A Hydrophilic/Hydrophobic Janus Inverse-Opal

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1 Supporting information A Hydrophilic/Hydrophobic Janus Inverse-Opal Actuator via Gradient Infiltration Dajie Zhang #, Jie Liu //#, Bo Chen *, Yong Zhao, Jingxia Wang * //, Tomiki Ikeda, Lei Jiang //. CAS Key Laboratory of Bio-inspired Materials and Interfacial Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, , P.R. China Key Laboratory of Phytochemical R&D of Hunan Province, Hunan Normal University, Changsha, , China Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing, , P.R. China // School of Future Technologies, University of Chinese Academy of Sciences, Beijing , China # Dajie Zhang and Jie Liu contributed equally to this work. Corresponding Author * jingxiawang@mail.ipc.ac.cn (Jingxia Wang). * dr-chenpo@vip.sina.com (Bo Chen). 1

2 1. Experimental: Synthesis of monodisperse core-shell latex particles Monodisperse latex particles of poly(styrene-methyl methacrylate-acrylic acid) (poly(st-mma- AA) were synthesized based on our previously reported method 1,2. Typically, 10 mmol MMA, mmol AA and mmol St were dispersed in 100 ml of water in which mmol sodium dodecyl benzene sulfonate and 6.30 mmol ammonium bicarbonate (buffer agent) were dissolved. The reaction mixture was kept at 70 C for 0.5 h. Then, the initiator, that is, an aqueous solution of 2.12 mmol ammonium peroxydisulfate, was added into the system. Polymerization was carried out at 80 C for 10 h with continuous stirring. The resulting latex particles were used directly without purification. 1. Wang, J. X.; Wen, Y. Q.; Ge, H. L.; Sun, Z. W.; Zheng, Y. M.; Song, Y. L.; Jiang, L. Simple Fabrication of Full Color Colloidal Crystal Films with Tough Mechanical Strength. Macromol. Chem. Phys. 2006, 207, Wang, J. X.; Zhang, Y. Z.; Wang, S. T.; Song, Y. L.; Jiang, L. Bioinspired Colloidal Photonic Crystals with Controllable Wettability, Acc. Chem. Rev. 2011, 44, Preparation of the PC template The PC template was prepared by vertically depositing a clean glass substrate in a vial containing the Poly(St-MMA-AA) colloidal suspensions at a concentration of 0.15% wt at 60 C under a relative humidity of 60% for 48 h. 2

3 2. Characterization of the Janus sample 2.1 Morphology characterization Figure S1. SEM images of the top side of poly(il-co-mma) inverse opal. 3

4 Figure S2. AFM images for the top side of poly(il-co-mma) inverse opal, with the corresponding roughness. 4

5 Figure S3. SEM images for the bottom side of poly(il-co-mma) inverse opal. Figure S4. AFM image for the bottom side of poly(il-co-mma) inverse opal. 5

6 Figure S5. Cross-section SEM images of poly(il-co-mma) inverse opal 6

7 Figure S6. SEM images of the composite sample before template removal. (A,B) Top Side, (C,D) bottom side and (E) cross-section More infiltration can be observed from the top part (A, B) compared with that bottom part (C, D). 7

8 2.2 Wettability for the top and bottom of the sample Figure S7. Water CA for top and bottom side of poly(il-co-mma) inverse opal with varying time. The sample was fabricated with varying PIL weight content. 8

9 2.3 Chemical composition Figure S8. FTIR spectra of poly(il-co-mma) inverse opal for the dry and humidity state Compared with the data of dry film, there is a shift from 3406 to 3402 cm -1 for hydrogen bonding in the spectra of film exposed to water vapor. Simultaneously, a shift from 3059 to 3086 cm -1 occurs for the sample, that can be identified as signal from methyl group. 9

10 3. Actuation behavior Figure S9. Optical photographs of poly(il-co-mma) inverse opal actuator during the response process in various solvent systems 10

11 Figure S10. (A) Curvature of a poly(il-co-mma) inverse opal actuator in water with different ethanol content; the insert is a photograph of the sample during the corresponding actuation process; (B) The time taken for the sample approaching the largest bending angle or bending rate of the sample in water with different ethanol content. In this case, the sample is made from 75% wt PIL inverse opals. Figure S11. Relationship between the bending angles with responsive time for the PIL inverse opal (100% wt PIL) 11

12 Figure S12. Relationship between the bending angle and responsive time for the poly(il-co- MMA) inverse opals (75% wt PIL) Figure S13. Relationship between the bending angle and response time for the poly(il-co-mma) inverse opal (50% wt PIL) 12

13 Figure S14. The reversibility of the actuation process for the as-prepared poly(il-co-mma) inverse opal actuator. 13

14 4. Calculation of solvent-induced stress-strain property for the as-prepared poly(il-co- MMA) inverse opal actuator. (1) [3] (2) [3] (3) In this case, is the diameter of the particles nm. is the diameter of the original pores nm measured from SEM image by using Nano Measurer 1.2 software. Besides, and, = (4) (5) E =1.168±0.049, it is measured by nano indentation. 3. Quan, M. H.; Yang, B.; Wang, J. X.; Yu, H. F.; Cao, X. Y. Simultaneous Microscopic Structure Characteristic of Shape-Memory Effect of Thermo-Responsive Poly (vinylidene fluoride-co-hexafluoropropylene) Inverse Opals. ACS Appl. Mater. Interfaces 2018, 10,

15 Table S1. Calculated solvent-induced strain-stress relationship of poly(il-co-mma) inverse opal actuator. 5. Actuation applications Figure S15. Photographs of poly(il-co-mma) inverse opal actuator (with a weight of 0.25 mg) loaded with cargo with a weight of (A) 0 mg (B) 0.51 mg (C) 1.15 mg and (D) 1.45 mg. For the sample loaded of cargo of 0.51 mg, can bend easily except prolonging the response time. There 15

16 is a great decrease for the bending angle of the sample when increasing the loaded weight to 1.15 and 1.45 mg. Figure S16. The influence of loaded cargo (with different weights) on the bending behavior of the as-prepared poly(il-co-mma) inverse opal actuator. The film easily bent into a concentric circular coil when an object with a weight of 0.51 mg was loaded onto it, except when the bending time was prolonged from 30 to 110 s (Figure S15). However, a remarkable decline in the largest bending angle of the film from 499 to 196 or 89 occurred when the weight of the lifted object was changed from 0 to 1.15 or 1.45 mg (approximately 5 times more than that of film s weight). 16

17 Movie S1 Actuation by water vapor. Film length, 12 mm; width, 1 mm; thickness, 20 µm, at real time Movie S2 Film with a hydrophobic upper surface bending out of water. Film length, 7 mm; width, 1.5 mm; thickness, 20 µm, at real time. Movie S3 Film with a hydrophilic upper surface bending toward the water. Film length, 6 mm; width, 2 mm; thickness, 20 µm, at real time Movie S4 Driving a mechanical axis by bending process of film. Film length, 12 mm; width, 3 mm; thickness, 20 µm, at 6X real time. 17

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