Controlling Radical Polymerization with Biocatalysts

Abstract

Reversible deactivation radical polymerization (RDRP) is a set of powerful and versatile methods for the synthesis of well-defined polymers. Over the past two decades, the engagement of biocatalysts, namely, enzymes and bacteria, has granted distinctive features to RDRP and propelled RDRP toward a more sustainable future. In this Perspective, we highlight the green conditions, oxygen tolerance, versatile function, and the ability to access difficult polymers in RDRP conducted by biocatalysis (bio-RDRP), discuss major considerations when conducting bio-RDRP, and point out the drawbacks and bottlenecks that limit its further development. The future of bio-RDRP may benefit from expanding the biocatalyst library, improving the redox potential of bacteria, enhancing the biocatalyst robustness, and in-depth mechanistic studies.

Strategies for Achieving Oxygen Tolerance in Reversible Addition–Fragmentation Chain Transfer Polymerization

“…It is noteworthy to mention that other oxidase enzymes, such as horseradish peroxidase (HRP), pyranose oxidase (P2Ox), and formate oxidase (FOx), have also been successfully employed in enzyme catalysis mediated RAFT polymerization (Table 3). [53][54][55][56][57]…”

Horseradish peroxidase-catalyzed polyacrylamide gels: monitoring their polymerization with BSA-stabilized gold nanoclusters and their functional validation in electrophoresis

“…12 Extensive research has shown that enzymatic polymerization is a friendly strategy for the preparation of mechanically robust nanocomposite hydrogels. [13][14][15][16][17] HRP is a very popular and efficient bioenzyme that has been researched in the preparation of hydrogel. [18][19][20] In 1992, Derango et al conducted an initial study that demonstrated the application of HRP and other oxidase enzymes as catalysts for the polymerization of vinyl monomers by free radicals.…”

Green synthesis of polymer materials via enzyme- initiated RAFT polymerization

“…In addition, it holds great promise as a powerful technique for modern polymer chemistry with broader scope for materials researchers and pharmacists 44,45 and has been recently reviewed elsewhere. 46–48 In 2011, di Lena and co-workers documented enzyme-mediated free radical polymerization of methacrylic monomers in water by using an initiating system that resembles activators regenerated by electron transfer-ATRP (ARGET-ATRP). 49,50 The system is based on the metalloenzymes ( i.e.…”