Homopolymer Self-Assembly via Poly(propylene Sulfone) Networks

Natural molecules such as peptides and DNA organize dynamically into hierarchical structures with diverse morphologies and sizes. The ability to mimic this self-assembly behavior in synthetic materials has remained an elusive goal. We report on poly(propylene sulfone), a synthetic homopolymer that self-assembles into nanoscale hydrogels of various morphologies including spherical, vesicular, and cylindrical in aqueous solution. Experiments and simulations demonstrate that while the polymer chains are roughly extended and minimally aggregated in DMSO, the addition of water overcomes the steric limitations imposed by the sulfones and induces formation of molecular networks through sulfone-sulfone bonding. Networks collapse and reorganize into distinct morphologies upon hydration, endowing an exceptional capability for capturing organic molecules. This simple system presents a robust platform for controlling nanofabrication.