pH-Responsive Membranes from Self-Assembly of Poly(2-(dimethylamino)ethyl methacrylate) Brush Silica Nanoparticles.

We have prepared novel pH-responsive nanoporous membranes by the self-assembly of silica nanoparticles carrying poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes with a degree of polymerization (DP) in the 100-450 range. The nanoparticles were prepared by surface-initiated ARGET-ATRP, and the membranes were assembled by pressure-driven deposition onto porous supports. The permeability and pore size of the resulting robust membranes were studied using water and hexane flux and filtration cutoff experiments. The pore size of the PDMAEMA "hairy" silica nanoparticle (HNP) membranes measured by water flux was ca. 22 nm and was mostly independent of the polymer brush length. We attributed this to a combination of the PDMAEMA brushes swelling and their permeability to water. In contrast, the pore size measured by hexane flux strongly depended on the DP. The flux and pore size of these membranes in water strongly depended on the pH. The pore size decreased by a factor of 1.6 when the pH was changed from neutral to acidic. pH-Responsive HNP membranes combine many attractive properties, including control over the filtration cutoff, responsive permeability, and high flux at low pressure. The reversible self-assembly of the PDMAEMA HNP membranes may help not only in their facile preparation but also in material recycling if biofouling occurs. The key features of the PDMAEMA HNP assemblies are attractive in membrane separations, molecular valves, and biosensors, where having precise control over the pore size and pore gating is highly desirable.