Swelling behavior and viscoelasticity of ultrathin grafted hyaluronic acid films

In this paper we study the effect of monovalent and divalent ions on the swelling behavior and viscoelastic parameters of ultrathin layers of the natural polyelectrolyte hyaluronic acid covalently coupled to glass substrates. A colloidal probe technique is applied for this purpose based on latex beads, hovering over the polymer cushion. By analyzing the vertical Brownian motion of these beads with reflection interference contrast microscopy (RICM) we determined the equilibrium layer thickness (with 3 nm vertical resolution), the interfacial interaction potential, and the characteristic mesh size limiting the hydrodynamic flow within the polyelectrolyte film as a function of the ionic strength. The experimental results are interpreted in terms of three different theoretical models: the polyelectrolyte brush approximation of Pincus [#!ref1!#], a modified polyelectrolyte brush approximation in the high salt concentration limit of Ross and Pincus [#!ref2!#] and the simple scaling approximation for neutral adsorbed polymers of de Gennes [#!ref3!#]. Within experimental error all of these different models fit our experimental data and yield comparable results for the equilibrium layer thickness. Moreover we determine a thickness dependent, effective surface coverage from both brush models. The hydrodynamic properties of the films are interpreted in terms of the Brinkmann model of elastic porous media by assuming an effective mesh size, which depends linearly on the Debye screening length. The salt induced condensation of the polyelectrolyte films can be described microscopically in terms of a progressive contraction of the mesh size with increasing salt concentration. Received 10 September 1998 and Received in final form 30 November 1998