Thermoresponsive Polymer Gating System on Mesoporous Shells of Silica Particles Serving as Smart Nanocontainers.

Spherical silica nanoparticles with solid cores and mesoporous shells (SCMS) were decorated with thermoresponsive polymer brushes that were shown to serve as macromolecular valves to control loading and unloading of a model dye within the mesopores. Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes were grafted from the surfaces of both solid core (SC) and SCMS particles of similar size using surface-initiated atom transfer radical polymerization. Both systems based on porous (SCMS-PNIPAM) and nonporous (SC-PNIPAM) particles were characterized using cryo-TEM, thermogravimetry and elemental analysis to determine the structure and composition of the decorated nanoparticles. The grafted PNIPAM brushes were found to be responsive to temperature changes enabling temperature-controlled gating of the pores. The processes of loading and unloading in the obtained systems were examined using a model fluorescent dye-rhodamine 6G. Polymer brushes in SCMS-PNIPAM systems were shown to serve as molecular valves enabling significant adsorption (loading) of the dye inside the pores with respect to the SC-PNIPAM (no pores) and SCMS (no valves) systems. The effective unloading of the fluorescent cargo molecules from the decorated nanoparticles was achieved in a water/methanol solution. The obtained SCMS-PNIPAM particles may be used as smart nanocontainers or nanoreactors offering also facile isolation from the suspension due to the presence of dense cores.