Fusion Growth of Two-Dimensional Disklike Micelles via Liquid-Crystallization-Driven Self-Assembly

Abstract

Liquid-crystallization-driven self-assembly (LCDSA) is an emerging strategy for constructing nanoassemblies, such as 1D cylindrical micelles with LC-like micellar cores. However, it is still unknown whether LCDSA can be applied to higher-dimensional self-assembly. Herein, we realize the growth of two-dimensional (2D) disklike micelles via LCDSA and reveal its mechanism. Disklike seeds are constructed through the self-assembly of poly(γ-benzyl l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) block copolymers in solution. In the micellar core, the PBLG rod blocks take a smectic LC-like packing manner. After PBLG-b-PEG unimers are added into the seed solution, they first self-assemble into small aggregates. The aggregates then fuse with the seed edges to achieve the epitaxial growth of the disklike micelles. Brownian dynamic simulations reveal that the rod blocks in the small aggregates rearrange themselves to match the LC-like structure of the seed core in the growth process. The contour area of the disklike micelles is dependent on the unimer-to-seed ratio, and the 2D growth kinetics can be well controlled to construct concentric disklike micelles. The observed growth behavior of disklike micelles extends the LCDSA from 1D to 2D and can address the challenge of the precise manipulation of 2D nanostructures.