Positive Charge Influences on the Surface Interactions and Cohesive Bonding of a Catechol-Containing Polymer.

Achieving robust underwater adhesion remains challenging. Through generations of evolution, marine mussels have developed an adhesive system that allows them to anchor onto wet surfaces. Scientists have taken varied approaches to developing mussel-inspired adhesives. Mussel foot proteins are rich in lysine residues, which may play a role in the removal of salts from surfaces. Displacement of water and ions on substrates could then enable molecular contact with surfaces. The necessity of cations for underwater adhesion is still in debate. Here, we examined the performance of a methacrylate polymer containing quaternary ammonium and catechol groups. Varying amounts of charge in the polymers were studied. As opposed to protonated amines such as lysine, quaternary ammonium groups offer a nonreactive cation for isolating effects from only charge. Results shown for dry bonding demonstrated that cations tended to decrease bulk cohesion while increasing surface interactions. Stronger interactions at surfaces, along with weaker bulk bonding, indicate that cations decreased the cohesive forces. When under salt water, overall bulk adhesion also dropped with higher cation loadings. Surface attachment under salt water also dropped, indicating that the polymer cations could not displace surface waters or sodium ions. Salt did, however, appear to shield bulk cation-cation repulsions. These studies help to distinguish influences upon bulk cohesion from attachment at surfaces. The roles of cations in adhesion are complex, with both cohesive and surface bonding being relevant in different ways, sometimes even working in opposite directions.