Abstract
The construction of hierarchical nanostructures with precise morphological and dimensional control has been one of the ultimate goals of contemporary materials science and chemistry, and the emulation of tailor-made nanoscale superstructures realized in the nature, using artificial building blocks, poses outstanding challenges. Herein we report a one-pot strategy to precisely synthesize hierarchical nanostructures through an in-situ initiation-growth process from a liquid crystalline block copolymer. The assembly process, analogous to living chain polymerization, can be triggered by small-molecule, macromolecule or even nanoobject initiators to produce various hierarchical superstructures with highly uniform morphologies and finely tunable dimensions. Because of the high degree of controllability and predictability, this assembly strategy opens the avenue to the design and construction of hierarchical structures with broad utility and accessibility.
Highlights
The construction of hierarchical nanostructures with precise morphological and dimensional control has been one of the ultimate goals of contemporary materials science and chemistry, and the emulation of tailor-made nanoscale superstructures realized in the nature, using artificial building blocks, poses outstanding challenges
The solution was held at 80 °C for 20 min and cooled to room temperature (20 °C), whereupon uniform cylindrical micelles are exclusively produced
As can be seen from the transmission electron microscopy (TEM, Fig. 1d) and atomic force microscopy (AFM, Fig. 1e), the initiation section in the middle of these cylindrical micelles appeared thicker than the growth sections at the two ends, resulted from the incorporation of phenylselenyl bromide (PhSeBr) in the initial stage of cylinder formation (Supplementary Figs. 1, 2)
Summary
The construction of hierarchical nanostructures with precise morphological and dimensional control has been one of the ultimate goals of contemporary materials science and chemistry, and the emulation of tailor-made nanoscale superstructures realized in the nature, using artificial building blocks, poses outstanding challenges. We report that a previously studied diblock copolymer illustrates striking and unforeseen combination of macromolecular and supramolecular assembly, providing an ideal system for the realization of a initiation-growth strategy, simultaneously producing hierarchical nanostructures with precisely controlled sizes and uniform morphologies This diblock copolymer P2VP68-b-PFMA41 (P2VP = poly(2-vinyl pyridine), PFMA = poly(2-(perfluorooctyl)ethyl methacrylate), the subscripts represent the numbers of repeating units) forms thermodynamic-favorable cylindrical micelles with a liquid crystalline (LC) micellar core from PFMA block[27,28,29]. We discover that by adding a small amount of initiators, which exhibits supramolecular interactions with the copolymer, the subsequent growth driven by the LC ordering effect of the copolymer can yield linear, branched, segmented, hairy plate-like, or star-like nanostructures in a one-pot manner This in situ initiated assembly approach, able to precisely tune the dimensions of resultant assemblies by carefully adjusting the initiator content and polymer concentration, presents a straightforward yet highly efficient and universal one-pot synthesis method to produce uniform hierarchical nanostructures
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