Responsive plasmonic assemblies of amphiphilic nanocrystals at oil-water interfaces

We report a new class of amphiphilic nanocrystals with mixed polymer brush coatings, which can spontaneously assemble into two-dimensional arrays at oil-water interfaces. The plasmon coupling of gold nanoparticles and nanorods in the assembly can be reversibly modulated by conformational changes of the stimuli-responsive polymer brushes. Amphiphilic gold nanocrystals (nanoparticles and nanorods) with mixed polymer brushes were synthesized via sequential "grafting to" (ligand exchange) and "grafting from" (surface initiated atom transfer radical polymerization) reactions. The integration of "grafting to" and "grafting from" reactions offers great flexibility for the surface modification of the nanocrystal scaffolds, allowing the combination of polymers with distinctly different properties on well-defined nanocrystals. For nanocrystals with poly(ethylene glycol) and poly(methyl methacrylate) coatings, the collective plasmonic property of the assembly can be tailored by changing solvent quality. In the case of the amphiphilic nanocrystal with poly(ethylene glycol) and poly(2-(diethylamino)ethyl methacrylate), the pH-sensitivity of poly(2-(diethylamino)ethyl methacrylate) provides an additional means to reversibly tune the assembly by varying the pH. All of the components, including nanocrystals, materials for self-assembled monolayers (polymers and biomacromolecules) on nanocrystal surfaces, and monomers suitable for surface-initiated living radical polymerization, in this construct have a wealth of possibilities available, indicating the potential of our strategy for developing hybrid materials with integrated and collective functionalities.