Polymer Science

One-pot synthesis of oxidation-sensitive supramolecular gels and vesicles

Authors

  • Aroa Duro-Castano University College London-Chemistry Department ,
  • Laura Rodriguez-Arco University College London-Chemistry Department & University of Granada ,
  • Lorena Ruiz-Perez Department of Chemistry, University College London, UK. Institute for the Physics of Living Systems, University College London, UK. The EPSRC/Jeol Centre for Liquid Phase Electron Microscopy, University College London, UK ,
  • Cesare De Pace University College London-Chemistry Department ,
  • Gabriele Marchello University College London-Chemistry Department ,
  • Carlos Noble-Jesus University College London-Chemistry Department ,
  • Giuseppe Battaglia University College London-Chemistry Department, Institute for Bioengineering of Catalunya (IBEC), The Barcelona Institute of Science and Technology, Barcelona (Spain). Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

Abstract

Polypeptide-based nanoparticles offer unique advantages from a nanomedicine perspective such as biocompatibility, biodegradability and stimuli-responsive properties to (patho)physiological conditions. Conventionally, self-assembled polypeptide nanostructures are prepared by first synthesizing their constituent amphiphilic polypeptides followed by post-polymerization self-assembly. Herein, we describe the one-pot synthesis of oxidation-sensitive supramolecular micelles and vesicles. This was achieved by polymerization-induced self-assembly (PISA) of the N-carboxyanhydride (NCA) precursor of methionine using polyethylene oxide as stabilizing and hydrophilic block in dimethyl sulfoxide (DMSO). By adjusting the hydrophobic block length and concentration we obtained a range of morphologies from spherical to worm-like micelles, to vesicles. Remarkably, the secondary structure of polypeptides greatly influenced the final morphology of the assemblies. Surprisingly, worm-like micellar morphologies were obtained for a wide range of methionine block lengths and solid contents, with spherical micelles restricted to very short hydrophobic lengths. Worm-like micelles further assembled into oxidation-sensitive, self-standing gels in the reaction pot. Both vesicles and worm-like micelles obtained using this method demonstrated to degrade under controlled oxidant conditions which would expand their biomedical applications such as in sustained drug release or as cellular scaffolds in tissue engineering.

Content

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Supplementary material

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Supplementary Materials
Supplementary methods (Dynamic Light Scattering (DLS), Rheological characterization of PEO125-PMET40 gels) Supplementary Figures S1-15, Supplementary Table 1
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Supplementary Video 1
Video illustrating the injectability of PEO125-PMET40 hydrogels in the laboratory settings.
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Supplementary Video 2
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40 that are imaged in globular structures. Video S1: dose rate: 0.6 e-/A2/s; total dose: 39.6 e-/A2. Video S4: dose rate: 0.7 e-/A2/s; total dose: 347.2 e-/A2.
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Supplementary Video 3
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40, imaged within the globular structures and their morphological changes due to the radical oxygen species induced by long exposure to the electron beam. Video S2: dose rate: 1495.89 e-/A2/s; total dose: 103216.4 e-/A2. Video S3: dose rate: 133.3 e-/A2/s; total dose: 29326.2 e-/A2. Video S5: dose rate: 33.3 e-/A2/s; total dose: 40626 e-/A2. Video S6: Dose rate: 9.19 e-/A2/s. Total dose: 40626 e-/A2.
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Supplementary Video 4
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40, imaged within the globular structures and their morphological changes due to the radical oxygen species induced by long exposure to the electron beam. Video S2: dose rate: 1495.89 e-/A2/s; total dose: 103216.4 e-/A2. Video S3: dose rate: 133.3 e-/A2/s; total dose: 29326.2 e-/A2. Video S5: dose rate: 33.3 e-/A2/s; total dose: 40626 e-/A2. Video S6: Dose rate: 9.19 e-/A2/s. Total dose: 40626 e-/A2.
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Supplementary Video 5
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40 that are imaged in globular structures. Video S1: dose rate: 0.6 e-/A2/s; total dose: 39.6 e-/A2. Video S4: dose rate: 0.7 e-/A2/s; total dose: 347.2 e-/A2.
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Supplementary Video 6
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40, imaged within the globular structures and their morphological changes due to the radical oxygen species induced by long exposure to the electron beam. Video S2: dose rate: 1495.89 e-/A2/s; total dose: 103216.4 e-/A2. Video S3: dose rate: 133.3 e-/A2/s; total dose: 29326.2 e-/A2. Video S5: dose rate: 33.3 e-/A2/s; total dose: 40626 e-/A2. Video S6: Dose rate: 9.19 e-/A2/s. Total dose: 40626 e-/A2.
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Supplementary Video 7
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40, imaged within the globular structures and their morphological changes due to the radical oxygen species induced by long exposure to the electron beam. Video S2: dose rate: 1495.89 e-/A2/s; total dose: 103216.4 e-/A2. Video S3: dose rate: 133.3 e-/A2/s; total dose: 29326.2 e-/A2. Video S5: dose rate: 33.3 e-/A2/s; total dose: 40626 e-/A2. Video S6: Dose rate: 9.19 e-/A2/s. Total dose: 40626 e-/A2.
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Supplementary Video 8
Liquid STEM video displaying the worm-like micelles of the oxidation-sensitive polymer PEO125-PMET40 that are imaged at the edge of the globular structures after long time exposure to the beam. Video of the droplet-like gel edge acquired by liquid-phase STEM. Video S7: dose rate: 22.69 e-/A2/s; total dose: 34670.32 e-/A2.