Mingjie Liu 1 , Yasuhiro Ishida 1 , Yasuo Ebina 2 , Takayoshi Sasaki 2 & Takuzo Aida 1,3

1. Paper Introduction 2014/01/17 Rika Ochi Nature Communications, 2013, 4:2029, DOI: 10.1038/ncomms3029 Photolatently modulable hydrogels using unilamellar titania nanosheets as photocatalytic crosslinkers Mingjie Liu1, Yasuhiro Ishida1, Yasuo Ebina2, Takayoshi Sasaki2& Takuzo Aida1,3 1 RIKEN Center for Emergent Matter Science. 2 National Institute for Materials Science, International Center for Materials Nanoarchitectonics, 3 Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo,

2. Hydrogels ・Soft mattermainly composed of water ・Various applications are expected. ex) Drug release, 3D cell culture, actuator ・In general, hydrogels have low mechanical strength Clay nanosheets Q. Wang, J. L. Mynar, M. Yoshida, E. Lee, M. Lee, K. Okuro, K. Kinbara & Takuzo Aida, Nature, 2010, 463, 339–343 . Mechanical strong hydrogels G3-binder ASAP G3-binder Physically crosslinking G3-binder+ sodium polyacrylate (ASAP) + Laponite (Silicate) [CNSs (negative)]/[G3-binder (positive)]/[ASAP(negative)] =18.0/2.0/6.0 mM; Recently, two dimensional nanosheets (disk-shaped clay nanosheets) have caught special attention as components of hydrogels.

3. This study Photolatently reactive hydrogels which can be activated by light Titania (Titanium oxide) : photocatalyst, nontoxic, biocompatible Water-soluble vinylmonomers Hydroxyl radical The use of unilamellar titania nanosheets (TiNSs) as photocatalystic crosslinking points.

4. Preparation and thermo-response of hydrogel Schematic illustration of TiNSs (0.4 wt%)-mediated photoinduced hydrogelation (l=260 nm, at 25 ℃ for 20 min) and pictures before and after the hydrogelation using IPAAm (10.0 wt%) as monomer

5. Thermoresponsive behavior of hydrogel IPAAm/TiNSs (10.0/0.4 wt%)at 25 and 40 ℃ In a patterned PDMS matrix （50-mm-thick film ） In a test tube PDMS= plastic Gel PDMS ＠300 nm Hydrogel sharply and reversibly changes, without any hysteresis, its optical transmittance in a very narrow temperature range of 32–33 ℃

6. Three-dimensional microstructure of hydrogel ANS Hydrophobic domain 10 mm (e) A three-dimensional microstructure of the hydrogel constructed with its sliced two-dimensional images, obtained at 34 ℃ by confocal fluorescence laser scanning microscopy, where the sample was doped with a fluorescent probe (8-anilino-1-naphthalenesulphonic acid ammonium salt). Submicron-sized tiny luminescent domains, which is advantageous for quick thermal shrinkage/swelling of polymer domains, certainly benefits from the mechanism of hydrogelation with photocatalytic TiNSs

7. Use as a thermoresponsive ion gate (f) Ion conductivities of the hydrogel at different temperatures in the range 23–38 C at an applied cell voltage of 100mV, where the sample (IPAAm/TiNSs=10.0/0.4 wt%) was doped with LiClO4 (dopant, 500 mM). Ion conductivity increased markedly at around the LCST.

8. Micropatterning of hydrogels With Ag nanocluster With poly(IPAAm) 500 mm 500 mm Figure 3. (a) Schematic illustration of micropatterning with poly(IPAAm) and Ag nanocluster in a hydrogel matrix, prepared with DMAAm/TiNSs/Laponite (8.0/3.0/3.0 wt%), upon light exposure through a patterned photomask.). (d) Change in surface plasmonic absorbance (500 nm) with light exposure time of Ag nanocluster. TiNSs areimmobilized at the crosslinking points therefore hardly diffuse inside the gel matrix. →Photo-micropatternig, microfabrication

9. Homo- and heterotropic conjugations of hydrogels [DMAAm/TiNSs/Laponite] = 8.0/3.0/3.0 wt% Light exposure(l>260 nm) for 20 min Homotropic conjugation Heterotropic conjugation 500% 550% PDMS= plastic ・Repeatable use (healing of damaged part) ・Strong attachment ・Heterotropic conjugation possibly expand the potential of hydrogel

10. Thermoresponsive hydrogel actuator Supplementary Figure S5. Thermoresponsive hydrogel actuator by lateral heterotropic conjunction of photolatently modulable hydrogel strips. (a) Schematic representation of a bimorph strip of laterally conjugated hydrogels with different thermoresponsive properties. The pink-colored and blue-colored layers were prepared with IPAAm/TiNSs (8.0/3.0 wt%) and DMAAm/TiNSs (8.0/3.0 wt%), respectively, in conjunction with Laponite (3.0 wt%). (b) Pictures of the bimorph strip at 25 (left) and 40 °C (right). Lateral photochemical conjunction of two hydrogel strips with different thermo-responsive properties provides a soft actuator that operates by a temperature change.

11. Summary ・By using titania authors developed ‘photolatently modulable’ hydrogels that are readily preparable and also postmodulable by light whenever needed. ・Consequently, TiNSs are immobilized at the crosslinking points in a polymer network and locally convert gelling water into hydroxyl radicals whenever exposed to light. ・This hydrogel would be useful for the development of materials. ex) controlled drug release, semisynthetic enzymes, and three-dimensional tissue engineering.

12. strain–stress curve