Synthesis and one‐dimensional assembly of cylindrical polymer nanoparticles prepared from tricomponent bottlebrush copolymers

Abstract

ABSTRACT Biological systems feature controlled assembly of well‐defined building blocks at different length scales. While major progress has been achieved in directing the assembly of synthetic molecular building blocks, controlled organization of nanostructured units into micro‐ and macroscale aggregates remains a challenge. Herein, we report the synthesis of well‐defined nanostructured building blocks, cylindrical polymeric nanoparticles with controlled dimensions and inner surface chemistry, and their dynamic anisotropic organization into one‐dimensional assemblies. Nanoparticle building blocks were produced by molecular templating of cylindrical bottlebrush copolymers featuring tricomponent side chains. The produced nanostructures were composed of a nonionic and bioinert polyethylene glycol (PEG) shell and stimuli‐responsive poly(methacrylic acid) (PMA) chains grafted on the interior. We show that pH‐dependent interactions between PMA chains exposed only at the nanoparticle ends lead to anisotropic end‐to‐end association of parent cylindrical nanostructures into elongated superstructures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3868–3874