A multiscale mechanics model for disordered biopolymer gels containing junction zones with variable length

Disordered biopolymer gels, such as those synthesized from polysaccharide and gelatin, play an important role in biomedical applications, particularly in tissue engineering. During the gelation process of these gels, polymer chains associate in the presence of gelling agents, forming physical cross-links known as the junction zones. In contrast to rubber-like networks, the resulting network comprises two main regions: the ordered region due to the junction zones and the amorphous region due to the unassociated chains. Under thermal fluctuations and/or external loading, the number and locations of junction zones can change leading to “zipping” (lengthening, i.e., expansion of the junction zones) and “unzipping” (shortening, i.e., shrinkage of the junction zones). This gives rise to intriguing features in biopolymer gels such as healing and damage-like energy dissipation. Despite the recognition of zipping and unzipping in such gels, the development of mathematical models that incorporate the microscopic mechanisms into the material’s macroscopic mechanical properties is still in its early stages. In this paper, we provide a systematic framework for such multiscale modeling. Several critical steps are taken to equip the eight-chain network model with a previously developed micromechanics model for a coil–rod structure, where the coil represents an unassociated chain and the rod represents a junction zone. Most importantly, for a network of coil–rod structures under zero stress, the rigidity induced by the rod leads to an end-to-end distance ($r_0$) for the coil–rod which is different from a classical result for a Gaussian coil: $\sqrt{n}b$ where $b$ is the Kuhn length and $n$ is the number of Kuhn segments in the coil. By relaxing the incompressible assumption in the original eight-chain model, $r_0$ is determined for the gel network, which depends on the length of the junction zone. Consequently, as the junction zone extends/shrinks following zipping/unzipping under an external load, an irreversible deformation can occur after unloading, consistent with experimentally observed “permanent set”. The extension/shrinkage of the junction zone is captured by statistical mechanics analysis in the grand canonical ensemble, which allows the exchange of segments between the coil and the rod, driven by the binding energy of polymer chain association. The model also includes explicit consideration of swelling and the influence of solvent molecules as a result of their mixing with the polymer chains in the gel network. With physically reasonable parameters, the proposed model is shown to provide good matching with experimental data on the uniaxial testing of alginate gels, revealing progressive unzipping during loading and partial re-zipping during unloading leading to the appearance of a permanent set. This formulation not only paves the way for more advanced studies of disordered biopolymer gels but also lays the groundwork for modeling hybrid gels that contain coil–rod structures as a component.