Biocatalytic "Oxygen-Fueled" Atom Transfer Radical Polymerization

Alan E Enciso; Liye Fu; Sushil Lathwal; Mateusz Olszewski; Zhenhua Wang; Subha R Das; Alan J Russell; Krzysztof Matyjaszewski

doi:10.1002/anie.201809018

Biocatalytic "Oxygen-Fueled" Atom Transfer Radical Polymerization

Angew Chem Int Ed Engl. 2018 Dec 3;57(49):16157-16161. doi: 10.1002/anie.201809018. Epub 2018 Nov 8.

Authors

Alan E Enciso¹, Liye Fu¹, Sushil Lathwal¹, Mateusz Olszewski¹, Zhenhua Wang¹, Subha R Das¹, Alan J Russell², Krzysztof Matyjaszewski¹

Affiliations

¹ Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA.
² Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, PA, 15213, USA.

PMID: 30329207
DOI: 10.1002/anie.201809018

Abstract

Atom transfer radical polymerization (ATRP) can be carried out in a flask completely open to air using a biocatalytic system composed of glucose oxidase (GOx) and horseradish peroxidase (HRP) with an active copper catalyst complex. Nanomolar concentrations of the enzymes and ppm amounts of Cu provided excellent control over the polymerization of oligo(ethylene oxide) methyl ether methacrylate (OEOMA₅₀₀ ), generating polymers with high molecular weight (M_n >70 000) and low dispersities (1.13≤Đ≤1.27) in less than an hour. The continuous oxygen supply was necessary for the generation of radicals and polymer chain growth as demonstrated by temporal control and by inducing hypoxic conditions. In addition, the enzymatic cascade polymerization triggered by oxygen was used for a protein and DNA functionalized with initiators to form protein-b-POEOMA and DNA-b-POEOMA bioconjugates, respectively.

Keywords: ATRP; enzymes; oxygen; polymerization; proteins.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.