Photoreaction of a hydroxyalkyphenone with the membrane of polymersomes: a versatile method to generate semipermeable nanoreactors

Mariana Spulber, Adrian Najer, Katharina Winkelbach, Olfa Glaied, Marcus Waser, Uwe Pieles, Wolfgang Meier, Nico Bruns

Research output: Contribution to journalArticle

75 Citations (Scopus)

Abstract

Block copolymer vesicles can be turned into nanoreactors when a catalyst is encapsulated in these hollow nanostructures. However the membranes of these polymersomes are most often impermeable to small organic molecules, while applications as nanoreactor, as artificial organelles, or as drug-delivery devices require an exchange of substances between the outside and the inside of polymersomes. Here, a simple and versatile method is presented to render polymersomes semipermeable. It does not require complex membrane proteins or pose requirements on the chemical nature of the polymers. Vesicles made from three different amphiphilic block copolymers (α,ω-hydroxy-end-capped poly(2-methyl-2-oxazoline)-block-poly(dimethylsiloxane)-block-poly(2-methyl-2- oxazoline) (PMOXA-b-PDMS-b-PMOXA), α,ω-acrylate-end-capped PMOXA-b-PDMS-b-PMOXA, and poly(ethylene oxide)-block-poly(butadiene) (PEO-b-PB)) were reacted with externally added 2-hydroxy-4′-2-(hydroxyethoxy)-2- methylpropiophenone under UV-irradiation. The photoreactive compound incorporated into the block copolymer membranes independently of their chemical nature or the presence of double bonds. This treatment of polymersomes resulted in substantial increase in permeability for organic compounds while not disturbing the size and the shape of the vesicles. Permeability was assessed by encapsulating horseradish peroxidase into vesicles and measuring the accessibility of substrates to the enzyme. The permeability of photoreacted polymersomes for ABTS, AEC, pyrogallol, and TMB was determined to be between 1.9 and 38.2 nm s-1. It correlated with the hydrophobicity of the compounds. Moreover, fluorescent dyes were released at higher rates from permeabilized polymersomes compared to unmodified ones. The permeabilized nanoreactors retained their ability to protect encapsulated biocatalysts from degradation by proteases.

LanguageEnglish
Pages9204-9212
Number of pages9
JournalJournal of the American Chemical Society
Volume135
Issue number24
DOIs
Publication statusPublished - 19 Jun 2013

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Nanoreactors
Block copolymers
Permeability
Membranes
Pyrogallol
Artificial Cells
Ethylene Oxide
Biocatalysts
Nanostructures
Polydimethylsiloxane
Enzymes
Horseradish Peroxidase
Hydrophobicity
Polyethylene oxides
Butadiene
Drug delivery
Hydrophobic and Hydrophilic Interactions
Fluorescent Dyes
Organic compounds
Polymers

Keywords

  • polymersomes
  • semipermeable nanoreactors
  • amphiphilic block copolymers

Cite this

Spulber, Mariana ; Najer, Adrian ; Winkelbach, Katharina ; Glaied, Olfa ; Waser, Marcus ; Pieles, Uwe ; Meier, Wolfgang ; Bruns, Nico. / Photoreaction of a hydroxyalkyphenone with the membrane of polymersomes : a versatile method to generate semipermeable nanoreactors. In: Journal of the American Chemical Society . 2013 ; Vol. 135, No. 24. pp. 9204-9212.
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Photoreaction of a hydroxyalkyphenone with the membrane of polymersomes : a versatile method to generate semipermeable nanoreactors. / Spulber, Mariana; Najer, Adrian; Winkelbach, Katharina; Glaied, Olfa; Waser, Marcus; Pieles, Uwe; Meier, Wolfgang; Bruns, Nico.

In: Journal of the American Chemical Society , Vol. 135, No. 24, 19.06.2013, p. 9204-9212.

Research output: Contribution to journalArticle

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T2 - Journal of the American Chemical Society

AU - Spulber, Mariana

AU - Najer, Adrian

AU - Winkelbach, Katharina

AU - Glaied, Olfa

AU - Waser, Marcus

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AU - Meier, Wolfgang

AU - Bruns, Nico

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