3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery

Transcription

1 [Supporting Information] 3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery Qianrong Fang,, Junhua Wang, Shuang Gu, Robert B. Kaspar, Zhongbin Zhuang, Jie Zheng, Hongxia Guo,, Shilun Qiu,*, and Yushan Yan*, State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun , P. R. China Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, DE 19716, USA College of Material Science and Engineering, Beijing University of Technology, Beijing , P. R. China Contents: Section 1. Materials and Characterization Section 2. Figures S1 S39 Section 3. Tables S1 S8 Section 4. References S1

2 Section 1. Materials and Characterization All starting materials and solvents, unless otherwise noted, were obtained from Aldrich Chemical Co. and used without purification. All products were isolated and handled under nitrogen using either glovebox or Schlenk line techniques. 1,3,5,7-tetraaminoadamantane (TAA) was synthesized by the method of literatures H NMR spectra were recorded on an AV400 NMR spectrometer. 13 C NMR spectra were recorded on an AVIII 500 MHz solid-state NMR spectrometer. FT-IR spectra were recorded on a Thermo Nicolet Nexus 470 spectrometer equipped with a MCT-A (mercury cadmium telluride) detector with 5 mg samples. TGA was carried out under nitrogen on a TGA/DSC 1 thermal analyzer from METTLER TOLEDO. PXRD data were collected on a Philips X Pert powder diffractometer using a Cu Kα source (λ = Å) over the range of 2θ = with a step size of 0.02 and 2 s per step. The sorption isotherm for N 2 was measured by using a Micromeritics ASAP 2020 analyzer with ultra-highpurity N 2 (99.999% purity). To estimate pore size distributions for PI-COFs, nonlocal density functional theory (NLDFT) was applied to analyze the N 2 isotherm on the basis of the model of N on carbon with slit pores and the method of non-negative regularization. UV-VIS spectra were measured on a Lambda 20 spectrophotometer. The SEM images were obtained on JEOL JSM7400F microscope, operating at an acceleration voltage of 3-10 kev and current of 10 µa. (1) Synthesis of PI-COF-4 A Pyrex tube measuring o.d. i.d. = 10 8 mm 2 was charged with PMDA (43.6 mg, 0.2 mmol) and TAA (19.6 mg, 0.1 mmol) in a mixed solution of NMP (0.2 ml), mesitylene (1.0 ml), and isoquinoline (0.02 ml). The tube was flash frozen at 77 K (LN 2 bath), evacuated to an internal pressure of 0.15 mmhg and flame sealed. Upon sealing the length of the tube was reduced to ca. 13 cm. The reaction mixture was heated at 160 C for 5 days to afford a brown precipitate which was isolated by filtration over a medium glass frit and washed with anhydrous tetrahydrofuran (THF, 20.0 ml). The product was immersed in anhydrous THF (20.0 ml) for 8 h, during which the activation solvent was decanted and S2

3 freshly replenished four times. The solvent was removed under vacuum at 85 C to afford PI-COF-4 as a brown powder (51.3 mg, 86%). Anal. Calcd for C 15 H 8 N 2 O 4 : C, 64.29; H, 2.88; N, Found: C, 63.78; H, 2.80; N, (2) Synthesis of PI-COF-5 Similar to PI-COF-4, PMDA (43.6 mg, 0.2 mmol) was treated with TAPM (38.1 mg, 0.1 mmol) in a mixed solution of NMP (0.2 ml), mesitylene (1.0 ml), and isoquinoline (0.02 ml). The tube was flash frozen at 77 K (LN 2 bath), evacuated to an internal pressure of 0.15 mmhg, and flame sealed. Upon sealing the length of the tube was reduced to ca. 13 cm. The reaction mixture was heated at 160 C for 5 days to afford a brown precipitate which was isolated by filtration over a medium glass frit and washed with anhydrous THF (20.0 ml). The product was immersed in anhydrous THF (20.0 ml) for 8 h, during which the activation solvent was decanted and freshly replenished four times. The solvent was removed under vacuum at 85 C to afford PI-COF-5 as a brown powder (63.3 mg, 81%). Anal. Calcd for C 45 H 20 N 4 O 8 : C, 72.58; H, 2.71; N, Found: C, 73.10; H, 2.77; N, (3) Drug loading and release The drug was loaded by immersing solvent-free samples in IBU hexane solution of a certain concentration. A typical procedure for loading IBU in PI-COF-4 or PI-COF-5 was as follows: 250 mg of PI- COF was suspended in 10 ml of 0.1 M IBU hexane solution under stirring for 2 h while preventing evaporation of hexane by covering with a cap. The drug-loaded sample was separated from solution by vacuum filtration, washed with hexane, and dried at room temperature. A typical procedure for releasing IBU from PI-COF-4 or PI-COF-5 was as follows: the drug-loaded PI-COF (100 mg) was placed in a vial and dipped in 2 ml of simulated body fluid (SBF, ph = 7.4, standard buffer solution from Fisher Chemical) at 37 C. At predetermined time intervals, the dissolution medium was replaced with 2 ml of fresh SBF and the withdrawn medium was used to determine the drug concentration. The IBU S3

4 concentration was analyzed by UV-VIS spectrophotometry with the help of a calibration curve. The release study was continued until no IBU was detectable in the withdrawn SBF. In addition, the procedure for loading and release captopril or caffeine was similar to those for IBU. S4

5 Section 2. Figures S1 S39 Figure S1. Size of TAA and TAPM measured from center of molecule to nitrogen atoms of amine groups. Figure S2. Size of bis-imide links measured from the tetrahedral centers. S5

6 Figure S3. SEM image of PI-COF-4. Figure S4. SEM image of PI-COF-5. S6

7 Figure S5. FT-IR spectra of PI-COF-4 (a, black), TAA (b, red), and PMDA (c, blue). Figure S6. FT-IR spectra of PI-COF-5 (a, black), TAPM (b, red), and PMDA (c, blue). S7

8 Figure S7. Solid-state 13 C NMR spectra of PI-COF-4 (a, black) and -5 (b, red). Asterisks (*) indicate peaks arising from spinning side bands. Figure S8. TGA of PI-COF-4. S8

9 Figure S9. TGA of PI-COF-5. Figure S10. IR of PI-COF-4 based on different time: (a) one day, (b) three days, and (c) five days. S9

10 Figure S11. IR of PI-COF-5 based on different time: (a) one day, (b) three days, and (c) five days. Figure S12. PXRD of PI-COF-4 based on different time: (a) one day, (b) three days, and (c) five days. S10

11 Figure S13. PXRD of PI-COF-5 based on different time: (a) one day, (b) three days, and (c) five days. Figure S14. Calculated PXRD pattern of PI-COF-4 based on the non-interpenetrated diamond net. S11

12 Figure S15. Calculated PXRD pattern of PI-COF-4 based on the 2-fold interpenetrated diamond net. Figure S16. Calculated PXRD pattern of PI-COF-4 based on the 3-fold interpenetrated diamond net. S12

13 Figure S17. Comparison of PXRD patterns for PI-COF-4: experimental (a, black) as well as calculated from the non- (b, green), 2-fold (c, red) or 3-fold (d, blue) interpenetrated diamond nets. Figure S18. Calculated PXRD pattern of PI-COF-5 based on the non-interpenetrated diamond net. S13

14 Figure S19. Calculated PXRD pattern of PI-COF-5 based on the 2-fold interpenetrated diamond net. Figure S20. Calculated PXRD pattern of PI-COF-5 based on the 3-fold interpenetrated diamond net. S14

15 Figure S21. Calculated PXRD pattern of PI-COF-5 based on the 4-fold interpenetrated diamond net. Figure S22. Comparison of PXRD patterns for PI-COF-5: experimental (a, black) as well as calculated from the non- (b, green), 2-fold (c, red), 3-fold (d, blue) or 4-fold (e, pink) interpenetrated diamond nets. S15

16 Figure S23. BET plot of PI-COF-4 calculated from N 2 adsorption isotherm at 77 K. Figure S24. BET plot of PI-COF-5 calculated from N 2 adsorption isotherm at 77 K. S16

17 Figure S25. Pore size distribution histogram of PI-COF-4 calculated from N 2 adsorption isotherm at 77 K. Figure S26. Pore size distribution histogram of PI-COF-5 calculated from N 2 adsorption isotherm at 77 K. S17

18 Figure S27. PXRD of PI-COF-4 (a, black) and IBU-loaded PI-COF-4 (b, red). Figure S28. PXRD of PI-COF-5 (a, black) and IBU-loaded PI-COF-5 (b, red). S18

19 Figure S29. SEM image of IBU-loaded PI-COF-4. Figure S30. SEM image of IBU-loaded PI-COF-5. S19

20 Figure S31. N 2 sorption isotherms of PI-COF-4 (a, red) and IBU-loaded PI-COF-4 (b, blue). Figure S32. BET plot of IBU-loaded PI-COF-4 calculated from N 2 adsorption isotherm at 77 K. S20

21 Figure S33. N 2 sorption isotherms of PI-COF-5 (a, red) and IBU-loaded PI-COF-5 (b, blue). Figure S34. BET plot of IBU-loaded PI-COF-5 calculated from N 2 adsorption isotherm at 77 K. S21

22 Figure S35. TGA of IBU. Figure S36. TGA of IBU-loaded PI-COF-4. S22

23 Figure S37. TGA of IBU-loaded PI-COF-5. Figure S38. Release profile of captopril-loaded 3D PI-COFs. Inset: the structure of captopril. C, black; H, gray; O, red; N, blue, S, yellow. S23

24 Figure S39. Release profile of caffeine-loaded 3D PI-COFs. Inset: the structure of caffeine. C, black; H, gray; O, red; N, blue. S24

25 Section 3. Tables S1 S8 Table S1. Unit cell parameters and fractional atomic coordinates for PI-COF-4 based on the noninterpenetrated diamond net. Space group I4 1 /amd (No. 141) Calculated unit cell a = b = Å, c = Å, α = β = γ = 90º Measured unit cell a = b = Å, c = Å, α = β = γ = 90º Pawley refinement R p = 4.58%; wr p = 7.95% atom x y z C C C C C C O N H H H S25

26 Table S2. Unit cell parameters and fractional atomic coordinates for PI-COF-4 based on the 2-fold interpenetrated diamond net. Space group P4 2 /n (No. 86) Calculated unit cell a = b = Å, c = Å, α = β = γ = 90º atom x y z C C C C C C C C O O N H H H H S26

27 Table S3. Unit cell parameters and fractional atomic coordinates for PI-COF-4 based on the 3-fold interpenetrated diamond net. Space group I4 1 /amd (No. 141) Calculated unit cell a = b = Å, c = 8.64 Å, α = β = γ = 90º atom x y z C C C C C C C C O O N H H H S27

28 Table S4. Unit cell parameters and fractional atomic coordinates for PI-COF-5 based on the noninterpenetrated diamond net. Space group I4 1 /amd (No. 141) Calculated unit cell a = b = Å, c = Å, α = β = γ = 90º atom x y z C C C C C C C C O N H H H S28

29 Table S5. Unit cell parameters and fractional atomic coordinates for PI-COF-5 based on the 2-fold interpenetrated diamond net. Space group P4 2 /n (No. 86) Calculated unit cell a = b = Å, c = Å, α = β = γ = 90º atom x y z C C C C C C C C C C C C O O N H H H H H S29

30 Table S6. Unit cell parameters and fractional atomic coordinates for PI-COF-5 based on the 3-fold interpenetrated diamond net. Space group I4 1 /amd (No. 141) Calculated unit cell a = b = Å, c = 7.84 Å, α = β = γ = 90º atom x y z C C C C C C C C C C C C O O N H H H H H S30

31 Table S7. Unit cell parameters and fractional atomic coordinates for PI-COF-5 based on the 4-fold interpenetrated diamond net. Space group P4/n (No. 85) Calculated unit cell a = b = Å, c = Å, α = β = γ = 90º Measured unit cell a = b = Å, c = Å, α = β = γ = 90º Pawley refinement R p = 6.83%; wr p = 9.62% atom x y z C C C C C C C C C C C C O O N H H H H H S31

32 Table S8. Parameters of drug loading and release amount in 3D PI-COFs. material drug loading capacity (wt%) PI-COF-4 PI-COF-5 release capacity (%) ibuprofen captopril caffeine ibuprofen captopril caffeine S32

33 Section 4. References (1) Newkome, G. R.; Nayak, A.; Behera, R. K.; Moorefield, C. N.; Baker, G. R. J. Org. Chem. 1992, 57, 358. (2) Senchyk, G. A.; Lysenko, A. B.; Boldog, I.; Rusanov, E. B.; Chernega, A. N.; Krautscheid, H.; Domasevitch, K. V. Dalton Trans. 2012, 41, (3) Fang, Q. R.; Gu, S.; Zheng, J.; Zhuang, Z. B.; Qiu, S. L.; Yan, Y. S. Angew. Chem., Int. Ed. 2014, 53, S33