Surface‐Reactive Patchy Nanoparticles and Nanodiscs Prepared by Tandem Nanoprecipitation and Internal Phase Separation

Nanoparticles with structural or chemical anisotropy are promising materials in domains as diverse as cellular delivery, photonic materials, or interfacial engineering. The surface chemistry may play a major role in some of these contexts. Introducing reactivity into such polymeric nanomaterials is thus of great potential, yet is still a concept in its infancy. In the current contribution, a simple nanoprecipitation technique leads to nanoparticles with diameters as low as 150 nm and well‐defined reactive surface patches of less than 30 nm in width, as well as surface‐reactive flat, disc‐like nanoparticles with corresponding dimensions, via an additional crosslinking/delamination sequence. To this aim, chemically doped block copolymers (BCPs) are employed. Control over morphology is attained by tuning preparation conditions, such as polymer concentration, solvent mixture composition, and blending with non‐functional BCP. Surface reactivity is demonstrated using a modular ligation method for the site‐selective immobilization of thiol molecules. The current approach constitutes a straightforward methodology requiring minimal engineering to produce nanoparticles with confined surface reactivity and/or shape anisotropy. Nanoparticles with surface‐expressed reactive patches and corresponding nanodiscs are prepared by a simple nanoprecipitation technique with functional block copolymers. The surface pattern formation is controlled by preparation conditions (concentration, solvent, and functionality). Spatially confined functionalization is demonstrated by grafting model thiol compounds. These nanomaterials are structurally approaching biological particles and are interesting building blocks for colloidal assemblies.