Neutral polymers partial exclusion in ionic solutions near charged membranes.

Abstract

Neutral polymers have become a useful tool in biophysics. They are currently used in a variety of single-channel conductance measurements, to change solution conductivity and viscosity, to induce osmotic stress in polymer-excluded regions, or simply as crowding agents. Many experiments involve the proximity of neutral polymers to charged membranes or their confinement in aqueous pores formed by protein channels with charged residues. A well-known phenomenon relevant to this problem is the polarization of a neutral particle with dielectric properties different from the surrounding medium under the effect of an electric field. This polarization causes a dielectrophoretic force when inhomogeneous electric fields act on the particle and it has been extensively used in many biomedical applications involving particle trapping and cell separation, among others. In addition, whenever a neutral particle perturbs the equilibrium electric double layer near a charged surface, the osmotic pressure gradient acts as a net repulsive force that pushes the particle away from that surface. Both the dielectrophoretic force and the hydrostatic force contribute to exclude a neutral particle from a charged surface, provided the polarizability is lower in the particle than in the solution. Here we report analytical predictions and simulations of the exclusion of polyethylene glycol (PEG) molecules of different molecular weight from charged surfaces. Molecular dynamics of PEG near charged DPPS membranes and neutral DPPC membranes show a region of PEG exclusion near the membrane-solution interface for charged membranes. The simulations also point to a preferential alignment of PEG molecules near the charged membrane. The simulations are confirmed by preliminary neutron reflectometry data, which are consistent with an exclusion region of concentrated PEG solutions near the highly charged silicon dioxide/water interface.