Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 Installing dynamic molecular photomechanics in mesopore: A multifunctional controlled-release nanosystem Yingchun Zhu *, Masahiro Fujiwara * * Kansai Center, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka , Japan. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai , China. m-fujiwara@aist.go.jp 1. Controlled-release experiments under various conditions. 2. Figure S1 Schematic reaction scheme of photo isomerization of azobenzene. UV Irradiation alone induces the cis-isomer form of azobenzene, following the process. Visible light irradiation alone results in the trans-isomer form, following the process. In the cases of irradiation with UV-Vis light, there is an intermediate state composed of both trans- and cis-forms in comparable amounts. In the dynamic state, photo isomerization takes place following both the process and the process. 3. Figure S2 Chemical structures of isomers of the azobenzene derivatives: phenylazo-n-(3-triethoxysilyl)-benzamide, calculated by using Chem 3D molecular modeling analysis software. 4. Figure S3 XRD patterns of samples of MCM-41. As-prepared MCM-41; Sample 1A; Sample 1B; Sample 1C 5. Figure S4 XRD patterns of samples of MCM-41. Sample 2A; sample 2B; sample 2C. 6. Figure S5 Nitrogen adsorption-desorption isotherms of MCM-41 samples. Sample 1A, sample 1B, Sample 1C, sample 1D, and sample 1E. 7. Figure S6 Pore size distributions of samples of MCM-41. Sample 1A; Sample 1B; Sample 1C; Sample 1D; and Sample 1E. 8. Figure S7 Nitrogen adsorption-desorption isotherms of MCM-41 samples.

3 Sample 2A, sample 2B, Sample 2C, sample 2D, and sample 2E. 9. Figure S8 Pore size distributions of samples of MCM-41. Sample 2A; sample 2B; sample 2C; sample 2D; and sample 2E. 10. Figure S9 Changes in UV-visible spectra of coumarin modified MCM-41 samples (Sample 2A) during UV irradiation (>310 nm). 11. Figure S10 Changes in UV-visible spectra of coumarin modified MCM-41 sample (Sample 2A irradiated with >310 nm UV) during UV irradiation (ca. 250 nm) 12. Figure S11 TGA-DSC profiles of samples of MCM-41. (a) Sample 1A; (b) Sample 2A; (c) Sample 1B; (d) Sample 2B. 13. Figure S12 TGA profiles of samples of MCM-41. (a) Sample 1C; (b) Sample 1E; (c) Sample 1D. 14. Figure S13 TGA profiles of samples of MCM-41. (a) Sample 2C; (b) Sample 2E; (c) Sample 2D.

4 Controlled-release experiments 1 g of modified mesoporous silica, samples 1B or 2B, was suspended in an n-hexane-ethanol (3:1 in volume) solution (20 ml) containing 1 g of cholesterol at 313 K for 3 or 5 days, respectively. The resulting solid was filtered off, dried at 323 K for 2 hours, rinsed with n-hexane for several times on a filter, and dried again at 333 K for 12 hours. The product from sample 1B is assigned as sample 1C. The product from sample 2B was photo-dimerized by irradiation with UV light of wavelength >310 nm for 30 minutes using a 450-W high-pressure mercury lamp through a Pyrex glass cooler. [4] After the dimerization, the solid was washed and dried again, assigned as sample 2C. The amounts of cholesterol in samples 1C and 2C were estimated from the difference between the initial and the recovered amounts. Sample 2C was photo-cleaved by irradiation of UV light at around 250 nm wavelengths for 2.5 minutes with a low-pressure mercury lamp through a quartz glass cooler. Samples 1C and 2C were then treated with n-hexane at room temperature under stirring with or without light irradiation. The UV-Vis source is a deep UV lamp, and the intensity and wavelength of the light source were regulated by light filters. In the release experiments for sample 2C, a sharp filter was used to eliminate the UV light shorted than 355 nm to avoid the interference with the coumarin derivative. Finally, the solid was descended, washed and dried at room temperature (samples 1D, 1E, 2D and 2E). The amounts of cholesterol in the filtrate and in mesoporous silica were analyzed using gas chromatography and thermogravimetric analysis.

5 Figure S1 Schematic reaction scheme of photo isomerization of azobenzene. UV Irradiation alone induces the cis-isomer form of azobenzene, following the process. Visible light irradiation alone results in the trans-isomer form, following the process. In the cases of irradiation with UV-Vis light, there is an intermediate state composed of both trans- and cis-forms in comparable amount. In the dynamic state, photo isomerization takes place following both the process and the process.

6 Figure S2 Chemical structures of isomers of the azobenzene derivative: phenylazo-n-(3-triethoxysilyl)-benzamide, calculated by using Chem 3D molecular modeling analysis software.

7 Figure S3 XRD patterns of samples of MCM-41. As-prepared MCM-41: with surfactants in the pores; Sample 1A: Empty MCM-41; Sample 1B: 5.6 wt% azobenzene grafted MCM-41; Sample 1C: 35.1 wt% cholesterol absorbed, 5.6 wt% azobenzene grafted MCM-41.

8 Figure S4 XRD patterns of samples of MCM-41. Sample 2A: 1.0 wt% coumarin grafted MCM-41; sample 2B: 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41; sample 2C: 32.5 wt% cholesterol absorbed, 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41.

9 Figure S5 Nitrogen adsorption-desorption isotherms of MCM-41 samples. Sample 1A (empty MCM-41), sample 1B (5.6 wt% azobenzene grafted MCM-41), Sample 1C (35.1 wt% cholesterol absorbed, 5.6 wt% azobenzene grafted MCM-41), sample 1D (released sample 1C, under irradiation with UV-Vis light, UV: 80 mw, 360 nm; Vis: 54 mw, 430 nm), and sample 1E (released sample 1C, without UV irradiation).

10 Figure S6 Pore size distributions of samples of MCM-41. Sample 1A: Empty MCM-41; Sample 1B: 5.6 wt% azobenzene grafted MCM-41; Sample 1C: 35.1 wt% cholesterol absorbed, 5.6 wt% azobenzene grafted MCM-41; sample 1D: released sample 1C, under irradiation with UV-Vis light, UV: 80 mw, 360 nm; Vis: 54 mw, 430 nm; and sample 1E: released sample 1C, without UV irradiation.

11 Figure S7 Nitrogen adsorption-desorption isotherms of MCM-41 samples. Sample 2A (1.0 wt% coumarin grafted MCM-41), sample 2B (1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41), Sample 2C (32.5 wt% cholesterol absorbed, 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41), sample 2D (released sample 2C, photo-cleaved, under irradiation with UV-Vis light, UV: 22 mw, 360 nm; Vis: 54 mw, 430 nm), and sample 2E (released sample 2C, without UV irradiation).

12 Figure S8 Pore size distributions of samples of MCM-41. Sample 2A: 1.0 wt% coumarin grafted MCM-41; sample 2B: 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41; sample 2C: 32.5 wt% cholesterol absorbed, 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41; sample 2D: released sample 2C, photo-cleaved, under irradiation with UV-Vis light, UV: 22 mw, 360 nm; Vis: 54 mw, 430 nm; and sample 2E: released sample 2C, without UV irradiation.

13 Figure S9 Changes in UV-visible spectra of coumarin modified MCM-41 samples (Sample 2A) during UV irradiation (>310 nm).

14 Figure S10 Changes in UV-visible spectra of coumarin modified MCM-41 sample (Sample 2A was previously irradiated with >310 nm UV) during UV irradiation with wavelength of ca. 250 nm

15 Figure S11 TGA-DSC profiles of samples of MCM-41. (a) Sample 1A (Empty MCM-41); (b) Sample 2A (1.0 wt% coumarin grafted MCM-41; (c) Sample 1B (5.6 wt% azobenzene grafted MCM-41Sample 1A); (d) Sample 2B (1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41).

16 Figure S12 TGA profiles of samples of MCM-41. (a) Sample 1C (35.1 wt% cholesterol absorbed, 5.6 wt% azobenzene grafted MCM-41); (b) sample 1E (released sample 1C, without UV irradiation); (c) Sample 1D (released sample 1C, under irradiation with UV-Vis light, UV: 80 mw, 360 nm; Vis: 54 mw, 430 nm).

17 Figure S13 TGA profiles of samples of MCM-41. (a) Sample 2C (32.5 wt% cholesterol absorbed, 1.0 wt% coumarin and 5.9 wt% azobenzene grafted MCM-41); (b) Sample 2E (released sample 2C, without UV irradiation); (c) Sample 2D (released sample 2C, photo-cleaved, under irradiation with UV-Vis light, UV: 22 mw, 360 nm; Vis: 54 mw, 430 nm).