Macromolecules 2005 38:3432-3441
We propose a theoretical investigation of the physical adsorption of neutral comb polymers with an adsorbing skeleton and nonadsorbing side chains on a flat surface. Such polymers are particularly interesting as “dynamic coating” matrices for bioseparations, especially for DNA sequencing, capillary electrophoresis, and lab-on-chips. Separation performances are increased by coating the inner surface of the capillaries with neutral polymers. This method allows one to screen the surface charges, thus preventing electro-osmosis flow and adhesion of charged macromolecules (e.g., proteins) on the capillary walls. We identify three adsorption regimes: a “mushroom” regime, in which the coating is formed by strongly adsorbed skeleton loops and the side chains anchored on the skeleton are in a swollen state, a “brush” regime, characterized by a uniform multichains coating with an extended layer of nonadsorbing side chains and a nonadsorbed regime. By using a combination of mean field and scaling approaches, we explicitly derive asymptotic forms for the monomer concentration profiles, for the adsorption free energy and for the thickness of the adsorbed layer as a function of the skeleton and side chains sizes and of the adsorption parameters. Moreover, we obtain the scaling laws for the transitions between the different regimes. These predictions can be checked by performing experiments aimed at investigating polymer adsorption, such as neutron or X-ray reflectometry, ellipsometry, quartz microbalance, or surface force apparatus.