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

• Published in: Macromolecular materials and engineering Vol. 302; no. 4; pp. np - n/a
• Main Authors: Gunkel‐Grabole, Gesine, Palivan, Cornelia, Meier, Wolfgang
• Format: Journal Article
• Language: English
• Published: Weinheim John Wiley & Sons, Inc 01.04.2017
• Subjects: amphiphilic polymers; Architecture; Assemblies; biocompatibility; Immobilization; Nanostructure; polymer micelles; polymersomes; Self assembly; Spacers; Substrates; Surface chemistry; surface modifications
• ISSN: 1438-7492; 1439-2054
• DOI: 10.1002/mame.201600363

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. Nanostructured surfaces are generated through covalent immobilization of spherical polymeric nanoarchitectures. Filled and hollow polymeric assemblies are formed from amphiphilic triblock copolymers and coupled to solid substrates in a biocompatible thiol–ene reaction, which is optimized to maintain structural integrity of the polymeric nanoarchitectures. This versatile strategy will enable engineering of nanostructured surfaces with added functionality in the future.