Molecular simulation of the diffusion mechanism of nanorods in cross-linked networks

We study the diffusion of rod-shaped nanocarriers with different rigidities and aspect ratios in cross-linked networks using coarse-grained molecular dynamics (CGMD) simulations. The diffusivity of the nanorods increases with a reduction in the rigidities of the nanorods and network, as well as with an increasing aspect ratio with respect to the same volume fraction of the nanorods. The nanorods show an anisotropic diffusion pathway through translocating along their major axes at short time scales, and the anisotropy of diffusion decreases at long time scales. Meanwhile, the diffusion of the nanorods shows a sub-diffusion regime that deviates from Brownian motion in most cases due to the trapping of the nanorods in a cage composed of the network. The nanorod could hop when it escapes from the cage and the hopping behavior depends on the rigidities of both the nanorod and network, as well as the local network density. The rotational motion of the trapped nanorod also enhances the probability of hopping. Our results may help in the understanding of the microscopic mechanism for the diffusion of rod-shaped and other relevant nanocarriers, in a cross-linked network environment.