Multiple hydrogen bonding mediates the formation of multicompartment micelles and hierarchical self-assembled structures from pseudo A-block-(B-graft-C) terpolymers

In this study, we report a simple but effective method for preparing various multi-compartment micelle structures: poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT) diblock copolymers blended with the adenine-terminated poly(ethylene oxide) (A-PEO) homopolymer to obtain pseudo A-b-(B-g-C)-type terpolymers stabilized through thymine-adenine (T-A) multiple hydrogen bonding interactions between PVBT and A-PEO segments in DMF (N,N-dimethylformamide) common solvent after the addition of H₂O or MeCN selective solvent. Transmission electron microscopy revealed several different multi-compartment micelle structures - raspberry-like spheres, core-shell-corona spheres, core-shell-corona cylinders, nanostructured vesicles, onion-like structures, segmented worm-like cylinders, and woodlouse-like structures - upon varying the molecular weight of the PS-b-PVBT block segments and the concentration of the selective solvent. Thus, we could induce changes in the multi-compartment micelle structures, similar to those of ABC miktoarm star terpolymers, through simple blending of PS-b-PVBT block copolymers with an A-PEO homopolymer.