Ion-Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra- and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co-solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion-specific interactions. In this study, we show for the first time that the ion-specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal- and ion-responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion-dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion-dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.