Forced desorption of polymers from interfaces

In the past decade it has become possible to directly measure the adsorption force of a polymer in contact with a solid surface using single-molecule force spectroscopy. A plateau force in the force-extension curve is often observed in systems of physisorbed or noncovalently bonded polymers. If a molecule is pulled quickly compared to internal relaxation, then nonequilibrium effects can be observed. Here we investigate these effects using statistical mechanical models and experiments with a spider silk polypeptide. We present evidence that most experiments showing plateau forces are done out of equilibrium. We find that the dominant nonequilibrium effect is that the detachment height h(max)(v) increases with pulling speed v. Based on a nonequilibrium model within a master-equation approach, we show the sigmoidal dependence of the detachment height on the pulling speed of the cantilever, agreeing with experimental data on a spider silk polypeptide. We also show that the slope with which the plateau forces detach is given by the cantilever force constant in both theory and experiment.