Enzyme-initiated free radical polymerizations of vinyl monomers using horseradish peroxidase

Kyle J. Rodriguez, Michela M. Pellizzoni, Robert J. Chadwick, Chao Guo, Nico Bruns

Research output: Chapter in Book/Report/Conference proceedingChapter

1 Citation (Scopus)


In this chapter, we highlight the use of horseradish peroxidase (HRP) as a catalyst to initiate free radical polymerizations of vinyl monomers under benign reaction conditions. A variety of vinyl monomers, including 4-acryloylmorpholine (AM), 2-hydroxyethyl methacrylate (HEMA), and poly(ethylene glycol) methyl ether acrylate (PEGA) were polymerized. The enzyme converts exogenous hydrogen peroxide into a usable radical source, which when coupled with a β-diketone, yields a radical that initiates chain growth in the presence of monomers. The resulting polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). By using enzymatic free radical polymerizations, polymers can be generated in a sustainable, environmentally-friendly, and scalable fashion.

Original languageEnglish
Title of host publicationMethods in Enzymology
EditorsNico Bruns, Katja Loos
Place of PublicationCambridge, MA
PublisherAcademic Press Inc.
Number of pages14
ISBN (Print)9780128170953
Publication statusPublished - 15 Oct 2019

Publication series

NameMethods in Enzymology
ISSN (Print)0076-6879
ISSN (Electronic)1557-7988


  • acrylates and methacrylates
  • enzymatic catalysis
  • free radical polymerization
  • horseradish peroxidase
  • oxidoreductase


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