Research ArticleCONDENSED MATTER PHYSICS

Molecular engineering of polymersome surface topology

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Science Advances  15 Apr 2016:
Vol. 2, no. 4, e1500948
DOI: 10.1126/sciadv.1500948
  • Fig. 1 Copolymers’ chemical structure and conformation.

    (A and B) Molecular structure of PMPC-PDPA (A) and PEO-PDPA (B) with the corresponding molecular models showing the most probable configuration of the chains at the hydrophilic/hydrophobic interface. The models are shown as isometric projections and hydrophobic and hydrophilic views. The structure was minimized using the semiempirical method PM7. (C and D) Molecular structure of the PEO-PDPA-PMPC triblock (C) and the occupancy of the two hydrophilic block PEO and PMPC are calculated using the semiempirical method PM7 and represented as isometric projection and top view (D). (E) Possible arrangements of the triblock PEO-PDPA-PMPC in a binary mixture with PMPC-PDPA diblock and in a ternary mixture with PMPC-PDPA and PEO-PDPA diblocks.

  • Fig. 2 Binary phase diagram.

    (A) Graph showing the average spacing of the domains formed on the PMPC-PDPA/PEO-PDPA-PMPC polymersomes surface as a function of triblock concentration. (B and C) TEM images (B) and coarse-grained models (C) shown with semitransparent top surface to simulate transmission imaging of PMPC-PDPA/PEO-PDPA-PMPC polymersomes at different triblock concentrations. (D) Comparison of the polymersome surface patterns visualized by TEM and obtained by the simulations. The TEM images are shown using a color palette calibrated with the grayscale. Scale bars, 20 nm; gold is used to represent the PMPC domains, and blue to represent the PEO domains.

  • Fig. 3 Coarse-grained simulation of PMPC-PDPA/PEO-PDPA-PMPC polymersomes at different triblock concentrations displayed with a nontransparent surface.

    Regions of interest extracted from the surface highlight our proposed mechanism of domain formation and its shape evolution as a function of triblock concentration. Gold is used to represent the PMPC domains, and blue to represent the PEO domains.

  • Fig. 4 Ternary phase diagram.

    (A) Diagram of PMPC-PDPA/PEO-PDPA-PMPC/PEO-PDPA polymersomes. (B) Graphical representation of the three different phases observed in the diagram. Scale bars, 20 nm.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/2/4/e1500948/DC1

    fig. S1. 1H NMR spectrum of PEO-PDPA-PMPC triblock copolymer in CDCl3/MeOH (3:1); composition: PEO45-PDPA60-PMPC12 (relative integration of protons e versus b/c and h).

    fig. S2. GPC trace of PEO-PDPA-PMPC triblock copolymer in 0.25% TFA aqueous solution, PDI = 1.13, superimposed to PEO45-PDPA60.

    fig. S3. Representative size distribution of PMPC-PDPA polymersomes containing different amounts of PMPC-PDPA-PEO triblock copolymers measured by dynamic light scattering.

    fig. S4. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (90:10).

    fig. S5. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (80:20).

    fig. S6. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (60:40).

    fig. S7. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (40:60).

    fig. S8. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (10:90).

    fig. S9. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:80:10).

    fig. S10 (A) Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:60:30). (B) Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:30:60).

    fig. S11. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (60:30:10).

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. 1H NMR spectrum of PEO-PDPA-PMPC triblock copolymer in CDCl3/MeOH (3:1); composition: PEO45-PDPA60-PMPC12 (relative integration of protons e versus b/c and h).
    • fig. S2. GPC trace of PEO-PDPA-PMPC triblock copolymer in 0.25% TFA aqueous solution, PDI = 1.13, superimposed to PEO45-PDPA60.
    • fig. S3. Representative size distribution of PMPC-PDPA polymersomes containing different amounts of PMPC-PDPA-PEO triblock copolymers measured by dynamic light scattering.
    • fig. S4. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (90:10).
    • fig. S5. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (80:20).
    • fig. S6. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (60:40).
    • fig. S7. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (40:60).
    • fig. S8. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO binary mixture (10:90).
    • fig. S9. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:80:10).
    • fig. S10. (A) Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:60:30). (B) Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (10:30:60).
    • fig. S11. Low-magnification image of PMPC-PDPA/PMPC-PDPA-PEO/PEO-PDPA ternary mixture (60:30:10).

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