Oxidation-responsive polymeric vesicles

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Vesicles formed in water by synthetic macro-amphiphiles have attracted much attention as nanocontainers having properties that extend the physical and chemical limits of liposomes. We sought to develop ABA block copolymeric amphiphiles that self-assemble into unilamellar vesicles that can be further oxidatively destabilized. We selected poly(ethylene glycol) (PEG) as the hydrophilic A blocks, owing to its resistance to protein adsorption and low toxicity. As hydrophobic B blocks, we selected poly(propylene sulphide) (PPS), owing to its extreme hydrophobicity, its low glass-transition temperature, and most importantly its oxidative conversion from a hydrophobe to a hydrophile, poly(propylene sulphoxide) and ultimately poly(propylene sulphone). This is the first example of the use of oxidative conversions to destabilize such carriers. This new class of oxidation-responsive polymeric vesicles may find applications as nanocontainers in drug delivery, biosensing and biodetection.

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Figure 1: Cryo-TEM of EG16PS50EG16 polymersomes.
Figure 2: Turbidity measurement on PEG–PPS–PEG polymersome suspensions during oxidation in excess H2O2.
Figure 3: 1H-NMR spectra of PEG–PPS–PEG polymersome suspensions in D2O before and after oxidation.
Figure 4: Cryo-TEM of PEG–PPS–PEG polymersome suspensions after exposure to H2O2.
Figure 5: 1H-PGSE NMR plots for polymersomes, oxidized block copolymer and reference PEG3400.
Figure 6: Two-dimensional NMR spectra of the oxidized block copolymer suspension in D2O.


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This research was supported in part by a grant from the Research Commission of the Swiss Federal Institute of Technology. Authors acknowledge Anita Saraf for the preliminary experimental work on copolymer oxidation, and Heinz Rüegger at ETH Zurich for discussions on NMR results.

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Correspondence to Nicola Tirelli or Jeffrey A. Hubbell.

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The authors declare no competing financial interests.

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Napoli, A., Valentini, M., Tirelli, N. et al. Oxidation-responsive polymeric vesicles. Nature Mater 3, 183–189 (2004) doi:10.1038/nmat1081

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