Morphological transition of nanostructures of self‐assembled block copolymers by stimuli‐induced conformational changes in the hydrophilic block

The morphological control of nanostructures created by the self‐assembly of macromolecular building blocks in solution has practical importance because the structural parameters of nanostructures greatly affect their physical and chemical behavior in solution, for example, pharmacokinetics. Herein, we report that the stimuli‐induced changes to the conformation of the hydrophilic polymer block of a block copolymer (BCP), in this case branched‐linear poly(ethylene glycol)‐b‐poly(styrene) BCPs, are translated to changes in the morphology of the BCP self‐assemblies in solution. Specifically, the cone angle between the poly(ethylene glycol) arms in the tri‐arm hydrophilic block equipped with pyridyl units in the scaffold can be changed by varying the self‐assembly conditions, thus affecting the packing parameter (p) of the BCP. Upon increasing the cone angle by protonating the pyridyl units, the self‐assembled BCP structures underwent changes consistent with a reduction in the p value. In contrast, the chelation of zinc metal cations (Zn2+) to the pyridyl groups resulted in the conformation of the hydrophilic block taking on a closed form, resulting in an apparent increase in the p value of the BCP. Our results could be applied to stimuli‐dependent morphological transitions of other self‐assembled BCP nanostructures in solution. In this study, the stimuli‐induced conformational changes in the hydrophilic polymer chain of poly(ethylene glycol) (PEG)‐b‐poly(styrene) (PS) block copolymer (BCP) were investigated. Depending on the self‐assembly conditions, the cone angle between the PEG arms equipped with pyridyl units in the scaffold in the tri‐arm hydrophilic block varies, thus affecting the packing parameter of the BCP. These results can be potentially applied to stimuli‐dependent morphological transitions of other self‐assembled BCP nanostructures in solutions.