A Polymer-Brush-Based Nanovalve Controlled by Nanoparticle Additives: Design Principles

Polymer-grafted surfaces and channels are increasingly used for the design of responsive materials and sensors due to robust performance and ease of use. Various strategies for the control of the nanoscale morphologies of such materials and devices are being tested. Entropic repulsion between the polymer chains in a grafted brush of sufficient density causes the chains to extend in the direction perpendicular to the grafting surface in comparison to the position of unattached polymers. When nanoparticles having attractive interactions with the polymers are introduced into the solvent, these nanoparticles tend to infiltrate into the brush and reduce its extension. Under certain conditions, a sharp reduction in brush height extension can occur over a narrow range of nanoparticle concentrations in solution. We describe a way of controlling transport through polymer-functionalized nanochannels with nanoparticle additives, relying on the physics of nanoparticles and polymer brushes under confinement, and we suggest a blueprint for the creation of a tunable nanovalve. The nanovalve is modeled as a cylinder with a polymer brush grafted on its inside surface. Brush properties such as the chain length and the grafting density are chosen so that the brush chains extend into the center of the cylinder in the absence of nanoparticles, occluding the flux of analyte molecules through the pore. When nanoparticles that are attracted to the polymers are introduced into solution, they infiltrate into the brush and partially collapse it against the cylindrical grafting surface, opening space in the center of the cylinder through which analyte molecules can flow. The operation of such a nanovalve is analyzed via self-consistent field theory calculations in the strong-stretching approximation. Self-consistent field analysis is supported by Langevin dynamics simulations of the underlying coarse-grained model of the polymer nanoparticle system.