Au@pNIPAM Thermosensitive Nanostructures: Control over Shell Cross‐linking, Overall Dimensions, and Core Growth

Thermoresponsive nanocomposites comprising a gold nanoparticle core and a poly(N‐isopropylacrylamide) (pNIPAM) shell are synthesized by grafting the gold nanoparticle surface with polystyrene, which allows the coating of an inorganic core with an organic shell. Through careful control of the experimental conditions, the pNIPAM shell cross‐linking density can be varied, and in turn its porosity and stiffness, as well as shell thickness from a few to a few hundred nanometers is tuned. The characterization of these core–shell systems is carried out by photon‐correlation spectroscopy, transmission electron microscopy, and atomic force microscopy. Additionally, the porous pNIPAM shells are found to modulate the catalytic activity, which is demonstrated through the seeded growth of gold cores, either retaining the initial spherical shape or developing a branched morphology. The nanocomposites also present thermally modulated optical properties because of temperature‐induced local changes of the refractive index surrounding the gold cores. Thermoresponsive nanocomposites comprising a gold nanoparticle core and a poly(N‐isopropylacrylamide) (pNIPAM) shell are successfully synthesized (see figure) by a two‐step protocol. Through careful control of the experimental conditions, the pNIPAM shell cross‐linking density can be varied, and in turn its porosity and stiffness, as well as shell thickness from a few to few hundred nanometers can be tuned. Additionally, the porous pNIPAM shells can be used to modulate the catalytic activity.