Probing pH-responsive interactions between polymer brushes and hydrogels by neutron reflectivity.

We investigated the effect of specific interactions on the structure of interfaces between a brush and a hydrogel on the polymer chain length scale. We used a model system for which the interactions between the brush and the gel are switchable. We synthesized weak polyelectrolyte brushes of poly(acrylic acid) and hydrogels of polyacrylamide and poly(N,N-dimethylacrylamide) which interact solely when the poly(acrylic acid) is mainly in its acidic form. The monomer density profiles of the poly(acrylic acid) brush immersed in pure deuterium oxide (D2O) or in contact with a D2O-swollen gel were determined by neutron reflectivity. At pH 2 when the brush is in its neutral form, it interacts with the gel by hydrogen bonds while at pH 9 when the brush is a polyelectrolyte it is not interacting with the gel. Our results show that the presence of interactions with the gel at pH 2 increases the swelling ratio of the brush relative to that in pure D2O, meaning that the brushes exhibit conformations which are more extended from the surface than in the absence of interactions.