How Does Gecko Keratin Stick to Hydrophilic and Hydrophobic Surfaces in the Presence and Absence of Water? An Atomistic Molecular Dynamics Investigation.

We developed a united-atom model of gecko keratin to investigate the influence of electrostatic and van der Waals contributions to gecko adhesion in scenarios representing gecko's natural habitats. The keratin model assumes that only intrinsically disordered regions directly contact the surface. Contact angles of two generic substrate surfaces that we created match those previously used in AFM experiments on gecko adhesion. Force probe molecular dynamics simulations pulling the keratin from the surface show that the pull-off force increases with increased water content and is inversely related to the water contact angle of the surface. This matches experimental trends. We investigated the number and charge density of keratin and water at the surface, confirming a water-mediating effect and are able to show that keratin folds polar groups to the hydrophilic surface. We decomposed energetic contributions during pull-off, and our computational model shows that in contrast to popular hypotheses, long-range electrostatic interactions determine much of the pull-off process. The contribution of electrostatics to adhesion may be in the order of the van der Waals contributions.