The role of hydrogen bonding in tethered polymer layers.

A molecular theory to study the properties of end-tethered polymer layers, in which the polymers have the ability to form hydrogen bonds with water, is presented. The approach combines the ideas of the single-chain mean-field theory to treat tethered layers with the approach of Dormidontova (Macromolecules, 2002, 35, 987.) to include hydrogen bonds. The generalization includes the consideration of position-dependent polymer-water and water-water hydrogen bonds. The theory is applied to model poly(ethylene oxide) (PEO), and the predictions are compared with equivalent polymer layers that do not form hydrogen bonds. It is found that increasing the temperature lowers the solubility of the PEO and results in a collapse of the layer at high enough temperatures. The properties of the layer and their temperature dependence are shown to be the result of the coupling between the conformational entropy of the chains, the ability of the polymer to form hydrogen bonds, and the intermolecular interactions. The structural and thermodynamic properties of the PEO layers, such as the lateral pressure-area isotherms and polymer chemical potentials, are studied as a function of temperature and type of tethering surface. The possibility of phase separation of the PEO layer at high enough temperature is predicted due to the reduced solubility induced by breaking of polymer-water hydrogen bonds. A discussion of the advantages and limitations of the theory, together with how to apply the approach to different hydrogen-bonding polymers, is presented.