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 aggregates. It is deduced that the main reason for the ellipse-to-vesicle transition of the aggregates is attributed to the breakage of ordered and dense packing of PBLG rods in the aggregate core by encapsulating AuNPs. This study deepens our understanding of the self-assembly behavior of rod-coil copolymer/nanoparticle mixtures and provides strategy for designing hybrid polypeptide nanostructures.
Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology , Shanghai 200237, China.
Chaoying
C
Yang
Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology , Shanghai 200237, China.
Qing
Q
Li
Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology , Shanghai 200237, China.
Chunhua
C
Cai
Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology , Shanghai 200237, China.
Jiaping
J
Lin