Nanoparticle-Induced Ellipse-to-Vesicle Morphology Transition of Rod–Coil–Rod Triblock Copolymer Aggregates

Cooperative self-assembly behavior of rod–coil–rod poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol)-block-poly(γ-benzyl-l-glutamate) (PBLG-b-PEG-b-PBLG) amphiphilic triblock copolymers and hydrophobic gold nanoparticles (AuNPs) was investigated by both experiments and dissipative particle dynamics (DPD) simulations. It was discovered that pure PBLG-b-PEG-b-PBLG copolymers self-assemble into ellipse-like aggregates, and the morphology transforms into vesicles as AuNPs are introduced. When the hydrophobicity of AuNPs is close to that of the copolymers, AuNPs are homogeneously distributed in the vesicle wall. While for the AuNPs with higher hydrophobicity, they are embedded in the vesicle wall as clusters. In addition to the experimental observations, DPD simulations were performed on the self-assembly behavior of triblock copolymer/nanoparticle mixtures. Simulations well reproduced the morphology transition observed in the experiments and provided additional information such as chain packing mode in a...