Research ArticleSUPRAMOLECULAR CHEMISTRY

Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release

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Science Advances  03 Aug 2016:
Vol. 2, no. 8, e1600480
DOI: 10.1126/sciadv.1600480
  • Fig. 1 Schematic representation.

    Schematic illustration of the synthesis of UiO-68-azo and further construction of RhB-loaded, β-CD–capped UiO-68-azo with azobenzene units as stalks encircled by β-CD on the surface. The trans-azobenzene is colored in green.

  • Fig. 2 Crystal structure and gas absorption behavior.

    (A) Crystal structure of UiO-68-azo. The azobenzene units were not located in the electron density map and are instead presented in an optimized position. (B) N2 adsorption isotherms of activated UiO-68-azo.

  • Fig. 3 PXRD patterns.

    (A to E) Simulated from the crystal structure of UiO-68-azo (A), fresh UiO-68-azo (B), RhB-loaded, β-CD–capped UiO-68-azo (C), RhB-loaded, β-CD–capped UiO-68-azo after UV irradiation (D), and RhB-loaded, β-CD–capped UiO-68-azo after addition of amantadine and then UV irradiation (E). The patterns were taken with crystals covered by a thin layer of water.

  • Fig. 4 On-command release.

    (A) Schematic illustration of the light-triggered release. The cis-azobenzene is colored in cyan. (B) Release profiles of RhB-loaded, β-CD–capped UiO-68-azo by UV irradiation.

  • Fig. 5 Step-by-step on-command release.

    (A) Schematic illustration of the step-by-step release. The cis-azobenzene is colored in cyan. (B) Release profiles of RhB-loaded, β-CD–capped UiO-68-azo by addition of amantadine and then UV irradiation.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/2/8/e1600480/DC1

    fig. S1. Synthesis of ligand 1.

    fig. S2. UV-visible spectra of ligand 1 after exposure to UV light for different times.

    fig. S3. 1H NMR spectra of ligand 1 before and after UV irradiation for 5 min.

    fig. S4. 1H NMR spectrum of digested UiO-68-azo.

    fig. S5. 1H NMR spectrum of ligand 1.

    fig. S6. N2 sorption isotherm of UiO-68-azo at 77 K before and after UV irradiation for 3 hours.

    fig. S7. Pore size distribution of UiO-68-azo before and after UV irradiation for 3 hours.

    fig. S8. Size comparison of RhB and the pore windows of UiO-68-azo.

    fig. S9. UV-visible spectra of the solution of mechanized UiO-68-azo after UV irradiation for different time.

    fig. S10. Release profile of uncapped RhB-loaded UiO-68-azo.

    fig. S11. UV-visible spectra of the solution of mechanized UiO-68-azo after addition of amantadine and then UV irradiation for different time.

    fig. S12. Release study of mechanized UiO-68-azo after addition of d-arabinose.

    fig. S13. Release study of mechanized UiO-68-azo after addition of 4-amino-1-naphthalenesulfonic acid sodium salt.

    fig. S14. Release study of mechanized UiO-68-azo after addition of sodium benzoate.

    fig. S15. Release study of mechanized UiO-68-azo after addition of ethanol.

    fig. S16. Release study of mechanized UiO-68-azo after addition of acetone.

    fig. S17. Release study of mechanized UiO-68-azo after addition of dimethyl sulfoxide.

    fig. S18. Release profile of uncapped RhB-loaded UiO-68-azo after UV irradiation.

    fig. S19. Release profile of uncapped RhB-loaded UiO-68-azo after addition of amantadine.

    fig. S20. Release profile of uncapped RhB-loaded UiO-68-azo after addition of d-arabinose.

    fig. S21. Thermogravimetric plot of UiO-68-azo.

    fig. S22. UV-visible spectra of Hepes buffer solution containing UiO-68-azo with different time.

    fig. S23. PXRD pattern of UiO-68-azo after being kept in a Hepes buffer solution for 3 hours.

    table S1. Crystal data and structure refinement for UiO-68-azo.

    Experiment details

    Simulation details

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Synthesis of ligand 1.
    • fig. S2. UV-visible spectra of ligand 1 after exposure to UV light for different times.
    • fig. S3. 1H NMR spectra of ligand 1 before and after UV irradiation for 5 min.
    • fig. S4. 1H NMR spectrum of digested UiO-68-azo.
    • fig. S5. 1H NMR spectrum of ligand 1.
    • fig. S6. N2 sorption isotherm of UiO-68-azo at 77 K before and after UV irradiation for 3 hours.
    • fig. S7. Pore size distribution of UiO-68-azo before and after UV irradiation for 3 hours.
    • fig. S8. Size comparison of RhB and the pore windows of UiO-68-azo.
    • fig. S9. UV-visible spectra of the solution of mechanized UiO-68-azo after UV irradiation for different time.
    • fig. S10. Release profile of uncapped RhB-loaded UiO-68-azo.
    • fig. S11. UV-visible spectra of the solution of mechanized UiO-68-azo after addition of amantadine and then UV irradiation for different time.
    • fig. S12. Release study of mechanized UiO-68-azo after addition of D-arabinose.
    • fig. S13. Release study of mechanized UiO-68-azo after addition of 4-amino-1-naphthalenesulfonic acid sodium salt.
    • fig. S14. Release study of mechanized UiO-68-azo after addition of sodium benzoate.
    • fig. S15. Release study of mechanized UiO-68-azo after addition of ethanol.
    • fig. S16. Release study of mechanized UiO-68-azo after addition of acetone.
    • fig. S17. Release study of mechanized UiO-68-azo after addition of dimethyl sulfoxide.
    • fig. S18. Release profile of uncapped RhB-loaded UiO-68-azo after UV irradiation.
    • fig. S19. Release profile of uncapped RhB-loaded UiO-68-azo after addition of amantadine.
    • fig. S20. Release profile of uncapped RhB-loaded UiO-68-azo after addition of D-arabinose.
    • fig. S21. Thermogravimetric plot of UiO-68-azo.
    • fig. S22. UV-visible spectra of Hepes buffer solution containing UiO-68-azo with different time.
    • fig. S23. PXRD pattern of UiO-68-azo after being kept in a Hepes buffer solution for 3 hours.
    • table S1. Crystal data and structure refinement for UiO-68-azo.
    • Experiment details

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