Modeling of Chemical Equilibria in Polymer and Polyelectrolyte Brushes

Abstract

This chapter discusses the application of a molecular theory to the study of polyelectrolyte brushes coupled to different chemical equilibria. In these systems, the segments in the polyelectrolyte can undergo reversible chemical reactions that modify their properties and, thus change the structure of the brush. Examples of chemical equilibria discussed in this chapter are acid‐base equilibria in weak polyelectrolyte brushes, redox equilibria in electroactive brushes, ligand‐receptor binding in brushes modified with biological receptors, and grafting equilibrium of polymer chains with an end‐group that can bind to the grafting surface. It is shown that, in all these examples, chemical reactivity within the brush can be very different to that in bulk solution due to the effects of the local environment and confinement at the nanoscale.