No abstract

Amphiphilic copolymers with bottlebrush architecture provide opportunities for the refinement of materials properties that may not be attainable from their linear analogues. In this study, we investigated the effect of polymer architecture on an interplay between molecular packing inside micelle cores, cargo loading, and core crosslinking. Four families of polylactide-b-poly(ethylene oxide) (PLA−PEO) bottlebrush block copolymers with different sidechain arrangements were synthesized by a combination of grafting-through and grafting-from methods. Copolymers with double-graft PLA side chains produced smaller and more uniform micelles than those with single-graft PLA branches. Photoactive coumarin groups, installed at PLA side chain ends, improved paclitaxel loading efficiencies of the copolymer micelles and allowed for the preparation of uniform, core-cross-linked PLA nanoparticles. The highest paclitaxel uptake (up to 30 wt % of the micelle core) was observed for micelles prepared from bottlebrush copolymers with branched PEO side chains, with paclitaxel uptake increasing with the size of PEO side chains. On the other hand, micelle photo-cross-linking efficiency was the highest (up to ∼90%) for copolymers with linear PEO side chains and decreased with increasing size of the hydrophilic headgroup. These trends were attributed to the decrease in molecular packing efficiency inside micelle cores for copolymers with larger and more rigid hydrophilic headgroups. For poorly packed micelles, paclitaxel loading improved core photo-cross-linking efficiencies, suggesting structural rearrangements inside micelles with cargo uptake. Preliminary results also showed that paclitaxel release from bottlebrush micelles was slowed down with increasing degree of core cross-linking.

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

Coumarin-based, photo-cross-linkable core–shell bottlebrush copolymers were synthesized by a grafting-from approach. Hollow cylindrical nanocapsules were generated by selective, metal-free shell photo-cross-linking followed by hydrolytic core removal.