for the amount of entanglement, the linking number, the average crossing number, the writhe of the chains and their PPs and the writhe of the entanglement strands all suggest a different response at the length scale of entanglement strands than that of the chains themselves and of the corresponding PPs. Our findings indicate that the chains first stretch at the level of entanglement strands and next the PP (tube) gets oriented with the "flow." These two phases of the extension and alignment of the chains coincide with two phases related to the disentanglement of the chains. Soon after the onset of external force the PPs attain a more entangled conformation, and the number of nontrivially linked end-to-end closed chains increases. Next, the chains disentangle continuously to attain an almost unentangled conformation. Using the linking matrix of the chains in the melt, we furthermore show that these phases are accompanied by a different scaling of the homogeneity of the global entanglement in the system. The homogeneity of the end-to-end closed chains first increases to a maximum and then decreases slowly to a value characterizing a completely unlinked system.

We develop topological methods for characterizing the relationship between polymer chain entanglement and bulk viscoelastic responses. We introduce generalized Linking Number and Writhe characteristics that are applicable to open linear chains. We investigate the rheology of polymeric chains entangled into weaves with varying topologies and levels of chain density. To investigate viscoelastic responses, we perform non-equilibrium molecular simulations over a range of frequencies using sheared Lees–Edwards boundary conditions. We show how our topological characteristics can be used to capture key features of the polymer entanglements related to the viscoelastic responses. We find there is a linear relation over a significant range of frequencies between the mean absolute Writhe W r and the Loss Tangent tan ( δ ) . We also find an approximate inverse linear relationship between the mean absolute Periodic Linking Number L K P and the Loss Tangent tan ( δ ) . Our results show some of the ways topological methods can be used to characterize chain entanglements to better understand the origins of mechanical responses in polymeric materials.

F ocusing on a small set of proteins that i) fold in a concerted, all-or-none (twostate) fashion and ii) do not contain knots or slipknots, we show that the Gauss linking integral, the torsion and the number of sequence-distant contacts provide information regarding the folding rate. Our results suggest that the global topology/geometry of the proteins shifts from right-handed to left-handed with decreasing folding rate, and that this topological change is associated with an increase in the number of more sequence-distant contacts.

We define the local periodic linking number, LK, between two oriented closed or open chains in a system with three-dimensional periodic boundary conditions. The properties of LK indicate that it is an appropriate measure of entanglement between a collection of chains in a periodic system. Using this measure of linking to assess the extent of entanglement in a polymer melt we study the effect of CReTA algorithm on the entanglement of polyethylene chains. Our numerical results show that the statistics of the local periodic linking number observed for polymer melts before and after the application of CReTA are the same.