Photoreaction of a Hydroxyalkyphenone with the Membrane of Polymersomes: A Versatile Method To Generate Semipermeable Nanoreactors

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 org. mols., 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 chem. 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-irradn. The photoreactive compd. incorporated into the block copolymer membranes independently of their chem. nature or the presence of double bonds. This treatment of polymersomes resulted in substantial increase in permeability for org. compds. 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 detd. to be between 1.9 and 38.2 nm s-1. It correlated with the hydrophobicity of the compds. 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 degrdn. by proteases. [on SciFinder(R)]