Ion transport and molecular organization are coupled in polyelectrolyte-modified nanopores

Chemically modified nanopores show a strong and nontrivial coupling between ion current and the structure of the immobilized species. In this work we study theoretically the conductance and structure in polymer modified nanopores and explicitly address the problem of the coupling between ion transport and molecular organization. Our approach is based on a nonequilibrium molecular theory that couples ion conductivity with the conformational degrees of freedom of the polymer and the electrostatic and nonelectrostatic interactions among polyelectrolyte chains, ions, and solvent. We apply the theory to study a cylindrical nanopore between two reservoirs as a function of pore diameter and length, the length of the polyelectrolyte chains, their grafting density, and whether they are present or not on the outer reservoir walls. In the very low applied potential regime, where the distribution of polyelectrolyte and ions is similar to that in equilibrium, we present a simple analytical model based on the combination of the different resistances in the system that describes the conductance in excellent agreement with the calculations of the full nonequilibrium molecular theory. On the other hand, for a large applied potential bias, the theory predicts a dramatic reorganization of the polyelectrolyte chains and the ions. This reorganization results from the global optimization of the different interactions in the system under nonequilibrium conditions. For nanopores modified with long chains, this reorganization leads to two interesting physical phenomena: (i) control of polyelectrolyte morphology by the direction and magnitude of ion-fluxes and (ii) an unexpected decrease in system resistance with the applied potential bias for long chains due to the coupling between polyelectrolyte segment distribution and ion currents.