Enhanced Heterogeneous Diffusion of Nanoparticles in Semiflexible Networks

The transport of nanoparticles in semiflexible networks, which form diverse principal structural components throughout living systems, is important in biology and biomedical applications. By combining large-scale molecular simulations as well as theoretical analysis, we demonstrate here that nanoparticles in polymer networks with semiflexible strands possess enhanced heterogeneous diffusion characterized by more evident hopping dynamics. Particularly, the hopping energy barrier approximates to linear dependence on confinement parameters in the regime of moderate rigidity, in contrast to the quadratic dependence of both its soft and hard counterparts. This nonmonotonic feature can be attributed to the competition between the conformation entropy and the bending energy regulated by the chain rigidity, captured by developing an analytical model of a hopping energy barrier. Moreover, these theoretical results agree reasonably well with previous experiments. The findings bear significance in unraveling the fundamental physics of substance transport confined in network-topological environments and would provide an explanation for the dynamics diversity of nanoparticles within various networks, biological or synthetic.

Automated summary

Through large-scale molecular simulations and theoretical analysis, it was found that nanoparticles in polymer networks with semiflexible strands exhibit enhanced heterogeneous diffusion characterized by hopping dynamics, with the hopping energy barrier approximating to linear dependence on confinement parameters in the regime of moderate rigidity. This nonmonotonic feature is attributed to the competition between conformation entropy and bending energy regulated by chain rigidity.