Self-assembly of polymer-tethered nanoparticles with uniform and Janus surfaces in nanotubes

Abstract

In this study, a coarse-grained molecular simulation was performed to investigate the morphologies and phase diagrams of self-assembled polymer-tethered nanoparticles (NPs) confined in nanotubes (NTs). Unlike ordinary NPs, polymer-tethered NPs have two distinct characteristic lengths, which are key factors that determine their self-assembly. Herein, two distinct types of NT walls and three types of polymer-tethered NPs were considered: hydrophilic and hydrophobic walls, and hydrophilic, hydrophobic, and Janus surfaces. First, the qualitative phase diagrams of the axial pressure, P_z, versus the ratio of the NT radius to the NP radius, L, were derived. The results revealed that diverse self-assembled morphologies, which are not formed in non-tethered NPs, were observed in the polymer-tethered NPs. For example, three types of ordered structures with different structural characteristic lengths, depending on P_z, were obtained. In addition, the effect of the chemical nature of the polymer-tethered NP surface on the self-assembled morphology confined in NTs was investigated. Clusters of water molecules were formed, particularly in the hydrophobic polymer-tethered NPs, and these clusters caused the structural distortion of the NP. Moreover, in the polymer-tethered NPs with the Janus amphiphilic surface, the hydrophobic and hydrophilic polymer tethered NPs assembled in the axial direction to form an ordered structure, and a double-helix structure was formed at L = 3.0 in the hydrophobic NT. The results of these simulations indicate that the self-assembly behaviours of polymer-tethered NPs can be qualitatively predicted based on the chemical nature of the NT walls and the surface design of the polymer-tethered NP.