Subin Sahu

Dehydration as a Universal Mechanism for Ion Selectivity in Graphene and Other Atomically Thin Pores

Ion channels play a key role in regulating cell behavior and in electrical signaling. In these settings, polar and charged functional groups, as well as protein response, compensate for dehydration in an ion-dependent way, giving rise to the ion selective transport critical to the operation of cells. Dehydration, though, yields ion-dependent free-energy barriers and thus is predicted to give rise to selectivity by itself. However, these barriers are typically so large that they will suppress the ion currents to undetectable levels. Here, we establish that graphene displays a measurable dehydration-only mechanism for selectivity of K+ over Cl-. This fundamental mechanism, one that depends only on the geometry and hydration, is the starting point for selectivity for all channels and pores. Moreover, while we study selectivity of K+ over Cl- we find that dehydration-based selectivity functions for all ions, that is, cation over cation selectivity (e.g., K+ over Na+). Its likely detection in graphene pores resolves conflicting experimental results, as well as presents a new paradigm for characterizing the operation of ion channels and engineering molecular/ionic selectivity in filtration and other applications.

Crossover behavior of the thermal conductance and Kramers' transition rate theory

Kramers’ theory frames chemical reaction rates in solution as reactants overcoming a barrier in the presence of friction and noise. For weak coupling to the solution, the reaction rate is limited by the rate at which the solution can restore equilibrium after a subset of reactants have surmounted the barrier to become products. For strong coupling, there are always sufficiently energetic reactants. However, the solution returns many of the intermediate states back to the reactants before the product fully forms. Here, we demonstrate that the thermal conductance displays an analogous physical response to the friction and noise that drive the heat current through a material or structure. A crossover behavior emerges where the thermal reservoirs dominate the conductance at the extremes and only in the intermediate region are the intrinsic properties of the lattice manifest. Not only does this shed new light on Kramers’ classic turnover problem, this result is significant for the design of devices for thermal management and other applications, as well as the proper simulation of transport at the nanoscale.