Research ArticleChemistry

A polyaromatic nanocapsule as a sucrose receptor in water

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Science Advances  25 Aug 2017:
Vol. 3, no. 8, e1701126
DOI: 10.1126/sciadv.1701126
  • Fig. 1 Cartoon representation of saccharide recognitions and structures of a polyaromatic nanocapsule and saccharides.

    Recognition of d-glucose (A) in a hydrogen-bonding cavity modeled after the binding site of sucrose hydrolase (E322Q-glucose complex) from Xanthomonas axonopodis pv. glycines (6) and (B) in a polyaromatic cavity. (C) Coordination-driven polyaromatic nanocapsule 1 and (D) its slice through the center of the crystal structure [space-filling model; substituents (R) are replaced by hydrogen atoms for clarity]. (E) d-Sucrose (2a), glucose derivatives 3a to 3c, and d-fructose (3d) used as guest molecules.

  • Fig. 2 Host-guest interactions between capsule 1 and monosaccharides.

    (A) Schematic representation of host-guest interactions between capsule 1 and d-glucose (3a) or pentamethylated α-d-glucose 3b in H2O. 1H NMR spectra (500 MHz, D2O, room temperature; left) and ESI-TOF MS spectra (H2O, room temperature, tetravalent molecular ion peak; right) of (B) a mixture of 1 and 3a, and (C) host-guest complex 13b.

  • Fig. 3 Encapsulation of d-sucrose within capsule 1 in water.

    (A) Schematic representation of host-guest interactions between capsule 1, d-glucose (3a), and d-fructose (3d) (left) and the encapsulation of d-sucrose (2a) within 1 (right). (B) 1H NMR and (C) 1H DOSY NMR spectra (500 MHz, D2O, room temperature) of 12a. (D) 1H NMR spectrum (500 MHz, D2O, room temperature) of a mixture of 3a and 3d with 1. (E) ESI-TOF MS spectrum (H2O, room temperature) of 12a. (F) Structure of 12a in water (left) and its slice through the center (right) (substituents and counterions are omitted for clarity). (G) van’t Hoff plot for the thermodynamic parameters of 12a.

  • Fig. 4 Selective recognition of d-sucrose and structures of disaccharides and artificial sugars.

    (A) Schematic representation of the selective encapsulation of d-sucrose (2a) from a mixture of 2a and d-trehalose (2b) by capsule 1. 1H NMR spectra (500 MHz, D2O, room temperature) of (B) 2a and 2b, (C) a mixture of 12a, 2a, and 2b, and (D) isolated 12a. (E) d-Lactose (2c), d-maltose (2d), d-cellobiose (2e), d-lactulose (2f), sucralose (4a), and aspartame (4b) used as guest molecules and (F) their optimized structures [density functional theory (DFT), B3LYP/6-31G(d); conductor-like polarizable continuum model (CPCM; H2O) level].

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/8/e1701126/DC1

    scheme S1. Host-guest interactions between 1 and 3a.

    scheme S2. Formation of 13b.

    scheme S3. Host-guest interactions between 1 and 2b.

    scheme S4. Formation of 14a.

    scheme S5. Selective encapsulation of 4a by 1 from a mixture of 2a and 4a.

    scheme S6. Competitive binding experiment of 4a and 4b by 1.

    fig. S1. 1H NMR spectra (500 MHz, D2O, room temperature) of 1 with various monosaccharides.

    fig. S2. ESI-TOF MS spectra (H2O, room temperature) of 1 with various monosaccharides.

    fig. S3. Temperature-dependent 1H NMR spectra (500 MHz, D2O) of 13b.

    fig. S4. 1H DOSY NMR spectrum (500 MHz, D2O, 25°C) of 13b.

    fig. S5. 1D NOESY spectrum (500 MHz, D2O, room temperature, irradiation at 7.96 ppm) of 13b.

    fig. S6. Concentration-dependent 1H NMR spectra (500 MHz, D2O, room temperature) of 13b.

    fig. S7. ESI-TOF MS spectrum (H2O, room temperature) of 13b at 5.0 μM.

    fig. S8. ESI-TOF MS spectrum (H2O, room temperature) of 13b.

    fig. S9. Optimized structure of 13b (R = -OCH3).

    fig. S10. 1H NMR spectra (500 MHz, D2O, room temperature) of 12a.

    fig. S11. 1H NMR spectra (500 MHz, D2O, 60°C) of 12a.

    fig. S12. 1H-1H Correlation spectroscopy (COSY) spectra (500 MHz, D2O, room temperature) of 12a.

    fig. S13. NOESY spectra (500 MHz, D2O, room temperature) of 12a.

    fig. S14. Homonuclear Hartmann-Hahn (HOHAHA) spectrum (500 MHz, D2O, 60°C) of 12a.

    fig. S15. Heteronuclear single quantum coherence (HSQC) NMR spectrum (500 MHz, D2O, 60°C) of 12a.

    fig. S16. 1H DOSY NMR spectrum (500 MHz, D2O, room temperature) of 12a.

    fig. S17. ESI-TOF MS spectrum (H2O, room temperature) of 12a.

    fig. S18. 1H NMR spectra (500 MHz, D2O, room temperature) of 1 with various disaccharides.

    fig. S19. Optimized structure of 12a (R = -OCH3).

    fig. S20. A snapshot of 12a (R = -OCH3) in water from molecular dynamics simulation.

    fig. S21. Temperature-dependent 1H NMR spectra (500 MHz, D2O) of 12a.

    fig. S22. Concentration-dependent 1H NMR spectra (500 MHz, D2O, 0.155 mM based on 1, room temperature) of 12a.

    fig. S23. Selective encapsulation of 2a from a mixture of 2a and 2b by 1.

    fig. S24. Selective encapsulation of 2a from a mixture of 2a and various disaccharides by 1.

    fig. S25. Encapsulation of 4a within 1.

    fig. S26. Encapsulation of 4b within 1.

    fig. S27. Concentration-dependent 1H NMR spectra (500 MHz, D2O, 0.8 mM based on 1, room temperature) of 14a and 14b.

    fig. S28. Competitive binding experiments of 2a and artificial sugars by 1.

    fig. S29. Competitive binding experiment of 4a and 4b by 1.

    table S1. Theoretical binding energies of host-guest complexes (R = -OCH3).

    table S2. Thermodynamic parameters of 12a.

    table S3. Binding constants of 1 toward 2a in water.

  • Supplementary Materials

    This PDF file includes:

    • scheme S1. Host-guest interactions between 1 and 3a.
    • scheme S2. Formation of 1⊃3b.
    • scheme S3. Host-guest interactions between 1 and 2b.
    • scheme S4. Formation of 1⊃4a.
    • scheme S5. Selective encapsulation of 4a by 1 from a mixture of 2a and 4a.
    • scheme S6. Competitive binding experiment of 4a and 4b by 1.
    • fig. S1. 1H NMR spectra (500 MHz, D2O, room temperature) of 1 with various monosaccharides.
    • fig. S2. ESI-TOF MS spectra (H2O, room temperature) of 1 with various monosaccharides.
    • fig. S3. Temperature-dependent 1H NMR spectra (500 MHz, D2O) of 1⊃3b.
    • fig. S4. 1H DOSY NMR spectrum (500 MHz, D2O, 25°C) of 1⊃3b.
    • fig. S5. 1D NOESY spectrum (500 MHz, D2O, room temperature, irradiation at 7.96 ppm) of 1⊃3b.
    • fig. S6. Concentration-dependent 1H NMR spectra (500 MHz, D2O, room temperature) of 1⊃3b.
    • fig. S7. ESI-TOF MS spectrum (H2O, room temperature) of 1⊃3b at 5.0 μM.
    • fig. S8. ESI-TOF MS spectrum (H2O) of 1⊃3b.
    • fig. S9. Optimized structure of 1⊃3b (R = -OCH3).
    • fig. S10. 1H NMR spectra (500 MHz, D2O, room temperature) of 1⊃2a.
    • fig. S11. 1H NMR spectra (500 MHz, D2O, 60ºC) of 1⊃2a.
    • fig. S12. 1H-1H Correlation spectroscopy (COSY) spectra (500 MHz, D2O, room temperature) of 1⊃2a.
    • fig. S13. NOESY spectra (500 MHz, D2O, room temperature) of 1⊃2a.
    • fig. S14. Homonuclear Hartmann-Hahn (HOHAHA) spectrum (500 MHz, D2O, 60ºC) of 1⊃2a.
    • fig. S15. Heteronuclear single quantum coherence (HSQC) NMR spectrum (500 MHz, D2O, 60ºC) of 1⊃2a.
    • fig. S16. 1H DOSY NMR spectrum (500 MHz, D2O, room temperature) of 1⊃2a.
    • fig. S17. ESI-TOF MS spectrum (H2O, room temperature) of 1⊃2a.
    • fig. S18. 1H NMR spectra (500 MHz, D2O, room temperature) of 1 with various disaccharides.
    • fig. S19. Optimized structure of 1⊃2a (R = -OCH3).
    • fig. S20. A snapshot of 1⊃2a (R = -OCH3) in water from molecular dynamics simulation.
    • fig. S21. Temperature-dependent 1H NMR spectra (500 MHz, D2O) of 1⊃2a.
    • fig. S22. Concentration-dependent 1H NMR spectra (500 MHz, D2O, 0.155 mM based on 1, room temperature) of 1⊃2a.
    • fig. S23. Selective encapsulation of 2a from a mixture of 2a and 2b by 1.
    • fig. S24. Selective encapsulation of 2a from a mixture of 2a and various disaccharides by 1.
    • fig. S25. Encapsulation of 4a within 1.
    • fig. S26. Encapsulation of 4b within 1.
    • fig. S27. Concentration-dependent 1H NMR spectra (500 MHz, D2O, 0.8 mM based on 1, room temperature) of 1⊃4a and 1⊃4b.
    • fig. S28. Competitive binding experiments of 2a and artificial sugars by 1.
    • fig. S29. Competitive binding experiment of 4a and 4b by 1.
    • table S1. Theoretical binding energies of host-guest complexes (R = -OCH3).
    • table S2. Thermodynamic parameters of 1⊃2a.
    • table S3. Binding constants of 1 toward 2a in water.

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