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Takuzo Aida Deputy Director, RIKEN Center for Emergent Matter Science Professor, School of Engineering, the University of Tokyo

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Takuzo Aida Deputy Director, RIKEN Center for Emergent Matter Science Professor, School of Engineering, the University of Tokyo 19 Japan Academy Prize to: Takuzo Aida Deputy Director, RIKEN Center for Emergent Matter Science Professor, School of Engineering, The University of Tokyo for “Studies on Precision Hierarchical Design of Innovative Soft Materials” Outline of the work: Prof. Takuzo Aida is a world-leading scientist involved in the development of innovative soft materials. Prof. Aida has been intensely engaged in exploiting the interactions between materials sciences and other scientific disciplines such as physics and life science. While researchers’ focus in molecular science is now shifting from highly diluted and well-equilibrated molecular systems to more complex, non-equilibrated systems in highly condensed phases, Prof. Aida discovered extrusion polymerization of olefins in 1999 using catalyst-immobilized nanoscopic channels of mesoporous silica (ref. 32). When ethylene is allowed to polymerize, polymer chains that are produced in nanopores are not allowed to fold but extruded unidirectionally like spider silk. The chains then assemble together into extended-chain crystalline fibers having ultrahigh mechanical properties. In general, highly anisotropic hierarchical structural ordering can provide materials with extraordinary properties. However, this process is known to be interfered by kinetic traps that emerge in the transition from nano to mesoscopic size regimes. Based on the seminal discovery of extrusion polymerization, Prof. Aida noticed how multivalent interactions and physical perturbations are useful for avoiding kinetic traps that prevent hierarchical structural ordering in highly condensed systems and properly connect the missing link between nano and meso-scale phenomena. From then on, he has been promoting this immature research field and has accomplished numerous seminal achievements for creating innovative soft materials. A hydrogel named “aquamaterial” is one of his successful achievements, which is rich in water (98%) but mechanically robust and moldable into any self-standing shape. This material can be readily prepared by adding a minute amount of a polymer “molecular glue” to an aqueous dispersion of clay nanosheets. In 2010, Prof. Aida reported this material in Nature (ref. 23) and gave a big impact to the related research field. The molecular glue in this hydrogel multivalently forms a crosslinked 3D network with clay nanosheets, wherein water molecules are entrapped and frozen. Different from hydrogels based on covalent linkages, aquamaterial can be readily prepared by non-experts using on-site water. The preconception that such supramolecular hydrogels are too weak for practical purposes has been casted aside. By increasing the nanosheet content, aquamaterial becomes much more robust and would not be easily disrupted even under a heavy weight. It is intriguing that such a mechanically robust material can be fabricated from water that covers 70% of the surface of our planet, having a minimum dependency on fossil fuels. While exploring the possibility of aquamaterial for future sustainable society, Prof. Aida reported the second-generation aquamaterial (ref. 13), as described below. Based on physical perturbations, Prof. Aida makes numerous achievements. One of them features the discovery of cofacial magneto-orientation of colloidally dispersed titanate nanosheets in water. With this cofacial geometry, a strong electrostatic repulsion emerges between nanosheets due to their surface charges 20 (ref. 5). Therefore, the dispersion spontaneously undergoes a quasi-crystalline order. Prof. Aida converts this anisotropic dispersion into a hydrogel for fixing the entropically demanding cofacial geometry. The resulting hydrogel is tolerant against a compression force applied orthogonally to the nanosheets but deforms largely and quickly in response to a shear force applied parallel to the nanosheets (refs. 6, 13 and 16). This mechanism is reminiscent of how articular tissues use bottle-brush charged polymers. The second-generation aquamaterial, if implantable, may shed light on the issue of articular decease. Use of electrostatically repulsive force for modulating mechanical properties is beyond one’s expectation but really like Prof. Aida’s approach. One of his early discoveries features light-harvesting antenna functions of dendrimers that progressively increase their branch density from the central core to the periphery. This work allowed him to stand on the world stage (ref. 33). Successful examples also include the first electroconductive and redox active nanotubes (refs. 14, 19, 26 and 29), which are recognized to show a big potential of self-assembly. The first example of chain-growth supramolecular polymerization, reported by Prof. Aida in 2015, makes it possible to control the length of non-covalently constructed polymer chains and their stereochemistry (refs. 2 and 11). This work updates the 100-year history of polymer chemistry. Bucky gels, reported by Prof. Aida in 2003, can be readily obtained by mechanical dispersion of carbon nanotubes in ionic liquids (ref. 30). Bucky gels enabled the development of the first battery-driven dry actuator that can be used for handy Braille devices. Through collaborative studies, bucky gels turn out to be useful for developing stretchable electronic devices essential for soft robotics and next-generation health care (refs. 24 and 25). As a recent extension of bucky gels, Prof. Aida developed oligomeric ionic liquids that enable microwave-triggered exfoliation of graphite into genuine single-layer graphene in more than 80% total recovery yield (ref. 7). As a recent big sensation, Prof. Aida developed a polymer glass that is highly robust mechanically but can self-heal even at ambient temperature when fractured surfaces are compressed together (ref. 1). This finding changed the long-term preconception in polymer science that only rubbers composed of floppy polymer chains are self-healable. In summary, Prof. Takuzo Aida developed a variety of conceptually new innovative soft materials that showed up multiple times in top journals. He has shown a large potential of Japanese research activity to the world and has attracted attention of many of his fans. His consistent challenging spirit for creative researches has been highly appreciated worldwide and influential across the border of different scientific disciplines. References (1) Y. Yanagisawa, Y. Nan, K. Okuro and T. Aida, “Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking”, Science 2018, 359, 72-76. (2) K. V. Rao, D. Miyajima, A. Nihonyanagi and T. Aida, “Thermally Bisignate Supramolecular Polymer- ization”, Nature Chem. 2017, 9, 1133-1139. (3) M. Ueda, K. Jorner, Y. M. Sung, T. Mori, Q. Xiao, D. Kim, H. Ottoson, T. Aida and Y. Itoh, “Energetics of Baird Aromaticity Supported by Inversion of Photoexcited Chiral [4n]annulene Derivatives”, Nature Commun. 2017, 8, Article No. 346. (4) H. Arazoe, D. Miyajima, K. Akaike, F. Araoka, E. Sato, T. Hikima, M. Kawamoto and T. Aida, “An Autonomous Actuator Driven by Fluctuations in Ambient Humidity”, Nature Mat. 2016, 15, 1084-1089. (5) K. Sano, Y. S. Kim, Y. Ishida, Y. Ebina, T. Sasaki, T. Hikima and T. Aida, “Photonic Water Dynamically Responsive to External Stimuli”, Nature Commun. 2016, 7, Article No. 12559. (6) Y. S. Kim, M. Liu, Y. Ishida, Y. Ebina, M. Osada, T. Sasaki, T. Hikima, M. Takata and T. Aida, “Thermoresponsive Actuation Enabled by Permittivity Switching in an Electrostatically Anisotropic 21 Hydrogel”, Nature Mat. 2015, 14, 1002-1007. (7) M. Matsumoto, Y. Saito, C. Park, T. Fukushima and T. Aida, “Ultrahigh-Throughput Exfoliation of Graphite into Pristine ‘Single-Layer’ Graphene using Microwaves and Molecularly Engineered Ionic Liquids”, Nature Chem. 2015, 7, 730-736. (8) C. Li, J. Cho, K. Yamada, D. Hashizume, F. Araoka, H. Takezoe, T. Aida and Y. Ishida, “Macroscopic Ordering of Helical Pores for Arraying Guest Molecules Noncentrosymmetrically”, Nature Commun. 2015, 6, Article No. 8418. (9) S. Chen, Y. Itoh, T. Masuda, S. Shimizu, J. Zhao, J. Ma, S. Nakamura, K. Okuro, H. Noguchi, K. Uosaki and T. Aida, “Subnanoscale Hydrophobic Modulation of Salt Bridges in Aqueous Media”, Science 2015, 348, 555-559. (10) M. Huang, C.-H. Hsu, J. Wang, S. Mei, X. Dong, Y. Li, M. Li, H. Liu, W. Zhang, T. Aida, W.-B. Zhang, K. Yue and S. Z. D. Cheng, “Selective Assemblies of Giant Tetrahedra via Precisely Controlled Positional Interactions”, Science 2015, 348, 424-428. (11) J. Kang, D. Miyajima, T. Mori, Y. Inoue, Y. Itoh and T. Aida, “A Rational Strategy for the Realization of Chain-Growth Supramolecular Polymerization”, Science 2015, 347, 646-651. (12) A. S. Tayi, A. Kaeser, M. Matsumoto, T. Aida and S. I. Stupp, “Supramolecular Ferroelectrics”, Nature Chem. 2015, 7, 281-294. (13) M. Liu, Y. Ishida, Y. Ebina, T. Sasaki, T. Hikima, M. Takata and T. Aida, “An Anisotropic Hydrogel with Electrostatic Repulsion between Cofacially Aligned Nanosheets”, Nature 2015, 517, 68-72. (14) T. Fukino, H. Joo, Y. Hisada, M. Obana, H. Yamagishi, T. Hikima, M. Takata, N. Fujita and T. Aida, “Manipulation of Discrete Nanostructures by Selective Modulation of Noncovalent Forces”, Science 2014, 344, 499-504. (15) S. Biswas, K. Kinbara, T. Niwa, H. Taguchi, N. Ishii, S. Watanabe, K. Miyata, K. Kataoka and T. Aida, “Biomolecular Robotics for Chemomechanically Driven Guest Delivery Fuelled by Intracellular ATP”, Nature Chem. 2013, 5, 613-620. (16) M. Liu, Y. Ishida, Y. Ebina, T. Sasaki and T. Aida, “Photolatently Modulable Hydrogels using Unilamellar Titania Nanosheets
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