Driving Polymer Brushes from Synthesis to Functioning

Abstract The great success of controlled radical polymerizations has encouraged researchers to develop more facile and robust approaches for surface‐initiated polymerizations (SIPs) to fabricate polymer brushes, even for non‐experts. In recent years, external‐stimuli‐mediated radical polymerization methods have come to the fore as SIPs because of their less rigorous synthetic procedures and high controllability, which expand the opportunities for synthesizing macromolecules with desired chemical compositions and structures, as well as tailor‐made polymers and bioconjugates that show broad applicability and physiological compatibility. This review discusses the latest developments in surface‐initiated polymerization methods, in particular, external‐stimuli mediated atom transfer radical polymerization (ATRP), photo‐induced polymerizations, and reversible addition‐fragmentation chain transfer (RAFT) polymerization, as well as other methods and their combination for the application in surface grafting. The implementation of these methods is of great interest due to their unique possibilities to temporally control a polymerization process, fast and straightforward polymerization, and environmentally benign features, which lead to established and emerging applications in biolubrication, antifouling, and biosensing.