Surface‐initiated PET‐RAFT polymerization under metal‐free and ambient conditions using enzyme degassing

Abstract

An open‐to‐air method for the efficient synthesis of surface‐tethered polymer brushes based on photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization is reported. Key to this approach is an enzyme‐assisted strategy using glucose oxidase to facilitate the in situ removal of oxygen during the polymerization process. Control experiments in the absence of glucose oxidase confirm the importance of enzymatic deoxygenation for successful polymerization of a variety of acrylamide, methacrylate, and acrylate monomers. In accordance with controlled polymerization kinetics, a linear increase in brush height as a function of irradiation time for a range of light intensities is demonstrated. Importantly, the use of light to mediate growth and the inherent monomer versatility of PET‐RAFT allow for the facile fabrication of well‐defined polymer brushes under aqueous conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 70–76

Crosslinked Polypeptide Films via RAFT‐Mediated Continuous Assembly of Polymers

“…[7c] Recently, Seo et al demonstrated the use of SI-PET-RAFT without RAFT agent in the solution to yield patternable polymer brushes. [25] This is in agreement with our results indicating polymerization is confined to the film surface. Thus, to observe the degree of polymerization occurring both with and without RAFT agent in solution, analysis of the aggregate size was performed.…”

Efficient Photoinitiated Polymerization-Induced Self-Assembly with Oxygen Tolerance through Dual-Wavelength Type I Photoinitiation and Photoinduced Deoxygenation

“…Over the past two decades, reversible deactivation radical polymerization (RDRP) has become an important method for the preparation of well-defined polymers with precise molecular weights, dispersity, architecture, end-group functionalities, and compositions . Reversible addition–fragmentation chain transfer (RAFT) polymerization is one of the major RDRPs due to its versatility to a wide range of monomers, mild reaction conditions, and absence of metal ions. − RAFT polymerization can be performed via either homogeneous polymerization (solution and bulk) or heterogeneous polymerization depending on the solubility of the monomer/polymer in the polymerization mixture.…”

New Light in Polymer Science: Photoinduced Reversible Addition-Fragmentation Chain Transfer Polymerization (PET-RAFT) as Innovative Strategy for the Synthesis of Advanced Materials

“…Moreover, Seo et al [ 89 ] exploited metal-free SI-PET-RAFT polymerization in order to fabricate 3D polymer brushes under aqueous conditions, using the photomask technology. Eosin Y was the photocatalyst of choice under green light (λ = 530 nm) and the oxygen tolerance was addressed by in situ enzyme degassing approach, using glucose oxidase (GOx).…”