“God Made the Bulk, the Surface was Invented by the Devil”: Topological Control Over the Interfacial Physico-Chemical Properties of Polymer Assemblies

The application of polymer topologies, beyond chain linearity, to yield polymer brushes enables to surpass the unique physicochemical properties of their linear equivalents. This is especially valid on flat surfaces (1), where the ultra-dense and highly compact character of cyclic brushes provide an enhanced steric stabilization of the interface and a superlubricious behavior. Alternatively, when cyclic brushes form shells on inorganic nanoparticles (NPs) (2), their extraordinary structural properties make them impenetrable and long-lasting shields, which extend the stability of NP dispersions and hinder any interaction with serum proteins. Polymer topological effects, typically observed in bulk or in solution are amplified by adding an additional boundary such as a grafting surface. Their precise tuning translates into materials with unprecedented properties that seem to confirm Wolfgang Pauli’s famous statement: “God made the bulk, the surface was invented by the devil.” (1) Angew. Chem., Int. Ed. 2016, 55, 15583. (2) Angew. Chem., Int. Ed. 2017, 56, 4507.