Thermoreversible Surface Polymer Patches: A Cryogenic Transmission Electron Microscopy Investigation

Hybrid core-shell type nanoparticles from gold nanoparticle cores and poly( N-isopropylacrylamide) shells were investigated with regard to their structural plasticity. Reversible addition-fragmentation chain transfer polymerization was used to synthesize well-defined polymers that can be readily anchored onto the gold nanoparticle surface. The polymer shell morphologies were directly visualized in their native solution state at high resolution by cryogenic transmission electron microscopy, and the microscopic results were further corroborated by dynamic light scattering. Different environmental conditions and brush architectures are covered by our experiments, which leads to distinct thermally induced responses. These responses include constrained dewetting of the nanoparticle surface at temperatures above the lower critical solution temperature of poly( N-isopropylacrylamide), leading to surface polymer patches. This effect provides a novel approach toward breaking the symmetry of nanoparticle interactions, and we show first evidence for its impact on the formation of colloidal superstructures.