Cross-linked pair of polymer chains under strong tension

TL;DR

This paper analyzes the elastic response and fluctuation suppression in two types of strongly stretched cross-linked polymer systems, providing analytic expressions and exploring crossover behaviors in binding regimes.

Contribution

It introduces analytic models for the tensile elasticity and fluctuation suppression in cross-linked polymers and a novel approach to polymer necklace binding behavior under tension.

Findings

Cross-linking suppresses transverse fluctuations without affecting tensile elasticity.

Analytic force--extension relations are derived for different polymer models.

Crossover between weak and strong binding regimes is characterized in polymer necklaces.

Abstract

We study two cross-linked polymer systems in the strong stretching regime. The first consists of two polymers sharing one endpoint, with the other two endpoints coupled by a harmonic potential. Within the weakly bending approximation, we analyze the tensile elastic response for freely jointed or wormlike chains; for the latter, the approximation applies either at large tension or at moderate tension with large persistence length (rodlike limit). We obtain analytic expressions for the force--extension relation and for the longitudinal and transverse mismatch of the cross-linked endpoints. In the thermodynamic limit, the cross-link does not affect the tensile elasticity, but it significantly suppresses transverse fluctuations, effectively forming a loop structure. The second system is a polymer necklace in the thermodynamic limit, composed of two strongly stretched polymers interconnected by a regular sequence of reversible cross-links. Using an analogy with a two-dimensional system of concatenated Gaussian loops ("Gaussian slinky"), we calculate the mean fraction of cross-linked sites as a function of the tensile force and find weak and strong binding regimes connected by a crossover. For shallow binding potential wells (compared with $k_{\rm{B}}T$), we employ a continuum description and exploit the mapping between directed polymers and a two-dimensional quantum particle to determine the crossover behavior and the mean transverse separation between the two polymer chains.