Research ArticleChemistry

Two-dimensional polymers with versatile functionalities via gemini monomers

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Science Advances  22 Nov 2019:
Vol. 5, no. 11, eaaw9120
DOI: 10.1126/sciadv.aaw9120
  • Fig. 1 Preparation and characterization of 2D net-poly(MA-11-2-11-MA).

    (A) Schematic illustration of the molecular structure of gemini monomer MA-11-2-11-MA and 2D net-poly(MA-11-2-11-MA). (B) AFM image and height analysis of the 2D net-poly(MA-11-2-11-MA) on the silicon substrate. Rq, root mean square roughness. (C) Simulation of the bilayer thickness with vertically arranged MA-11-2-11-MA monomers using Materials Studio. (D) TEM image of the freestanding film of 2D net-poly(MA-11-2-11-MA).

  • Fig. 2 DPD simulation of 2D net-poly(MA-11-2-11-MA).

    (A) Schematic illustration of the coarse-grained model of MA-11-2-11-MA. (B) Left: A representative snapshot of the MA-11-2-11-MA bilayer before polymerization. The conversion ratio of methacrylate groups is 0%. Right: Density profile of each component distributed in the vertical direction. Alkyl segments (black), ammonium groups (blue), methacrylate groups (red), and water (yellow). (C) Snapshots of MA-11-2-11-MA bilayers at increasing conversion ratios of methacrylate groups. (D) Left: A representative snapshot of the net-poly(MA-11-2-11-MA) bilayer after polymerization. The inset represents a top view of the poly(methacrylate) sublayer. The conversion ratio of the methacrylate groups is 98%. Right: Density profile of each component distributed in the vertical direction.

  • Fig. 3 NMR characterization of MA-11-2-11-MA assembly before and after polymerization.

    (A) Schematic illustration of the proton number in MA-11-2-11-MA. (B) 1H NMR spectra of MA-11-2-11-MA assembly in D2O at 65°C (top) and the corresponding ROESY spectra by the selective irradiation of proton H-9 (bottom). (C) ROESY spectra of MA-11-2-11-MA assembly by the selective irradiation of H-9 at increased conversion ratios of methacrylate groups. The conversion ratios were estimated from the FT-IR spectra.

  • Fig. 4 Functionalization of 2D net-poly(MA-11-2-11-MA).

    (A) Chemical structures of the monomeric derivatives (MA-11-F; F, various functional groups) and copolymerization with MA-11-2-11-MA. (B) Fluorescence films of net-poly(MA-11-2-11-MA)-co-(MA-11-F) (F = RhB, Fls, or Pyr) in number and letter shapes (scale bar, 500 μm). (C) Fluorescence microscope images of net-poly(MA-11-2-11-MA)-co-(MA-11-C≡C)–coated silica wool after post-polymerization functionalization with RhB-EO4-N3, Fls-EO4-N3, and Pyr-EO4-N3 via click reactions (scale bars, 200 μm).

  • Fig. 5 Microstructures of 2D net-poly(MA-11-2-11-MA)-co-(MA-11-RhB).

    (A to C) TEM images of net-poly(MA-11-2-11-MA)-co-(MA-11-RhB)–coated silica microspheres, microrods, microboards (insets), and the corresponding hollow capsules. (D to F) Fluorescence microscopy images of net-poly(MA-11-2-11-MA)-co-(MA-11-RhB)–coated silica microspheres, microrods, microboards (insets), and the corresponding hollow capsules.

  • Fig. 6 Surface modification and antibacterial property of 2D copolymers.

    (A) Quartz cuvettes, copper coins, and sulfonated polystyrene petri dishes before (left) and after (right) coating with fluorescent net-poly(MA-11-2-11-MA)-co-(MA-11-RhB). Images in the top series are photographs, and those in the bottom series are the corresponding fluorescence images. (Photo Credit: Yang Li, Jilin University). (B) Cotton gauze before (left) and after coating with fluorescent net-poly(MA-11-2-11-MA)-co-(MA-11-RhB) and thoroughly washing (right) (Photo Credit: Yang Li, Jilin University). (C) Proliferation of S. aureus released from the cotton gauze without (left) and with (right) net-poly(MA-11-2-11-MA)-co-(MA-11-RhB) (Photo Credit: Yang Li, Jilin University). (D) SEM images of S. aureus on the cotton gauze without (left) and with (right) net-poly(MA-11-2-11-MA)-co-(MA-11-RhB).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/11/eaaw9120/DC1

    Fig. S1. The CMC and the adsorption behavior of MA-11-2-11-MA.

    Fig. S2. Preparation of net-poly(MA-11-2-11-MA) on the silicon wafer.

    Fig. S3. Molecular orientation of MA-11-2-11-MA in multilayer films.

    Fig. S4. XPS spectra of C1s of net-poly(MA-11-2-11-MA).

    Fig. S5. AFM indentation experiments on 2D net-poly(MA-11-2-11-MA).

    Fig. S6. NMR characterization of individually dispersed MA-11-2-11-MA.

    Fig. S7. DPD simulation of net-poly(MA-11-2-11-MA)-co-(MA-11-2-Me3).

    Fig. S8. Functionalization of 2D net-poly(MA-11-2-11-MA).

    Fig. S9. Preparation of the net-poly(MA-11-2-11-MA)-co-(MA-11-RhB) capsules.

    Table S1. Repulsion parameters used in the DPD simulations.

  • Supplementary Materials

    This PDF file includes:

    • Fig. S1. The CMC and the adsorption behavior of MA-11-2-11-MA.
    • Fig. S2. Preparation of net-poly(MA-11-2-11-MA) on the silicon wafer.
    • Fig. S3. Molecular orientation of MA-11-2-11-MA in multilayer films.
    • Fig. S4. XPS spectra of C1s of net-poly(MA-11-2-11-MA).
    • Fig. S5. AFM indentation experiments on 2D net-poly(MA-11-2-11-MA).
    • Fig. S6. NMR characterization of individually dispersed MA-11-2-11-MA.
    • Fig. S7. DPD simulation of net-poly(MA-11-2-11-MA)-co-(MA-11-2-Me3).
    • Fig. S8. Functionalization of 2D net-poly(MA-11-2-11-MA).
    • Fig. S9. Preparation of the net-poly(MA-11-2-11-MA)-co-(MA-11-RhB) capsules.
    • Table S1. Repulsion parameters used in the DPD simulations.

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