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

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, Pz, 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 Pz, 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.