Filling polymersomes with polymers by peroxidase-catalyzed atom transfer radical polymerization

Maria Valentina Dinu, Mariana Spulber, Kasper Renggli, Dalin Wu, Christophe A. Monnier, Alke Petri-Fink, Nico Bruns

Research output: Contribution to journalArticlepeer-review

43 Citations (Scopus)


Polymersomes that encapsulate a hydrophilic polymer are prepared by conducting biocatalytic atom transfer radical polymerization (ATRP) in these hollow nanostructures. To this end, ATRPase horseradish peroxidase (HRP) is encapsulated into vesicles self-assembled from poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) diblock copolymers. The vesicles are turned into nanoreactors by UV-induced permeabilization with a hydroxyalkyl phenone and used to polymerize poly(ethylene glycol) methyl ether acrylate (PEGA) by enzyme-catalyzed ATRP. As the membrane of the polymersomes is only permeable for the reagents of ATRP but not for macromolecules, the polymerization occurs inside of the vesicles and fills the polymersomes with poly(PEGA), as evidenced by 1H NMR. Dynamic and static light scattering show that the vesicles transform from hollow spheres to filled spheres during polymerization. Transmission electron microscopy (TEM) and cryo-TEM imaging reveal that the polymersomes are stable under the reaction conditions. The polymer-filled nanoreactors mimic the membrane and cytosol of cells and can be useful tools to study enzymatic behavior in crowded macromolecular environments. A hydrophilic polymer is synthesized in polymersome nanoreactors by enzyme-catalyzed atom transfer radical polymerization (ATRP). To this end, polymersomes are permeabilized by photoreaction with a hydroxyalkylphenone. As the polymersome membrane is permeable for the monomer but not for the resulting polymer, the synthesized polymer fills the vesicles, transforming them from hollow spherical objects to polymer-filled polymersomes.

Original languageEnglish
Pages (from-to)507-514
Number of pages8
JournalMacromolecular Rapid Communications
Issue number6
Early online date23 Jan 2015
Publication statusPublished - 1 Mar 2015


  • amphiphilic block copolymer vesicles
  • atom transfer radical polymerization (ATRP)
  • bio-inspiration
  • biocatalysis
  • nanoreactors


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