Nanostructured Surfaces through Immobilization of Self-Assembled Polymer Architectures Using Thiol-Ene Chemistry

An efficient strategy for engineering nanostructured surfaces by coupling soft polymeric nanoarchitectures to functionalized surfaces is presented. Self-assembly of polymeric nanoarchitectures from amphiphilic triblock copolymers can yield both filled and hollow spherical nanoarchitectures, depending on the properties of the polymer chosen. These nanoarchitectures are immobilized on solid substrates via a biocompatible thiol-ene reaction, and conditions are optimized to maintain structural integrity of polymeric assemblies. Two routes of surface modification are also implemented to allow inclusion of a polymeric spacer that can mediate between soft polymeric assemblies and solid substrates. Nanostructured surfaces with both filled and hollow nanoarchitectures attached to the surface directly or with a spacer are successfully generated with this protocol. This concept of generating nanostructured surfaces using preassembled polymeric architectures is an important step toward active surfaces, because entrapment of active molecules in the nanoarchitectures prior to their immobilization opens the door to easy generation of surfaces with predetermined activities.