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Oxygen-Tolerant RAFT Polymerization Initiated by Living Bacteria

Bennett, Mechelle R.; Moloney, Cara; Catrambone, Francesco; Turco, Federico; Myers, Benjamin; Kovacs, Katalin; Hill, Philip J.; Alexander, Cameron; Rawson, Frankie J.; Gurnani, Pratik

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Mechelle R. Bennett

Francesco Catrambone

Federico Turco

Benjamin Myers

Associate Professor

Pratik Gurnani


Living organisms can synthesize a wide range of macromolecules from a small set of natural building blocks, yet there is potential for even greater materials diversity by exploiting biochemical processes to convert unnatural feedstocks into new abiotic polymers. Ultimately, the synthesis of these polymers in situ might aid the coupling of organisms with synthetic matrices, and the generation of biohybrids or engineered living materials. The key step in biohybrid materials preparation is to harness the relevant biological pathways to produce synthetic polymers with predictable molar masses and defined architectures under ambient conditions. Accordingly, we report an aqueous, oxygen-tolerant RAFT polymerization platform based on a modified Fenton reaction, which is initiated by Cupriavidus metallidurans CH34, a bacterial species with iron-reducing capabilities. We show the synthesis of a range of water-soluble polymers under normoxic conditions, with control over the molar mass distribution, and also the production of block copolymer nanoparticles via polymerization-induced self-assembly. Finally, we highlight the benefits of using a bacterial initiation system by recycling the cells for multiple polymerizations. Overall, our method represents a highly versatile approach to producing well-defined polymeric materials within a hybrid natural-synthetic polymerization platform and in engineered living materials with properties beyond those of biotic macromolecules.


Bennett, M. R., Moloney, C., Catrambone, F., Turco, F., Myers, B., Kovacs, K., …Gurnani, P. (2022). Oxygen-Tolerant RAFT Polymerization Initiated by Living Bacteria. ACS Macro Letters, 11(8), 954-960.

Journal Article Type Article
Acceptance Date Jul 5, 2022
Online Publication Date Jul 12, 2022
Publication Date Aug 16, 2022
Deposit Date Jul 13, 2022
Publicly Available Date Jul 15, 2022
Journal ACS Macro Letters
Electronic ISSN 2161-1653
Publisher American Chemical Society (ACS)
Peer Reviewed Peer Reviewed
Volume 11
Issue 8
Pages 954-960
Keywords Materials Chemistry, Inorganic Chemistry, Polymers and Plastics, Organic Chemistry
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