Subdiffusion of sticky dendrimers in an associative polymer network

TL;DR

This study uses simulations to explore how dendrimers move and deform in associative polymer networks, revealing how stickiness and interactions influence their subdiffusive behavior and network structure.

Contribution

It provides new insights into the effects of dendrimer-network interactions on diffusion and network deformation, incorporating hydrodynamic effects and comparing sticky versus non-sticky dendrimers.

Findings

Sticky dendrimers exhibit subdiffusive motion at high attraction strengths.

Non-sticky dendrimers shrink with increasing network concentration.

Dendrimer interactions significantly alter local network mesh size.

Abstract

We investigate the static and dynamic properties of dendrimers diffusing through a network of linear associative polymers using coarse-grained Brownian dynamics simulations. Both dendrimers and network chains are modelled as bead-spring chain polymers, with hydrodynamic interactions incorporated for the accurate prediction of dynamic properties. Linear chains form a network via the associating groups distributed along their backbones, and the dendrimers interact attractively or repulsively with the network, enabling a direct comparison of sticky and non-sticky behaviour of dendrimers. Structural analysis reveals that while non-sticky dendrimers shrink with increasing network concentration, similar to linear polymer behaviour, sticky dendrimers exhibit stretching at low concentrations due to binding interactions. Dendrimer dynamics are largely insensitive to network architecture but are strongly influenced by the strength of dendrimer-network interactions. Increasing attraction to the network leads to subdiffusive motion and non-Gaussian displacement statistics, even when dendrimers are smaller than the average mesh size. The long-time diffusivity aligns with theoretical predictions for nanoparticle transport in polymer networks. Additionally, dendrimers deform the network locally, altering the mesh size distribution depending on their stickiness. These findings offer insight into the interplay between macromolecular architecture, binding interactions, and transport in polymeric environments.