Noncovalent Postmodification Guided Reversible Compartmentalization of Polymeric Micelles

Abstract

Compartmentalized micelles (CMs) are promising tailor-made soft matters that mimic natural designed structures and functions. Despite the structure of complex CMs, manipulating CM structures accessibly and reversibly remains elusive. Here, we report the fabrication of CMs via a generally valid noncovalent postmodification process. Starting from precursor micelles (PMs) based on one diblock copolymer, aromatic modification leads to the compartmentalization of PMs into well-defined spherical CMs. Control over compartment number, size and distribution in CMs, and segment distribution in their linear hierarchical assemblies is attained by simply tuning the postmodification degree and solvent composition. We also demonstrate the reversible transformation between PM and CMs during several heating–cooling cycles, which endows the micelles with potential in reversible functional transitions in situ close to nature’s capability. Moreover, both hierarchically assembled or ill-structured micelles can rearrange into homogeneous CMs after one heating–cooling cycle, featuring the postmodification guided compartmentalization strategy with unprecedented micelle reproducibility.

Controllable Copolymerization of Polymeric Micelles for the Construction of Supramolecular Chains

“…One-dimensional (1D) nanomaterials are of special interest due to their promising properties in a diverse range of applications. − Enthusiastic efforts have been devoted to fabricating 1D nanomaterials. − Recently, stepwise self-assembly has emerged as an effective bottom-up approach, wherein the hierarchical structures are closely related to the precise control of the precursors. − In a pioneer work, Müller and co-workers proposed a strategy for creating programmable multicompartment structures. , A variety of supracolloidal polymers were obtained from preassembled micelles with tunable patches by substantially changing the solution environment, which emphasizes the importance of the morphological control of the micellar subunits. − Chen and co-workers provided a noncovalent postmodification strategy of mixing aromatic modifiers to manipulate the compartmentalization process of precursor micelles . These micelles can further assemble into 1D linear mesoscale chains via attraction among insoluble compartments, and the assembly pathway also depends on their structures.…”

“…19−21 Chen and co-workers provided a noncovalent postmodification strategy of mixing aromatic modifiers to manipulate the compartmentalization process of precursor micelles. 22 These micelles can further assemble into 1D linear mesoscale chains via attraction among insoluble compartments, and the assembly pathway also depends on their structures.…”