Excluded volume effects in macromolecular forces and ion-interface interactions

TL;DR

This study investigates how excluded volume effects influence forces and ion interactions in charged nanopores, revealing a transition from attraction to repulsion with increasing pore size and highlighting the importance of core interaction range.

Contribution

It introduces a new variational approach to analyze ion-interface interactions, extending previous models to include surface charge effects and core interactions in nanopores.

Findings

Transition from attractive to repulsive interplate pressure with pore size

Range of core interactions critically affects ionic rejection and pressure

Excluded volume effects are key to ion specificity and macromolecular stability

Abstract

A charged Yukawa liquid confined in a slit nanopore is studied in order to understand excluded volume effects in the interaction force between the pore walls. A previously developed self-consistent scheme (S. Buyukdagli el al., J. Stat. Mech. P05033 (2011)) and a new simpler variational procedure that self-consistently couple image forces, surface charge induced electric field and pore modified core interactions are used to this aim. For neutral pores, it is shown that with increasing pore size, the theory predicts a transition of the interplate pressure from an attractive to a strongly repulsive regime associated with an ionic packing state, an effect observed in previous Monte Carlo simulations for hard core charges. The role of the range of core interactions in the ionic rejection and interplate pressure is thoroughly analyzed. We show that the physics of the system can be split into two screening regimes. The ionic packing effect takes place in the regime of moderately screened core interactions characterized with the bare screening parameter of the Yukawa potential b<3/lB, where lB is the Bjerrum length. In the second regime of strongly screened core interactions b>3/lB, solvation forces associated with these interactions positively contribute to the ionic rejection driven by electrostatic forces and enhance the magnitude of the attractive pressure. The pronounced dependence of the interplate pressure and ionic partition coefficients on the magnitude and the range of core interactions indicates excluded volume effects as an important ion specificity and a non-negligible ingredient for the stability of macromolecules in electrolyte solutions.