Dissipative particle dynamics simulations of H-shaped diblock copolymer self-assembly in solvent

We examine the self-assembly of H-shaped block-copolymers as the function of the middle block to branch length ratio and interaction between the middle and branch blocks differing in their solvophobicity. The work shows that the examined H-shaped polymers readily transition from uniform mixing of the polymer species to domain formation and a variety of advanced assembly configurations including vesicles, onion-like, and multicompartment aggregates. We identify the polymer conformational and packing changes involved to extract governing interactions and molecule features giving rise to the different assembly structures. The findings are discussed in terms of the H-shaped polymer architecture and polymer assemblies. We conclude that the assembly structure is governed by the molecular level local curvature induced by the varying conformations of the polymers. The findings highlight that for H-shaped polymers the degree of polymerization and polymer chemistries in terms of solvation and mixing characteristics of the blocks are keys to controlling the assembling structures. [Display omitted] ●Computer modelling reveals guidelines for tuning assembly of H-shaped polymers.●Assembly phase diagram for self-assembling structures reported.●Interactions governing assembly structure and design guidelines for it extracted.