Predicting protracted binding kinetics of polymers: Integral of first-passage times.

Abstract

Capturing protracted binding kinetics of polymers onto the surface of nanoobjects is crucial for the rational design of multifunctional nanostructures, such as patchy nanoparticles and nanodrug carriers. Recently, we developed a method-integral of first-passage times (IFS)-to successfully predict nonequilibrium, kinetically stable superstructures fabricated by two star polymers. However, whether the protracted binding kinetics predicted by IFS corresponds to the actual polymer adsorption has only been incompletely explored. In this paper, we clarify this issue by using IFS to study polymer adsorption with binding ends onto a planar wall as an example. At low free-energy barriers, the IFS-predicted polymer binding kinetics is consistent with those extracted from direct simulations. At high free-energy barriers, the protracted polymer adsorption predicted by IFS coincides with those measured in experiments. Our findings demonstrate the feasibility of IFS to study long-lived formation kinetics of polymer nanostructures by spanning timescales from picoseconds to macroscopic minutes, which establishes a foundation to use IFS in different applications.