Ion-water and water-water interactions in a gramicidinlike channel: effects due to group polarizability and backbone flexibility.

In the gramicidin channel, ionic transport and water transport occur simultaneously. Gramicidin's transport properties are influenced by ionic interactions with both the polypeptide and the channel waters. We present results of molecular dynamics studies on a series of alkali metal ions interacting with a water-filled gramicidinlike channel (a configurationally constrained polyglycine analog) at the dimer junction, in mid-monomer, and near the channel entrance. We investigate details of both short and long range ion-water and water-water correlation; these are notably dependent on the explicit consideration of polarizability and the degree of backbone flexibility. The nature of ion-water and water-water correlations changes as ionic size decreases and these changes may be augmented or attenuated by manipulation of the two parameters under study. Incorporating polarizability generally shortens ion-water distances and enhances ion-induced electrostriction (decreased water-water separations), while simultaneously reducing the long range orientational correlation of the single filing waters within the channel. Increasing flexibility predictably results in a broadening of the distribution of water-water and ion-water separations and contributes to the loss of long range orientational correlations. Both effects are ion specific; Cs+ and Na+ interact with the channel in distinctly different ways, while K+ represents an intermediate case more closely resembling Cs+. Our results demonstrate that incorporation of polarizability in the potential function has significant effects on the properties of channel water and, consequently, on the ionic transport process. While ion-water and water-water distances are decreased due to this feature, thereby fostering longer ranged correlations within the channel, enhanced interactions between water molecules and peptide groups tend to mitigate this effect. Possible implications for the multiple occupancy states of gramicidin and long range information transfer via a single file water chain are considered.