Polyelectrolyte brushes: counterion distribution and complexation properties

The structure of dense grafted polyelectrolyte layers has been studied with a combination of neutron reflectivity and infrared spectroscopy techniques. The polyelectrolyte brushes were made of poly(styrene sulfonate) neutralized by different counterions. Small counterions are distributed throughout the brush in order to ensure a highly local electroneutrality. In addition, they can be readily exchanged with other small ions. On the other hand, macromolecular counterions (as well as some proteins) are irreversibly trapped by the brush, but are located outside the grafted layer and cannot reach the surface.