Simulation study on the effect of polydisperse nanoparticles on polymer diffusion in crowded environments

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 41; pp. 28252 - 28262
• Main Authors: Hua, Dao-Yang, Luo, Meng-Bo
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 25.10.2023
• Subjects: Adsorption; Chains (polymeric); Cubic lattice; Diffusion coefficient; Nanoparticles; Polydispersity; Polymers
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp03641c

The diffusion of polymer chains in a crowded environment with large and small immobile, attractive nanoparticles (NPs) is studied using Langevin dynamics simulations. For orderly distributed NPs on the simple cubic lattice, our results show that the diffusion of polymer chains is dependent on the NP-NP distance or lattice distance d . At low d where NPs are placed closely, subdiffusion occurs at a sufficiently high polydispersity of NPs, PD. Both the apparent diffusion coefficient and subdiffusion exponent of polymer chains decrease with increasing PD, attributed to the adsorption of polymers on NP clusters formed by larger NPs. At large d , normal diffusion is always observed, and the diffusion coefficient increases with increasing PD. The reason is that, at high PD, the difference between single large NP adsorption and double large NP adsorption is reduced, which increases the exchange of a polymer between the two adsorption states. Finally, the impact of size polydispersity of NPs on the diffusion of polymer chains in a crowded environment with randomly distributed NPs is also investigated. The results show that the position disorder of NPs enhances the subdiffusion of the system. Polymer chains sub-diffuse at a sufficiently high polydispersity of nanoparticles due to the adsorption on nanoparticle clusters formed by larger nanoparticles. The disorder of nanoparticles enhances the subdiffusion of polymer chains.