Underwater Adhesion of Multiresponsive Complex Coacervates

Many marine organisms have developed adhesives that are able to bond under water, overcoming the challenges associated with wet adhesion. A key element in the processing of several natural underwater glues is complex coacervation, a liquid-liquid phase separation driven by complexation of oppositely charged macromolecules. Inspired by these examples, the development of a fully synthetic complex coacervate-based adhesive is reported with an in situ setting mechanism, which can be triggered by a change in temperature and/or a change in ionic strength. The adhesive consists of a matrix of oppositely charged polyelectrolytes that are modified with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) grafts. The adhesive, which initially starts out as a fluid complex coacervate with limited adhesion at room temperature and high ionic strength, transitions into a viscoelastic solid upon an increase in temperature and/or a decrease in the salt concentration of the environment. Consequently, the thermoresponsive chains self-associate into hydrophobic domains and/or the polyelectrolyte matrix contracts, without inducing any macroscopic shrinking. The presence of PNIPAM favors energy dissipation by softening the material and by allowing crack blunting. The high work of adhesion, the gelation kinetics, and the easy tunability of the system make it a potential candidate for soft tissue adhesion in physiological environments.