Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 36, Issue 6, Pages 507-514Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.201400642
Keywords
amphiphilic block copolymer vesicles; atom transfer radical polymerization (ATRP); biocatalysis; bio-inspiration; nanoreactors
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Funding
- Swiss National Science Foundation [200021_140693, PP00P2_123373, PP00P2_144697]
- Swiss National Science Foundation (National Centre of Competence in Research Bio-Inspired Materials)
- Holcim Stiftung Wissen
- Marie Curie Actions of the European Commission
- Swiss Nanoscience Institute
- Dr. Alfred Bretscher Fund
- Swiss National Science Foundation (SNF) [200021_140693, PP00P2_144697] Funding Source: Swiss National Science Foundation (SNF)
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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 H-1 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.
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