Research ArticleSUPRAMOLECULAR CHEMISTRY

Structural water as an essential comonomer in supramolecular polymerization

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Science Advances  15 Nov 2017:
Vol. 3, no. 11, eaao0900
DOI: 10.1126/sciadv.aao0900
  • Fig. 1 Water-activated supramolecular polymerization.

    Chemical structures of (A) TC7 and (B) the control compounds TC6 and DC7. (C) Images of the TC7 samples with different water content [TC7n-H1 is used to abbreviate samples with TC7: water (H) ratio of n: 1 (w/w)]. (D) Fibers drawn from TC710-H1 (i and ii); fiber of TC73-H1 injected to hexane (rhodamine B was added to the glue to make it clearly visible) (iii); fiber generated by coating glass slides with TC75-H1 and then pulling them apart (at 80°C) (iv).

  • Fig. 2 The nature of water molecules in TC7-H materials.

    (A) ATR-IR spectra of TC7 samples prepared with H2O and D2O (TC710-H1 and TC710-D1). (B) H/D exchange experiments conducted on TC710-D1 adhesive (for details, see the Supplementary Materials). (C) The dependence of DC conductivity σdc versus 1/T for TC7-H materials with different water content. (D) Dielectric loss versus frequency for TC7-H materials with different water content at a temperature of −100°C: Frequency dependence of loss peaks due to hydrogen bonding between TC7 and water (maxima labeled in pink) and between two adjacent TC7 molecules (red labels). (E) Averaged hydrogen-bond strengths (EHB) of crown ether–water systems with different number of water molecules (Nwater) as obtained from the density functional theory (DFT) calculations: Some representative molecular structures are shown here (inserted chemical structures) and in fig. S26. The gray, red, and white spheres are carbon, oxygen, and hydrogen atoms, respectively. Hydrogen-bonds are indicated by short black-dashed lines. Blue horizontal–dashed and dot-dashed lines represent the theoretical and experimental EHB’s of bulk ice Ih, respectively.

  • Fig. 3 Application of TC710-H1 materials as adhesive materials.

    (A) A cartoon representation of the adhesion procedure. (B to D) Macroscopic adhesive behavior of TC710-H1 materials on hydrophilic surface. The adhesion areas are 9.0 × 8.0 cm2 (B), 4.5 × 1.0 cm2 (C), and 4.0 × 2.5 cm2 (D), respectively.

  • Fig. 4 Measurements of pull-off adhesion strength.

    (A) Illustration of the pull-off adhesion test. (B) Comparison of the adhesion effect of TC710-H1 and commercially available adhesive poly(vinyl acetate) (PVA) glue at 25°C. (C) Adhesion strength of TC710-H1 at different temperatures. (D) Recycling tests of TC710-H1 at 25°C.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/11/eaao0900/DC1

    Materials and Methods

    scheme S1. Synthesis of TC7 and control compounds.

    scheme S2. Pull-off test of control compounds.

    fig. S1. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC7.

    fig. S2. 13C NMR spectrum (100 MHz, CDCl3, 25°C) of TC7.

    fig. S3. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of DC7.

    fig. S4. 13C NMR spectrum (100 MHz, CDCl3, 25°C) of DC7.

    fig. S5. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC6.

    fig. S6. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC6.

    fig. S7. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC-open.

    fig. S8. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC-open.

    fig. S9. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC8.

    fig. S10. 1H NMR spectrum (125 MHz, CDCl3, 25°C) of TC8.

    fig. S11. 13C NMR spectrum (400 MHz, CDCl3, 25°C) of TCB.

    fig. S12. 1H NMR spectrum (125 MHz, CDCl3, 25°C) of TCB.

    fig. S13. 1H NMR spectrum (500 MHz, CDCl3, 25°C) of TC7A.

    fig. S14. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC7A.

    fig. S15. PXRD pattern of dry TC7.

    fig. S16. IR spectrum of dry TC7.

    fig. S17. IR spectra of TC710-H1 and TC710-D1.

    fig. S18. Water absorbance curves of TC7 under ambient conditions (25°C, 40% RH).

    fig. S19. DSC measurements of TC710-H1.

    fig. S20. SEM images of TC710-H1 adhesive.

    fig. S21. Storage (Gʹ) and loss (G″) moduli of TC710-H1 (red circles) and TC75-H1 (blue circles) at 25°C.

    fig. S22. Rheological performance of TC7-H materials at different temperatures.

    fig. S23. H/D exchange experiments of TC710-D1 adhesive.

    fig. S24. SAXS of the TC710-H1 adhesive at 25°C.

    fig. S25. SAXS of the TC71-H1 adhesive at 25°C.

    fig. S26. The real part of the complex conductivity versus frequency of a TC75-H1 adhesive at the indicated temperatures.

    fig. S27. [d log σdc/ dT]−1/2 versus T for TC7-H materials with different water contents.

    fig. S28. H-bonding interactions between neighboring water molecules in the crystal structure of water (ice).

    fig. S29. Detailed atomic structures of crown ether units connected by water molecules.

    fig. S30. Tensile adhesion strength measurements of TC7-H adhesives.

    fig. S31. Macroscopic tests of adhesion behavior of TC710-H1.

    fig. S32. Tack tests of TC710-H1 adhesive at different temperature.

    fig. S33. TGA measurements of TC7-H adhesive materials.

    movie S1. Pulling a fiber from TC710-H1 adhesive material.

    movie S2. Fibers pulled from TC710-H1 under optical microscopy.

    movie S3. Injectable supramolecular adhesive from TC73-H1.

    movie S4. Macroscopic TC710-H1 adhesion property.

    References (4252)

  • Supplementary Materials

    This PDF file includes:

    • Supplementary Materials and Methods
    • scheme S1. Synthesis of TC7 and control compounds.
    • scheme S2. Pull-off test of control compounds.
    • fig. S1. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC7.
    • fig. S2. 13C NMR spectrum (100 MHz, CDCl3, 25°C) of TC7.
    • fig. S3. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of DC7.
    • fig. S4. 13C NMR spectrum (100 MHz, CDCl3, 25°C) of DC7.
    • fig. S5. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC6.
    • fig. S6. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC6.
    • fig. S7. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC-open.
    • fig. S8. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC-open.
    • fig. S9. 1H NMR spectrum (400 MHz, CDCl3, 25°C) of TC8.
    • fig. S10. 1H NMR spectrum (125 MHz, CDCl3, 25°C) of TC8.
    • fig. S11. 13C NMR spectrum (400 MHz, CDCl3, 25°C) of TCB.
    • fig. S12. 1H NMR spectrum (125 MHz, CDCl3, 25°C) of TCB.
    • fig. S13. 1H NMR spectrum (500 MHz, CDCl3, 25°C) of TC7A.
    • fig. S14. 13C NMR spectrum (125 MHz, CDCl3, 25°C) of TC7A.
    • fig. S15. PXRD pattern of dry TC7.
    • fig. S16. IR spectrum of dry TC7.
    • fig. S17. IR spectra of TC710-H1 and TC710-D1.
    • fig. S18. Water absorbance curves of TC7 under ambient conditions (25°C, 40% RH).
    • fig. S19. DSC measurements of TC710-H1.
    • fig. S20. SEM images of TC710-H1 adhesive.
    • fig. S21. Storage (Gʹ) and loss (G″) moduli of TC710-H1 (red circles) and TC75-H1 (blue circles) at 25°C.
    • fig. S22. Rheological performance of TC7-H materials at different temperatures.
    • fig. S23. H/D exchange experiments of TC710-D1 adhesive.
    • fig. S24. SAXS of the TC710-H1 adhesive at 25°C.
    • fig. S25. SAXS of the TC71-H1 adhesive at 25°C.
    • fig. S26. The real part of the complex conductivity versus frequency of a
      TC75-H1 adhesive at the indicated temperatures.
    • fig. S27. d log σdc/dT−1/2 versus T for TC7-H materials with different water contents.
    • fig. S28. H-bonding interactions between neighboring water molecules in the crystal structure of water (ice).
    • fig. S29. Detailed atomic structures of crown ether units connected by water molecules.
    • fig. S30. Tensile adhesion strength measurements of TC7-H adhesives.
    • fig. S31. Macroscopic tests of adhesion behavior of TC710-H1.
    • fig. S32. Tack tests of TC710-H1 adhesive at different temperature.
    • fig. S33. TGA measurements of TC7-H adhesive materials.
    • Legends for movies S1 to S4
    • References (42–52)

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    Other Supplementary Material for this manuscript includes the following:

    • movie S1 (.mp4 format). Pulling a fiber from TC710-H1 adhesive material.
    • movie S2 (.mp4 format). Fibers pulled from TC710-H1 under optical microscopy.
    • movie S3 (.mp4 format). Injectable supramolecular adhesive from TC73-H1.
    • movie S4 (.mp4 format). Macroscopic TC710-H1 adhesion property.

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