(464e) Tuning Underwater Adhesion with Cation-Pi Interactions

Cation–π interactions feature prominently in the self-assembly and adhesion of many biological molecules, including the adhesion proteins of several marine organisms. Although the origin of cation–π bonds in isolated pairs has been extensively studied, the mechanism of cation–π-interactions in molecular films remains uncharted. Here we discuss nanoscale force measurements demonstrating that the cohesive properties of simple aromatic and lysine-rich peptides rival those of the strong adhesion exhibited by adhesion proteins of the marine mussel. More broadly, we demonstrate that interfacial confinement fundamentally alters the energetics of cation–π-mediated assembly, and we discuss how this insight can be used to tune self-assembly and adhesion in peptide-based biomaterials.