Ionic Transport in Electrostatic Janus Membranes. An Explicit Solvent Molecular Dynamic Simulation.

Janus, or two-sided, charged membranes offer promise as ionic current rectifiers. In such systems, pores consisting of two regions of opposite charge can be used to generate a current from a gradient in salinity. The efficiency of nanoscale Janus pores increases dramatically as their diameter becomes smaller. However, little is known about the underlying transport processes, particularly under experimentally accessible conditions. In this work, we examine the molecular basis for rectification in Janus nanopores using an applied electric field. Molecular simulations with explicit water and ions are used to examine the structure and dynamics of all molecular species in aqueous electrolyte solutions. For several macroscopic observables, the results of such simulations are consistent with experimental observations on asymmetric membranes. Our analysis reveals a number of previously unknown features, including a pronounced local reorientation of water molecules in the pores, and a segregation of ionic species that had not been anticipated by previously reported continuum analyses of Janus pores. Using these insights, a model is proposed for ionic current rectification in which electric leakage at the pore entrance controls net transport.

A structural indicator for water built upon potential energy considerations.

We introduce a parameter-free structural indicator to classify local environments of water molecules in stable and supercooled liquid states, which reveals a clear two-peak distribution of local properties. The majority of molecules are tetrahedrally coordinated (T molecules), via low-energy hydrogen bonds. The minority component, whose relative concentration decreases with a decrease in the temperature at constant pressure, is characterized by prevalently three-coordinated molecules, giving rise to a distorted local network around them (D molecules). The inter-conversion between T and D molecules explains the increasing specific heat at constant pressure on cooling. The local structure around a T molecule resembles the one found experimentally in low-density amorphous ice (a network structure mostly composed by T molecules), while the local structure around a D molecule is reminiscent of the structural properties of high-density amorphous ice (a network structure composed by a mixture of T and D molecules).