WATER IN CHANNEL-LIKE CAVITIES - STRUCTURE AND DYNAMICS

Ion channels contain narrow columns of water molecules. It is of inter est to compare the structure and dynamics of such intrapore water with those of the bulk solvent. Molecular dynamics simulations of modified TIP3P water molecules confined within channel-like cavities have been performed and the orientation and dynamics of the water molecules ana lyzed. Channels were modeled as cylindrical cavities with lengths rang ing from 15 to 60 Angstrom and radii from 3 to 12 Angstrom. At the end of the molecular dynamics simulations water molecules were observed t o be ordered into approximately concentric cylindrical shells. The wat ers of the outermost shell were oriented such that their dipoles were on average perpendicular to the normal of the wall of the cavity. Wate r dynamics were analyzed in terms of self-diffusion coefficients and r otational reorientation rates. For cavities of radii 3 and 6 Angstrom, water mobility was reduced relative to that of simulated bulk water. For 9- and 12-Angstrom radii confined water molecules exhibited mobili ties comparable with that of the bulk solvent. If water molecules were confined within an hourglass-shaped cavity (with a central radius of 3 Angstrom increasing to 12 Angstrom at either end) a gradient of wate r mobility was observed along the cavity axis. Thus, water within simp le models of transbilayer channels exhibits perturbations of structure and dynamics relative to bulk water. In particular the reduction of r otational reorientation rate is expected to alter the local dielectric constant within a transbilayer pore.