Synthesis and Directed One-Dimensional Self-Assembly of Dumbbell-Shaped Single-Chain Particles

Abstract

Dumbbell-shaped single-chain particles (DSCPs) with distinct sphere-rod-sphere morphology were synthesized through intrachain photo-crosslinking of anthracene-functionalized polymer chains within an ABA triblock copolymer precursor, where the polymer chains are tethered at both sides of the middle comb-like block. The amphiphilic nature of the DSCPs, arising from the spatial segregation of hydrophilic spheres and hydrophobic rods, drives their self-assembly in mixed THF/H₂O solvent systems. The self-assembly behavior can be modulated by adjusting the rod-to-sphere volume ratio, leading to one-dimensional (1D) nanostructures with fiber-like and supercoiled morphologies. The rigidity imparted by both the intrachain crosslinked spherical heads and the hydrophobic rod ensures directional stacking and assembly, facilitating the formation of ordered 1D nanostructures. This study highlights the critical role of both the rigidity imparted by the crosslinking and the distinct shape-amphiphilicity of the DSCPs in directing their self-assembly into 1D nanostructures, offering valuable insights into the design of anisotropic nanomaterials for applications in nanomedicine, nanocomposites, and functional nanodevices.