Sulfone-Modulated Aqueous Polymerization-Induced Self-Assembly: Tailoring Adaptive Nanostructures via Competing Supramolecular Interactions

The integration of supramolecular chemistry with polymerization-induced self-assembly (PISA) offers a promising avenue to advance the design and functionality of nanomaterials. Here, we elucidate the role of sulfone bonding in aqueous block copolymer (BCP) self-assembly by evaluating the aqueous PISA behaviors of sulfone-functionalized BCPs and the stimuli-responsive properties of the resulting assemblies. A series of 2-(alkylsulfonyl)ethyl acrylamides were designed for aqueous PISA, in which the sulfone moiety not only enhances monomer water solubility but also stabilizes polymer assemblies through sulfone bonding. Systematic variation of the alkyl tail revealed distinct PISA behaviors, where shorter tails favored sulfone-bond-dominated assembly, while longer tails introduced competitive hydrophobic interactions. This interplay between sulfone bonding and hydrophobicity enabled the fabrication of polymer assemblies with programmable ion-responsive morphology transitions. Our findings provide fundamental insights into the role of supramolecular interactions in PISA and establish a versatile strategy for engineering adaptive nanomaterials.