Polymer End Group Control through a Decarboxylative Cobalt-Mediated Radical Polymerization: New Avenues for Synthesizing Peptide, Protein, and Nanomaterial Conjugates

Meri Ayurini; Peter G Chandler; Paul D O'Leary; Ruoxin Wang; David Rudd; Karen D Milewska; Lara R Malins; Ashley M Buckle; Joel F Hooper

doi:10.1021/jacsau.1c00453

Polymer End Group Control through a Decarboxylative Cobalt-Mediated Radical Polymerization: New Avenues for Synthesizing Peptide, Protein, and Nanomaterial Conjugates

JACS Au. 2021 Nov 30;2(1):169-177. doi: 10.1021/jacsau.1c00453. eCollection 2022 Jan 24.

Authors

Meri Ayurini^{1

2}, Peter G Chandler³, Paul D O'Leary¹, Ruoxin Wang⁴, David Rudd⁵, Karen D Milewska⁶, Lara R Malins⁶, Ashley M Buckle³, Joel F Hooper¹

Affiliations

¹ Department of Chemistry, Monash University, Clayton, 3800 Victoria, Australia.
² Chemistry Department, Universitas Pertamina, South Jakarta 12220, Indonesia.
³ Department of Biochemistry and Molecular Biology, Biomedicine Discovery Institute, Monash University, Clayton, 3800 Victoria, Australia.
⁴ Department of Chemical Engineering, Monash University, Clayton, 3800 Victoria, Australia.
⁵ Monash Institute of Pharmaceutical Science, Parkville, 3052 Victoria, Australia.
⁶ Research School of Chemistry, Australian National University, Acton, 2601 Australian Capital Territory, Australia.

Abstract

Cobalt-mediated radical polymerizations (CMRPs) have been initiated by the radical decarboxylation of tetrachlorophthalimide activated esters. This allows for the controlled radical polymerization of activated monomers across a broad temperature range with a single cobalt species, with the incorporation of polymer end groups derived from simple carboxylic acid derivatives and termination with an organozinc reagent. This method has been applied to the synthesis of a polymer/graphene conjugate and a water-soluble protein/polymer conjugate, demonstrating the first examples of CMRP in graphene and protein conjugation.