annual report 2019 · 2020. 3. 19. · 7. processing of feeble magnetic materials under a magnetic...

Faculty of Environmental Sciences Department of Applied Chemistry for Environment

Graduate School of Environmental Sciences

Department of Applied Chemistry for Environment

Annual Report 2019

Index

Reports from Research Groups

Kawakami Laboratory ▪▪▪▪▪ 1

Masuda Laboratory ▪▪▪▪▪ 7

Asayama Laboratory ▪▪▪▪▪ 9

Kubo Laboratory ▪▪▪▪▪ 11

Setaka Laboratory ▪▪▪▪▪ 14

Kanamura Laboratory ▪▪▪▪▪ 16

Kajiwara Laboratory ▪▪▪▪▪ 19

Takagi Laboratory ▪▪▪▪▪ 21

Uchiyama Laboratory ▪▪▪▪▪ 25

Shishido Laboratory ▪▪▪▪▪ 29

Shudo Laboratory ▪▪▪▪▪ 32

Colloquium ▪▪▪▪▪ 33


Kawakami Laboratory

■MembersHiroyoshi KAWAKAMIProfessor / Dr. Eng.Polymer Chemistry, Functional Polymers, NanofiberEngineering, Biomaterials, Epigenetics Engineering, FreeRadical ScienceRm. 9-638, +81-42-677-1111 Ext. [email protected]

Masafumi YAMATO Associate Professor / Dr. Eng. Polymer Science, Magneto-Science Rm. 9-137, +81-42-677-1111 Ext. 4837 [email protected]

Kiyoshi SATO Associate Professor / Dr. Eng. Synthetic Organic Chemistry, Molecular Recognition, Heterocyclic Chemistry, Physical Organic Chemistry Rm. 9-349, +81-42-677-1111 Ext. 4886 [email protected]

Manabu TANAKA Associate Professor / Dr. Eng. Polymer Chemistry, Polymer Energy Materials, Fuel Cells, Secondary Batteries, Nanofibers, Polymer Membranes Rm. 9-639, +81-42-677-1111 Ext. 4586 [email protected]

Doctor’s course - 2 Master’s course - 19 Bachelor 4 - 8

■Outlines of the Research

1. Study of Functional Polymer MembraneHiroyoshi KAWAKAMI, Masafumi YAMATO,Manabu TANAKA

Membrane-based gas separations have tremendous potential as energy-efficient alternatives or removal material of greenhouse gasses, such as carbon dioxide (CO2). Recently, we have reported that novel composite membranes composed of the fluorinated polyimide or polymers of intrinsic microporosity (PIM) and surface-modified silica nanoparticles exhibit high gas permeability and selectivity.

In this year, we found that the expansion of the nano-space which was formed on the surface of silica nanoparticles leads to an increase in gas permeability of composite membranes. The temperature dependence of the composite membrane containing surface-modified nanoparticles was also clarified. We have also started research on the development of composite membranes with asymmetric structures.

Figure 1. Enhancement of gas permeability by expansion of nano-space.

2. Study of Polymer Electrolyte MembraneHiroyoshi KAWAKAMI, Manabu TANAKA

Polymer electrolyte fuel cells have attracted much attention as clean and sustainable energy systems. We have reported composite polymer electrolyte membranes based on phytic acid (Phy)-doped polybenzimidazole nanofibers (PBINF) showed outstanding fuel cell performances under low relative humidity conditions.

In this year, we fabricated novel polymer composite membranes containing proton conductive nanofibers that have proton conductivity inside nanofibers, inter-connected structures to construct continuous proton conductive pathway, and surface-modified structures with acid and/or zwitterion molecules.. The novel polymer composite membranes showed higher proton conductivity than the conventional composite membranes, especially under low humidity conditions, which are assumed as future fuel cell operation conditions.

Figure 2. Approaches to improve proton conductivity on the nanofiber composite membranes.

3. Study of Electrospun NanofibersHiroyoshi KAWAKAMI, Manabu TANAKA

Recently, nano-scale fibers prepared through an electrically charged jet of polymer solution/melt (electrospinning) have received a lot of attention. Nanofibers have several inherent characteristics including high surface area, unique optical and physicochemical properties originated from the nano-size, and alignment of polymer chains in the nanofibers. The diameter of nanofiber is one of the most important factors to effect on such unique characteristics. Ultrafine nanofibers with their diameters less than 50 nm were also obtained.

In this year, we mainly focused on the fabrication of the polymer composite membranes containing polar crystalline poly(vinylidene difluoride) nanofibers for the secondary battery applications. The novel lithium ion conductive nanofiber composite membranes showed high lithium ion conductivity and good charge-discharge properties.

Figure 3. Schematic illustration of the lithium ion battery using the lithium ion conductive polymer nanofiber composite membrane.

4. Design of Multi-electron Redox CatalystsHiroyoshi KAWAKAMI, Kiyoshi SATO

② NF連結性向上

① NF内部もプロトン伝導に活用

③ 表面プロトン伝導層の拡大

① Utilization of inside nanofiber

③ Surface-modification

② Connected

1


Native metallo-enzymes facilitate various types of chemical reactions under mild conditions in water. Thus, an artificial metal complex as a bioinspired metallo-enzyme has application potential for wide field of chemistry such as energy chemistry and medicinal chemistry. In this year, we have prepared a novel dinuclear metalloporphyrin bearing six phenolic OH substituents spatially closed to the metal centers. The metal complex acts as a proton-coupled multi-electron catalysis for electrochemical CO2 reduction by an efficient combination of the metal centers and OH groups. Figure 4. Proton-coupled multi-electron redox catalyst for electrocatalytic CO2 reduction. 5. Study of Epigenetics Engineering Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA

The development and maintenance of an organism is orchestrated by a set of chemical reactions that switch parts of the genome off and on at strategic times and locations. Epigenetics is the study of these reactions and the factors that influence them.

In this year, we have prepared novel anionic polymers for the artificial epigenetic control of the chromatin conformations. The anionic oligo- and poly-peptides successfully delivered to nucleus and show regulation of gene expressions. We also prepared a liposome nanocarrier capable of induction of mitophagy of damaged mitochondria to suppress cellular senescence. These biomaterials will provide new treatment strategies for acquired diseases caused by epigenomic modifications and regenerative therapy (adoptive cellular immunotherapy). Figure 5. Epigenetic gene expression control by chromatin conformations. 6. Study of Free Radical Control by Artificial Enzyme Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA

Superoxide dismutase (SOD) or catalase (CAT) are well known to efficiently eliminate superoxide radicals or hydrogen peroxide as the most important antioxidants. We demonstrated that a water-soluble cationic Mn-porphyrin with SOD activity or catalase activity exhibited anticancer activity as well as antioxidative activity.

In this year, we have prepared a cationic manganese N-confused porphyrin (MnNCP) as a coreductant-free catalyst for ONOO- disproportionation. The pyridinium-appended tetracationic MnNCP showed a higher ONOO- eliminating activity than that of previous reported metal porphynoids under physiological conditions without coreductants. Furthermore, synthesis of MnNCP dimer, expected a multiple antioxidant activity, is now under investigation. Figure 6. Cationic-N-confused Mn-porphyrin (MnNCP) with peroxynitrite eliminating activity. 7. Processing of feeble magnetic materials under a magnetic field Masafumi YAMATO Controls of higher-order structure of feeble magnetic materials by using a magnetic field have been studied in order to improve some properties and to reveal new functions of the materials. In this year, we focused on research of anisotropic organic / inorganic hybrid gels. The plane orientation of the clay in the nano composite gel was achieved by using a rotating magnetic field. The resulting gel showed anisotropy in Young's modulus and swelling. We succeeded in producing the nanocomposite gels with mechanical anisotropy. Figure 7. Schematic drawing of plane orientation of clay by rotating magnetic field and stress-strain curves of nanocomposite gels preparing in a rotating magnetic field. ■Papers with Peer Review 1. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi

Kawakami, "Fabrication and characterizations of soft and flexible Poly(dimethylsiloxane)-incorporated network polymer electrolyte membranes", Polymer, 186,122045 (2020).

2. Yuki Kudo, Hiroto Mikami, Manabu Tanaka, Tadayuki Isaji, Kazutoshi Odaka, Masafumi Yamato, Hiroyoshi Kawakami, "Mixed matrix membranes comprising a polymer of intrinsic microporosity loaded with surface-modified non-porous pearl-necklace nanoparticles", Journal of Membrane

N

N N

N

N+

HO OH

OH

OH

HO OH

Fe

Rotating MF

2


Science, 597, 117627 (2020). 3. Naoki Sakaguchi, Manabu Tanaka, Masafumi Yamato,

Hiroyoshi Kawakami, "Superhigh CO2-Permeable Mixed Matrix Membranes Composed of a Polymer of Intrinsic Microporosity (PIM-1) and Surface-Modified Silica Nanoparticles", ACS Applied Polymer Materials, 1, 2516-2524 (2019).

4. Tsukasa Watanabe, Yuta Inafune, Manabu Tanaka, Yasumasa Mochizuki, Futoshi Matsumoto, Hiroyoshi Kawakami, "Development of all-solid-state battery based on lithium ion conductive polymer nanofiber framework", Journal of Power Sources, 423, 255-262 (2019).

5. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, "Free-standing polydimethylsiloxane-based cross-linked network solid polymer electrolytes for future lithium ion battery applications", Electrochimica Acta, 307, 148-156 (2019).

6. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, "Bifunctional poly(ethylene glycol) based crosslinked network polymers as electrolytes for all-solid-state lithium ion batteries", Polymer International, 68, 684-693 (2019).

7. Taku Ibaraki, Manabu Tanaka, Hiroyoshi Kawakami, "Fast surface proton conduction on acid-doped polymer nanofibers in polymer electrolyte composite membranes", Electrochimica Acta, 296, 1042-1048 (2019).

8. Kosuke Chikuma, Kohei Arima, Yutaro Asaba, Riku Kubota, Shoichiro Asayama, Kiyoshi Sato, Hiroyoshi Kawakami, "The potential of lipid-polymer nanoparticles as epigenetic and ROS control approaches for COPD", Free Radical Research, 1-12 (2019).

9. Riku Kubota, Shoichiro Asayama, Hiroyoshi Kawakami, "Catalytic antioxidants for therapeutic medicine", Journal of Materials Chemistry B, 7, 3165-3191 (2019).

10. Yuki Kobayashi, Sakura Taneichi, Hiroyoshi Kawakami, Yoichi Negishi, Shoichiro Asayama, "Plasmid DNA Mono-Ion Complex for in Vivo Sustainable Gene Expression", ACS Omega 4, 11464–11471 (2019).

11. Fuminori Ito, Hidetaka Yamada, Kiyoshi Kanamura & Hiroyoshi Kawakami, "Preparation of Biodegradable Polymer Nanospheres Containing Manganese Porphyrin (Mn-Porphyrin)", Journal of Inorganic and Organometallic Polymers and Materials, 29, 1010–1018 (2019).

■Books 1. Manabu Tanaka, Hiroyoshi Kawakami, “Nanofibers:

Fabrication and Applications”, Technical Information Institute (Tokyo, Japan), p263-269 (2019). (in Japanese)

2. Manabu Tanaka, Hiroyoshi Kawakami, “Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation”, Fuel Cell, 19, 1, p29-33 (2019) (in Japanese)

3. Hiroto Mikami, Takuya Muramoto, Eiko Ito, Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami, “Fabrication and Characterizations of Polymers of Intrinsic Microporosity Gas Separation Membrane for High Gas Permeability, Proceeding of 27th Japan Polyimide Conference, p38-41 (2019) (in Japanese)

4. Masafumi Yamato ， ”Development of High Thermal Conductivity Materials-For Further Improvement of Thermal Conductivity-(Chapter 3, Section 6, Filler

Orientation Control Technology Using Magnetic Field)”, Technical Information Institute (Tokyo, Japan), 132-140 (2019). (in Japanese)

5. Masafumi Yamato, Kohki Takahashi,, Study in interaction between organic molecules and clay using magnetic alignment, 2018 Annual report of high field laboratory for superconducting materials in institute for materials research at Tohoku university，p.p. 158-159 (2019) (in Japanese)

■Invited Lectures 1. Masafumi Yamato, Thermal and magnetic properties of

polymer, 2019Basic seminar of polymer science for young engineers, Oct. 2019 Hiratsuka, Japan (in Japanese).

2. Masafumi Yamato, Understanding the supercooling of crystalline polymers and controlling the orientation by magnetic field，25th Research meeting of Magneto-science Society of Japan, Dec. 2019, Tokyo Japan (in Japanese)

3. Manabu Tanaka, Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation, The 26th Fuel Cell Symposium, May 2019, Tokyo Japan (in Japanese)

4. Manabu Tanaka, Fabrication and Battery Applications of Ion Conductive Polymer Nanofibers, Lecture at Kanagawa University, Sep. 2019, Yokohama Japan (in Japanese)

5. Manabu Tanaka, Development of Polymer Nanofiber Composite Membranes for Next-generation Fuel Cells, The 161st lecture meeting of Hydrogen Energy System Society of Japan, Jan. 2020, Tokyo Japan (in Japanese)

■Academic Meeting 1. Kosuke Chikuma, Kohei Arima, Riku Kubota, Kiyoshi Sato,

Hiroyoshi Kawakami, A novel approach by ROS inhibiton and HDAC2 activation for COPD treatment, The 9th Biennial Meeting of Society for Free Radical Research-Asia (Kyoto International Community House), P15, April 2019(in English)

2. M. Yamato, H. Kawakami，Study on gas permeation in surface-modified silica nanoparticle containing composite membrane with high gas permeability，41st annual meeting of membrane science of Japan, May 2019, Tokyo, Japan (in Japanease).

3. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi Kawakami, Enhancement of proton conductivity of composite electrolyte membrane by nanofiber containing polyvinylphosphonic acid, 39 th The Membrane Society of Japan, (Waseda University), P–16S (May 2019)

4. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami，Secondary battery characteristics of Lithium ion conductive nanofiber composite membrane, 41th Annual Meeting on The Membrane Society of Japan, Waseda University, P-17S May 2019 (in Japanese)

5. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers. 41th Annual Meeting of the Membrane Society of Japan (Waseda University), P–19S, May 2019 (in Japanese)

6. Xinming Qi, Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, Lithium ion conductive characteristics of ionic liquid containing cross-linked polymer electrolyte membranes, 41th Annual Meeting of The Membrane Society of Japan (Waseda University), P-33S, May 2019 (in Japanese)

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7. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Noriyuki Hirota, Adsorption behavior of NIPAm to clay, 41th The Membrane Society of Japan, (Waseda University), P-26S (May, 2019) (in Japanese)

8. M. Yamato, K. Komine, T. Miyazaki, H. Kawakami, Study in adsorption of NIPAm on clay using NMR and magneto birefringence measurements, 68th SPSJ annual meeting, May 2019, Osaka, Japan (in Japanease)

9. Manabu TANAKA, Takahiro OGURA, Hiroki HARADA, Motoki NISHIZAWA, Hiroyoshi KAWAKAMI, Fabrication and characterization of novel electrolyte composite membranes based on polymer nanofibers for fuel cell operation at unhumidified high temperature. The 68th SPSJ Annual Meeting (Osaka International Conference Center), May 2019 (in Japanese)

10. Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Evaluation of secondary battery characteristics of lithium salt-added nanofiber composite electrolyte membranes, The 68th SPSJ Annual Meeting (Osaka International Conference Center), 2H18, May 2019 (in Japanese)

11. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation, The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 1Pf084, May 2019 (in Japanese)

12. Yu Matsuda, Shun Nakazawa, Masahumi Yamato, Tanaka Manabu, Hiroyoshi Kawakami. Lithium ion conductive characteristics of n anofibers with spontaneous polarization. The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 2H17, May 2019 (in Japanese)

13. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of various polymer nanofibers. The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 1Pe083, May 2019 (in Japanese)

14. Kazuma Komine, Masafumi Yamato, and Hiroyoshi Kawakami, Evaluation of N-isopropylacrylamide adsorbed on clay using NMR., 19-1 Research Group on Nuclear Magnetic Resonance (Tokyo University of Marine Science and Technology), P-04, May 2019.

15. Ayano Imai, Hiroto Mikami, Eiko Ito, Manabu Tanaka, Hiroyoshi Kawakami, Effect of chemical modification on CO2 permeability of polymer composite membranes containing surface-modified silica nanoparticles, The 36th International Conference of Photopolymer Science and Technology, Makuhari Messe, Japan, B1-02, June 2019 (in Japanese)

16. Kosuke Chikuma, Kohei, Arima, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kawakami, COPD treatment by the synergistic effect of ROS elimination and HDAC2 activation, The 72nd Annual Meeting of Society for Free Radical Research JAPAN (Hokkaido Prefectural Citizens Activity Center), P-14, June 2019(in Japanese)

17. Ayano Imai, Hiroto Mikami, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Influence of surface-modified structures of silica nanoparticles on gas permeation properties of polymer composite membranes, The Annual Meeting of the Society of Fiber Science and Technology (Tower Hall Funabori), 2B06, June 2019(in Japanese)

18. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi Kawakami, Evaluation of Fuel Cell Characteristics of Composite Electrolyte Membrane with Polyvinylphosphonic Acid Containing Nanofiber, The Annual Meeting of the Society of Fiber Science and Technology, Japan(Tower Hall Funabori), 2P216 (June 2019）

19. Motoki Nishizawa, Takahiro Ogura, Manabu Tanaka, and Hiroyoshi Kawakami, Preparation of proton conductive nanofibers containing sulfonic acid and phosphonic acid and their application to fuel cells, The Annual Meeting of the Society of Fiber Science and Technology, Japan(Tower Hall Funabori), 3F02 (June 2019）

20. Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Preparation and evaluation of secondary battery using lithium salt-added nanofiber composite electrolyte, The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 2B12, June 2019 (in Japanese)

21. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation and application for secondary battery, The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 1P219, June 2019 (in Japanese)

22. Yu Matsuda, Shun Nakazawa, Masahumi Yamato, Tanaka Manabu, Hiroyoshi Kawakami. Lithium ion conductive characteristics of nanofibers contained lithium salt. The Annual Meeting of The Society of Fiber and Technology (Tower Hall Funabori), 2B11, June 2019 (in Japanese)

23. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers. The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 2P215, June 2019 (in Japanese)

24. Risa Mitsuhashi, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kawakami, Control of DNA methylation by epigenetics control carrier in cancer cell, 48th Medical macromolecular symposium, P3, July 2019, Tokyo, Japan (in Japanese)

25. Takeru Yamazaki, Kohei Arima, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kwakami, Inhibition of ROS induced epithelial-to-mesenchymal transition by functional nano-particle, 48th Medical macromolecular symposium, P22, July 2019, Tokyo, Japan (in Japanese)

26. Y. Okazaki, M. Yamato, T. Kato，Construction of a spiral structure mimicking crustaceans using liquid crystal of cellulose nanocrystal，23rd symposium on liquid-crystalline chemistry, July 2019, Yokohama, Japan (in Japanese).

27. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Preparation and evaluation of surface-modified pearl-necklace nanoparticles containing PIM-1 composite membrane with high gas permeability, The 4th International Symposium on Hydrogen Energy‒based Society (Tokyo Metropolitan University), P-24, Aug. 2019

28. Xinming Qi, Hiroyoshi Kawakami, Manabu Tanaka, Lithium ion conductive characteristics of cross-linked polymer electrolyte membranes containing ionic liquid, The 4th International Symposium on Hydrogen Energy‒based Society, TMU (Aug 2019)

29. Motoki Nishizawa, Risa Sakaguchi, Manabu Tanaka, and Hiroyoshi Kawakami, Fabrication and characteristic evaluation of composite electrolyte membranes containing proton conductive polymer nanofibers for fuel cells, International Seminar on Green Energy Conversion 2019,

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(Yamanashi University), (August, 2019) 30. Yu Matsuda, Manabu Tanaka, and Hiroyoshi Kawakami,

Lithium Ion Conductive Characteristics of composite Electrolyte Membranes Consisted of Polymer Nanofibers, International Seminar on Green Energy Conversion 2019, (Yamanashi University), (August, 2019)

31. Manabu TANAKA, Takahiro OGURA, Motoki NISHIZAWA, Moeri SHIMIZU, Hiroyoshi KAWAKAMI, Development of Nanofiber Composite Membranes Consisted of Non-Sulfonated Polymer Matrix for Reduction of Fuel Cell Cost, The 68h Symposium on Macromolecules (Fukui University) 2I10 (September 2019) (in Japanese)

32. Yu Matsuda, Mitsuki Ohiai, Syun Nakazawa, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami. Ion conductive characteristics and secondary battery application of composite electrolyte membranes consisted of nanofibers containing lithium salts. 68h Symposium on Macromolecules (Hukui University) 1I15 (September 2019) (in Japanese)

33. Yu Matsuda, Manabu Tanaka, Masahumi Yamato, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of nanofibers with polar groups. 68h Symposium on Macromolecules (Hukui University) 2Pf070 (September 2019) (in Japanese)

34. Minami Kawai, Riku Kubota, Kiyoshi, Sato, Hiroyoshi Kawakami, Formation of inclusion complexes between metalloporphyrins and cucurbituril, 69th Conference of Japan Society of Coordination Chemistry (Nagoya University, Higashiyama campus), 1PF-003 (September 2019)

35. M. Yamato, T. Nakaoji, K. Komine, H. Kawakami, Mechanical Anisotropy of MMT-NC Gel Prepared in Magnetic Field, 80th JSAP Autumn Meeting, Sep. 2019, Sapporo, Japan (in Japanease).

36. M. Yamato, K. Komine, T. Miyazaki, H. Kawakami, Study in adsorption of NIPAm on Montmollironite using magneto birefringence measurements and quantitative NMR measurement, the 43rd Annual Conference on MAGNETICS in Japan, Sep. 2019, Kyoto, Japan (in Japanease).

37. S. KAJIYAMA, M. NAKAYAMA, A. KUMAMOTO, M. YAMATO, Y. IKUHARA, T. KATO, Morphological and Orientational Control of Liquid-Crystalline Colloidal Particles, Japanese Liquid Crystal Conference 2019, Sep. 2019, Tsukuba, Japan (in Japanese)

38. M. Yamato, T. Miyazaki, H. Kawakami, Measurement of magneto-birefringence of clay dispersion containing NIPAM, 12th Annual Meeting of the Magneto-Science Society of Japan, Nov. 2019, Nagaoka, Japan (in Japanease).

39. Kosuke Chikuma, Kohei, Arima, Kiyoshi Sato, Hiroyoshi Kawakami, Development of mitophagy-induced nanocarriers for the suppression of cellular senescence, The 57th Annual Meeting of the Japanese Society for Artificial Organs (Osaka International Convention Center), YP05-5, November 2019(in Japanese)

40. Yu Matsuda, Mitsuki Ohiai, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami, Evaluation of all-solid-state secondary battery composed of lithium salt-containing nanofibers, Membrane Symposium 2019, Osaka, (November, 2019)

41. Manabu Tanaka, Takahiro Ogura, Motoki Nishizawa, Moeri

Shimizu, Hiroyoshi Kawakami, Fabrication and Evaluation of Proton Conductive Nanofiber Composite Membranes Utilizing Non-sulfonated Polymer Matrix, The 60th Battery symposium, Kyoto International Conference Center, 1C04 (November, 2019)

42. Yuta Inafune, Mitsuki Ochiai, Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and evaluation of all-solid-state secondary batteries consisted of lithium salt-containing PVDF nanofiber composite polymer electrolyte membranes, The 60th Battery symposium, Kyoto International Conference Center, 3F23 (November, 2019)

43. Yu Matsuda, Mitsuki Ohiai, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami. Ion conductive mechanism analysis and all-solid-state battery application of composite polymer electrolyte membranes consisted of nanofibers containing lithium salts. The 60th Battery Symposium in Japan, Japan (Kyoto International Convention Center), (November 2019) (in Japanese)

44. Wataru Murata, Yuta Inafune, Manabu Tanaka, Hiroyoshi kawakami, Fabrication and evaluation of composite polymer electrolyte membranes based on lithium ion conductive PEO-grafted polyimide nanofibers, 27th symposium of polyimide and Aromatic polymer, Tokyo institute of Technology, Japan, P18 (November, 2019) (in Japanese)

45. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Hirota Noriyuki, Adsorption behavior analysis using in-situ magneto-birefringence and quantitative NMR, 87th Musashino area polymer association, (Tokyo Metropolitan University), Poster (November, 2019) (in Japanese)

46. Takeru Yamazaki, Kiyoshi Sato, Hiroyoshi Kawakami, Regulation of the transition to cancer stem cells by nanoparticles exhibiting antioxidant and epigenetic control activities, The 41st Annual Meeting of the Japanese Society for Biomaterials, Tsukuba International Congress Center, P108, (November, 2019) (in Japanese)

47. Kazuma Komine, Takashi Nakaozi, Masafumi Yamato, and Hiroyoshi Kawakami, Mechanical properties of MMT-NC gel prepared in rotating magnetic field, 14th Annual Meeting of the Magneto-Science Society of Japan (City Hall Plaza Aore Nagaoka), P-25, November 2019.

48. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Preparation and evaluation of gas permeation properties of PIM-1 composite membranes containing surface-modified pearl-necklace silica nanoparticles, The 57th Annual Meeting (Tokyo University of Marine Science and Technology), P-10, Dec. 2019

49. Hiroki Harada, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and fuel cell characterizations of composite electrolyte membranes composed of proton conductive nanofibers modified with zwitterion for high proton conductivity at high temperature and low humidity, The 57th Annual Meeting of Polymer and Water (Tokyo University of Marine Science and Technology), P-11, Dec. 2019

50. Ayano Imai, Naoki Sakaguchi, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Gas Permeation Properties of PIM-1 Composite Membranes Containing Surface-modified Silica Nanoparticles, CEMSupra (Tokyo University Ito International Research Center) , December 2019

51. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami,

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Property Evaluation of Lithium Salt-containing Polymer Nanofiber Composite Electrolyte Membrane and Lithium Ion Secondary Battery Characteristics, CEMS International Symposium on Supramolecular Chemistry & Functional Materials 2019 (CEMSupra 2019), Tokyo, P-60 (December, 2019)

52. Yoshihiro HOSOKAWA, Kohei MOCHIZUKI, Masanari NAKAYAMA, Akihito KUMAMOTO, Yuichi IKUHARA, Masafumi YAMATO, Taiki HOSHINO, Takashi KATO, Liquid-Crystalline Inorganic/Organic Nano-Hybrids Obtained through Biomineralization-Inspired Processes, the 16th Pacific Polymer Congress, Dec. 2019, Suntec, Singapore,

53. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Hirota Noriyuki, Study in Adsorption behavior of organic molecules to clay using *in-situ* magneto-birefringence and quantitative NMR, The 67th JSAP Spring Meeting, (Sophia University), 14p-PA1-2 (March, 2020) (in Japanese)

54. Takashi Nakaoji, Masafumi Yamato, Hiroyoshi Kawakami, Mechanical and optical properties of hydrogels cross-linked physically by clays, 25th Meeting of Magneto-Science Society of Japan 2019 (Nihon University), P4 (December, 2019)

55. Kosuke Chikuma, Kiyoshi Sato, Hiroyoshi Kawakami, Consideration of suppression of cellular senescence by functional nano-carrier inducing mitophagy, The 19th Congress of Japanese Society for Regenerative Medicine (Pacifico Yokohama), March 2020(in Japanese)

56. Shiori Higashi, Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami, Gas permeation properties of polymer membranes containing surface-modified pearl-necklace shaped nanoparticles, the SJEJ 85th Annual Meeting / IChES 2020 (Kansai University), PE302 (March, 2020) (in Japanese)

■Patents 1. JP2019-189994,A "Lithium ion conductive nanofiber,

Fabrication, Nanofiber assembly, Composite, Solid Polymer Electrolyte, and Lithium ion battery, Hiroyoshi Kawakami, Manabu Tanaka, Shun Nakazawa, Kaito Takenaka

2. JP2019-183379,A "Nanofiber, Nanofiber assembly, Composite membrane, Solid polymer electrolyte, and Lithium ion battery, Hiroyoshi Kawakami, Manabu Tanaka, Tsukasa Watanabe

■Awards 1. Prize for Encouragement, H30 Fuel Cell Development

Information Center (FCDIC), Manabu Tanaka, Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation

2. Student poster award, The 68th SPSJ Annual Meeting, Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation

3. Student poster award, the 68th SPSJ Annual Meeting, Motoki Nishizawa, Manabu Tanaka, Hiroyoshi Kawakami, Enhancement of proton conductivity of composite electrolyte membrane by nanofiber containing polyvinylphosphonic acid

4. Student poster award, 2019 Annual Meeting on The Society

of Fiber Science and Technology, Japan, Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation and application for secondary battery.

5. Student poster award, 2019 Annual Meeting on The Society of Fiber Science and Technology, Japan, Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers.

6. Best Poster Award, The 57th Annual Meeting of the Japanese Society for Artificial Organs, Kosuke Chikuma, Kohei, Arima, Kiyoshi Sato, Hiroyoshi Kawakami, Development of mitophagy-induced nanocarriers for the suppression of cellular senescence

7. Student poster award, 27th symposium of polyimide and Aromatic polymer, Wataru Murata, Yuta Inafune, Manabu Tanaka, Hiroyoshi kawakami, Fabrication and evaluation of composite polymer electrolyte membranes based on lithium ion conductive PEO-grafted polyimide nanofibers

8. Student Poster Award, The 57th Annual Meeting of Polymer and Water, Hiroki Harada, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and fuel cell characterizations of composite electrolyte membranes composed of proton conductive nanofibers modified with zwitterion for high proton conductivity at high temperature and low humidity

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Masuda Laboratory

■Members

Hideki Masuda

Professor/ Dr. Eng.

Electrochemistry, Nano Fabrication, Functional Electrode

Rm. 9-147, +81 426 77 2843

[email protected]

Takashi Takei

Associate Professor /Dr. Eng.

Solid surface chemistry, interface and colloid science

Rm. 9-136, +81 426 77 2822

[email protected]

Takashi Yanagisita

Associate Professor/ Dr. Eng.

Electrochemistry, Functional Metal Oxide Film

Rm. 9-140,+81 426 77 1111 (Ext. 4931)

[email protected]

Master’s course -10

Bachelor 4 -6


(1) Fabrication of Nanofilters by Electrochemical Process

Hideki MASUDA, Takashi YANAGISHITA

For the fabrication of ordered nanofilere membranes, we

have investigated anodization process of Al. The size and

interval of holes could be controlled by adjusting the anodization

conditions. Metal and semiconductor nanohole array structures

have been also fabricated using an anodic porous alumina as a

template. For the replacement of the ordered hole-array structure

with other materials we developed a two-step replication process

in which formation of a replicated negative and subsequent

preparation of a replicated positive give the nanohole structure

identical to that of mother structure of anodic orous alumina.

Metal (Au, Pt, Ni) and semiconductor (TiO2, ZnO, CdS)

nanohole arrays have been fabricated using the two-step process.

Detailed conditions for the precise replication were examined

experimentally, and new applications, such as optical devices

and detector for low energy ions, have been developed

SEM image of anodic porous alumina

(2) Preparation of Ordered Nanostructures by Nanoimprinting

Using Ordered Anodic Porous Alumina Molds


Ordered pillar array and hole array patterns were fabricated

by nanoimprinting using anodic porous alumina. Patterned

surface prepared by this process could be used for the

antirefrection surface and surper hydrophobic surface.

(3). Fabrication of Enagy Devices Based on Ordered Anodic

Porous Alumina


For the preparation of uniform sized nanoparticles, we have

introduced membrane emeulsification process using ordered

anodic porous alumina. The present process is simple and can be

used as a high-throughput process for forming monodispersed

nanoparticles of metal oxides. The monodispersed nanoparticles

prepared by this process will be useful as electrode active

materials in the Li ion batteries to improve the properties.

(4) Study of Self-ordering Mechanism of the Cell Arrangement

of Anodic Porous Alumina

Hideki MASUDA

Regularity of the holearray structure of the anodic porous

alumina which is used as mother template is important to

improve the regularity of the obtained metal and semiconductor

nanohole arrays. To improve the regularity of the holearray

structure of the anodic porous alumina, anodizing conditions

were explored, and self-ordering of the anodic oxide film was

newly discovered in sulfuric acid solution. The detailed

mechanism of the self-ordering of the anodic porous alumina is

currently being investigated.

(5)Evaluation of Pore Structures of Highly Ordered Porous

Alumina by Nitrogen Adsorption Method

Takashi Takei, Takashi Yanagishita, Hideki Masuda

The pore size distribution and surface area of highly ordered

porous alumina have been investigated by the nitrogen

adsorption method.

■Papers with Peer Review

1. T. Yanagishita, A. Kato, T. Kondo, and H. Masuda,

Preparation of Freestanding Tubular Alumina Through-

Hole Membranes by Two-Layer Anodization, Jpn. J. Appl.

Phys., 59, 038002 (2020).

2. T. Yanagishita, H. Awata, K. Kobayashi, T. Kondo, and H.

Masuda, Preparation of Polymer Nanofibers with

Controlled Diameters by Continuous Spinning Using

Ordered Anodic Porous Alumina as Spinneret, Chem. Lett.,

48, 86 (2019).

3. T. Yanagishita, G. Otain, H. Onomoto, T. Kondo, and H.

Masuda, One-Pod Preparation of Anodic Porous Alumina

Molds with Tapered Holes for Moth-Eye Structures by

Nanoimprinting, Jpn. J. Appl. Phys., 58, 068005 (2019).

■Reviews and Books

See the annual report in Japanese (6 articles)

■Invited Lectures

＊International

1. T. Yanagishita, T. Kondo, and H. Masuda

Ordered Nanoporous Semiconductors with Controlled

Geometrical Structures by Anodization Process

235th Electrochemical Society Meeting, 2019/5，US.

2. H. Masuda

Fabrication of Highly Ordered Anodic Porous Alumina and

Its Functional Applications

3rd International Symposium on AST 2019，2019/6，Awaji.

7


3. T. Yanagihsita, T. Kondo, and H. Masuda

High Throughput Preparation of Through-Hole Membranes

with Ordered Hole Arrangement

3rd International Symposium on AST 2019，2019/6，Awaji.

＊Domestic


■Academic Meeting

＊International

1. T. Kondo, R. Otsuki, K. Matsuo, T. Yanagishita, and H.

Masuda, Anisotropic Anode Etching of Al and its Optical

Application, 3rd International Symposium on AST2019, ，

2019/6, Awaji.

2. T. Kondo, T. Yanagishita, H. Masuda, Thermal Radiation

Control Structure Obtained by Anisotropic Anode Etching

of Al, ANZCOP 2019-SPIE, 2019/12，Australia.

＊Domestic


■Patents


■Awards


8

Asayama Laboratory

■Members

Shoichiro ASAYAMA

Associate Professor / Dr. Eng.

Biomaterials, Drug Delivery System, Biomedical Polymers,

Biomolecular Engineering, Biochemistry

Rm. 9-651, +81-42-677-1111 Ext. 4976

[email protected]


Bachelor 4 -3


To improve human health and quality of life (QOL), we have

designed new biomaterials. Especially, we have designed new

drug delivery system (DDS) for advanced and homogeneous

medicine as follows:

1. Nucleic Acid (Plasmid DNA, various RNAs) Delivery

System

Shoichiro ASAYAMA

As water-soluble (liquid-phase) biomaterials, the carriers of

nucleic acid as a macromolecular drug have been designed for

unmet medical needs. Recently, the mono-ion complex (MIC)

to make plasmid DNA (pDNA), as a gene, highly condensed has

been formed for delivery to in vivo unexplored space (Figure 1).

Figure 1. Delivery to in vivo unexplored space by the mono-

ion complex (MIC).

In this year, mono-cationic PEGs with an amide or ester

spacer between a terminal cation and PEG have been synthesized.

Furthermore, a di-cationic PEG with an ester spacer has been

synthesized. The mono-ion complex (MIC) and di-ion

complex (DIC) of plasmid DNA (pDNA) with the resulting

PEGs have been formed. The structure-activity relationship of

in vivo gene delivery by use of the MIC and DIC have been

demonstrated.

2. Bioactive Substance (Zn2+, protein) Delivery System

Shoichiro ASAYAMA

To give DDS carrier the ability for definitive treatment, we

have designed pH-sensitive polyvinylimidazole (PVIm)

derivateives as intelligent materials to change their structure and

function in respons to external stimuli. Recently, Zn2+ delivery

to liver is applied for remote control of hypoglycemic hormone

(Figure 2).

Figure 2. Remote control of hypoglycemic hormone in blood.

In this year, the zinc porphyrin-carbohydrate conjugate (ZnP-

Lac) has been synthesized for cellspecific delivery of Zn2+ ions.

The resulting ZnP-Lac without cytotoxicity was added to HepG2

cells as a human liver model. The intracellular uptake of Zn2+

treated with ZnP-Lac was higher than that with ZnCl2 alone.

These results suggest that the ZnP-Lac delivered Zn2+ by the

recognition of lactose with an asialoglycoprotein receptor

(ASGP-R) on the HepG2 cell.

3. Biomaterials with Funtional Surface

Shoichiro ASAYAMA

As water-insoluble (splid-phase) biomaterials, to design

medical devices working in vivo or ex vivo with efficient

biocompatibility, we have recently applied cholesterol end-

modified poly(ethylene glycol), that is, Chol-PEG, as DDS

carrier to the non-covalent modification of solid surface (Figure

3).

Figure 3. Development of novel bio-function by Chol-PEG.

In this year, the modification density of cholesterol end-

modified PEG (Chol-PEG) to poly(propylene) (PP) surface, and

the molecular weight dependence of Chol-PEG-modified PP

surface on the adsorption of biomolecules and blood constituent

cells were examined. As a result, the design of the bio-inert

surface with Chol-PEG with molecular weight of 2,000 has been

succeeded. The resulting bio-inert surface is expected to be

applied for in vivo implanted devices.

Delivery to Unexplored Space

Disease

NN

C(CH2)n

O

H2N PEG

+

+

+

+ Mono-Ion Complex【MIC】

Pancreas

Zn2+

Liver

Insulin

Insulin

secretion

Survival insulin

to whole body

Protein

CH

CH2

N

N

xCH

CH2

N

N

1-x-yCH

CH2

N

N

y

+

(CH2)nCH3Zn2+

OCH3O CH2CH2O CH2CH2CH2Nn

C

H

O

H3C

CH3

H3C

CH3

H3C

Most S im p le

Non cova len t

PEGyla t ion

By-product by conventional

covalent PEGylation

7 8 9 10 11 12

Elution volume / mL

Insulin

Surface modification

with biocompatibility

9


1. Yuki Kobayashi, Sakura Taneichi, Hiroyoshi Kawakami,

Yoichi Negishi, Shoichiro Asayama, Plasmid DNA mono-ion

complex for in vivo sustainable gene expression, ACS Omega, 4,

11464-11471 (2019).

2. Riku Kubota, Shoichiro Asayama, Hiroyoshi Kawakami,

Catalytic antioxidants for Therapeutic Medicine, Journal of

Materials Chemistry B, 7, 3165-3191 (2019).

3. Akito Endo, Shoichiro Asayama, Preparation of Zn2+-chelated

carboxymethyl poly(1-vinylimidazole) for intracellular Zn2+

delivery, Journal of Minerals and Materials Characteriza-tion

and Engineering, 7, 213-220 (2019).

4. Kosuke Chikuma, Kohe Arima, Yutaro Asaba, Riku Kubota,

Shoichiro Asayama, Kiyoshi Sato, Hiroyoshi Kawakami, The

potential of lipid-polymer nanoparticles as epigenetic and ROS

control approaches for COPD, Free Radical Research, in press

(2019).

5. Shoichiro Asayama, Molecular design of polymer-based

carriers for plasmid DNA delivery in vitro and in vivo (Highlight

Review). Chemistry Letters, 49, 1-9 (2020).

6. Akito Endo, Taiga Nagakura, Hiroyoshi Kawakami, Shoichiro

Asayama, Synthesis and characterization of lactosylated poly(1-

vinylimidazole) for cell-specific plasmid DNA carrier, Internal

Medicine and Care, 4, 1-5 (2020).

■Academic Meeting


10


Kubo Laboratory

■Members

Yuji Kubo

Professor /Dr. Eng.

Organic Chemistry, Supramolecular Chemistry, Functional Dye

Room: 9-539 TEL: +81-42-677-3134

e-mail: [email protected]

J. Yan Mulyana

Associate Professor / Ph.D. Coordination Chemistry, Photochemistry

Room: 9-149 TEL: +81-42-677-2823


Ryuhei Nishiyabu

Assistant Professor / Dr. Eng. Supramolecular Chemistry, Organic Chemistry, Matetials

Chemistry

Room: 9-438 TEL: +81-42-677-1111 (Ext. 4941)


Doctor’s course -3


Bachelor 4 -8


1. Synthesis of dye-sensitized photocatalysts for Hydrogen

Production by Water Splitting

Yuji Kubo

Abstract

A visible-to-near-infrared (visible-to-NIR) light-driven

photocatalyst was prepared by loading a boron-dipyrromethene

(BODIPY)-phenothiazine conjugate dye as a photosensitizer on

hierarchical porous TiO2 semiconductor. The loaded dye

showed panchromatic sensitization of the porous TiO2 and the

system exhibited hydrogen generation. This study provides

important information for the development of metal-free

organic photosensitizers with a wide spectral response up to the

NIR region for photocatalytic water-splitting hydrogen

production.

Figure 1. Dye-sensitized photocatalytic hydrogen production

by water splitting.

2. Synthesis of photosensitizers for application in

dye-sensitized solar cells

Yuji Kubo

This study has been collaborated with Prof. Dr. Şule

ERTEN-ELA (Solar Energy Institute, Ege University).

Abstract

Much attention has been devoted to the synthesis of dyes

that absorb near-infrared (NIR) radiation because of numerous

demands for them as functional materials. In this work, we

have tried to propose NIR absorbing photosensitizers

applicable to dye-sensitized solar cell (DSSC) devices.

Figure 2. Chemical structure of a sensitizer for application in

p-typed DSSC and EQE spectrum the dye-loaded p-type DSSC.

3. Synthesis of selenium-containing dyes as photosensitizers

for triplet–triplet annihilation upconversion

Yuji Kubo

Abstract

A series of selenium-containing BODIPY dyes were

synthesized as photosensitizers for triplet–triplet annihilation

upconversion (TTA-UC). The bis(phenylselanyl)-BODIPY

dyes with different substituents at the phenylselanyl groups

absorbed visible light and exhibited fluorescence with a low

fluorescence quantum yield. The low value was ascribed to

heavy atom effects. When TTA-UC systems comprising these

dyes as triplet donors and pelyrene as a triplet acceptor

perylene were set up, substituent-dependent TTA-UC behaviors

were observed.

Figure 3. Selenium-containing BODIPYs as sensitizers for

triplet–triplet annihilation upconversion.

4. Synthesis of Near Infrared (NIR) Light Absorbing Dye for

Photodetectors

Yuji Kubo

Abstract

A series of thieno[1,3,2]oxazaborinine-containing

aza-BODIPYs (1–3) were newly prepared as near infrared NIR

absorbing dyes. As a potential device application, the 3-loaded

film was prepared on indium tin oxide (ITO). The film showed

a NIR absorption band at 827 nm with a wide spectral range. Its

applicability as a NIR photodetector was evaluated through

fabrication of a single-component device. The ITO/3 (85

nm)/Al (100 nm) device produced a photocurrent of 9.57 × 10−7

A cm−2 at a bias potential of 1 V upon illumination at 850 nm

and a fluence of 130 μW cm−2.

Figure 4. Chemical structures of thieno[1,3,2]oxazaborinine

-containing aza-BODIPYs (1–3) and J–V curves of a 3-loaded

device (ITO/3 (85 nm)/Al (100 nm)) measured in the dark

(blue) and under illumination (red) at 850 nm (130 μW cm−2).

5. Room-temperature phosphorescence-active boronate

particles as ratiometric afterglow sensors

11


Yuji Kubo and Ryuhei Nishiyabu

Abstract:

We found that boronate particles (BP), as a self-assembled

system prepared by sequential dehydration of

benzene-1,4-diboronic acid with pentaerythritol, showed

greenish room-temperature phosphorescence. This emission

was observed in both solid and dispersion state in water and

ratiometric afterglow sensing of water content in an organic

solvent was achieved by grafting of a rhodamine onto the

surface of BP.

Figure 5. Ratiometric afterglow sensing of water content in an

organic solvent by room-temperature phosphorescence-active

boronate particles (BP).

6. Synthesis of nanostructured BiVO4/TiO2 modified with dye

and co-catalyst molecules for photo-induced water oxidation

Mulyana J. Yan

Abstract

The titanium oxide (TiO2)-coated bismuth vanadate

(BiVO4) photoanode surface-modified with a ruthenium

complex (Rutbipy dye) and a porphyrin copper complex

(CuTCPP) co-catalyst features a cascade hole transfer from

BiVO4 to the dye and to the co-catalyst molecule, which

improves the PEC performance.

Figure 6. The structure of the TiO2-coated BiVO4 photoanode

surface-modified with Rutbipy dye and CuTCPP co-catalyst.

7. Boronate sol–gel method for one-step fabrication of

polyvinyl alcohol hydrogel coatings by simple cast- and

dip-coating techniques

Ryuhei Nishiyabu and Yuji Kubo

Abstract

The self-assembly of polyvinyl alcohol (PVA) and

benzene-1,4-diboronic acid (DBA) is employed as a sol–gel

method for one-step fabrication of hydrogel coatings with

versatile functionalities. A mixture of PVA and DBA in aqueous

ethanol is prepared as a coating agent. The long pot life of the

mixture allows for the coating of a wide range of materials with

hydrogel films by simple cast- and dip-coating techniques.

Figure 7. Boronate sol–gel method for one-step fabrication of

polyvinyl alcohol hydrogel coatings by a simple dip-coating

technique.

8. Accurate chiral pattern recognition for amines from just a

single chemosensor

Yuji Kubo

This study was collaborated with Tsuyoshi Minami (Institute of

Industrial Science, The University of Tokyo).

Abstract

The current work proposes a novel determination method

for enantiomeric excess (ee) in (mono- and di-) amines using

molecular self-assembly. A pyridine-attached binaphthyl

derivative ((R)-1) exhibits fluorescence responses based on

imine formation between the aldehyde group of (R)-1 and

target chiral amines (i.e. cyclohexane diamine (CHDA),

2-amino-1,2-diphenylethanol (ADPE),

1,2-diphenylethylenediamine (DPDA), 1-amino-2-indanol

(AID), and leucinol in the presence of zinc(II) ions (Zn2+).

Because of the multi-optical responses which are derived from

the variation of chiral complexes, pattern recognition-based

discrimination (i.e. linear discriminant analysis (LDA)) has

been achieved for five types of enantiomeric pairs of amines.

Possessing such a discrimination capability in combination

with data processing (LDA and an artificial neural network)

allows accurate determination (prediction error < 1.8%) of

the % ee of individual targets such as CHDA which is one of

the main components of pharmaceutical drugs. The simple

molecular self-assembled system enabled simultaneous

multi-chiral discrimination and % ee determination of unknown

samples.

Figure 8. Enantioselective response for optically ative

diamines by self-assembled chiral chemosensors.


1. Y. Sasaki, S. Kojima, V. Hamedpour, R. Kubota, S.

Takizawa, I. Yoshikawa, H. Houjou, Y. Kubo and T. Minami,

Accurate chiral pattern recognition for amines, albeit a

single chemosensor. Chem. Sci., 2020, accepted. DOI:

10.1039/D0SC00194E

2. M. Hoshi, R. Nishiyabu, Y. Hayashi, S. Yagi and Y. Kubo,

Room-temperature phosphorescence-active boronate

particles: characterization and ratiometric afterglow-sensing

behavior via surface grafting of Rhodamine B. Chem. Asian

J., 2020, accepted. DOI: 10.1002/asia.201901740

3. R. Nishiyabu, Y. Takahashi, T. Yabuki, S. Gommori, Y.

Yamamoto, H. Kitagishi and Y. Kubo, Boronate sol–gel

method for one-step fabrication of polyvinyl alcohol

hydrogel coatings by simple cast- and dip-coating

techniques. RSC Adv., 2020, 20, 86‒94. DOI:

10.1039/C9RA08208E

12


4 Y. Kubo, T. Shimada, K. Maeda

and Y. Hashimoto,

Thieno[1,3,2]oxazaborinine-con

taining aza-BODIPYs with near

infrared absorption bands:

synthesis, photophysical

properties, and device

application. New J. Chem., 2020,

44, 29-37. DOI:

10.1039/C9NJ04612G

5. Y. Higashino, S. Erten-Ela and

Y. Kubo, π-Expanded dibenzo-BODIPY with near-infrared

light absorption: investigation of photosensitizing properties

of NiO-based p-type dye-sensitized solar cells. Dyes and

Pigments, 2019, 170, 107613. DOI:

10.1016/j.dyepig.2019.107613

6. U. Pratomo, I. Purnama and Y. J. Mulyana, Photo-induced

water oxidation via cascade charge transfer on

nanostructured BiVO4/TiO2 modified with dye and

co-catalyst molecules, Inorg. Chim. Acta, 2020, 500,

119223. DOI: 10.1016/j.ica.2019.119223

7. O. Suryani, Y. Higashino, H. Sato and Y. Kubo,

Visible-to-near-infrared light-driven photocatalytic

hydrogen production using dibenzo-BODIPY and

phenothiazine conjugate as organic photosensitizer. ACS

Appl. Energy Mater., 2019, 2, 448‒458. DOI:

10.1021/acsaem.8b01474

■Invited Lectures

1. Near-infrared absorbing dibenzo-BODIPYs; Synthesis,

properties, and applications, Yuji Kubo, Lecture at Ege

University (Izmir, Turkey), July 22, 2019.

2. Solid-State Emissive Chemosensors based on Boronate

Supramolecules, Yuji Kubo, 3rd Asian Conference on

Chemosensors and Imaging Probes" (Asian-ChIP 2019),

Amritsar, India, November 7, 2019.

3. Preparation of solid catalysis and solid-based

luminescence materials based on boronate supramolecules,

Yuji Kubo, 19-2 Research group on supramolecules (The

Society of Polymer Science), Tokyo, January 24, 2020 (in

Japanese).

4. Synthesis of visible light and near-infrared absorbing dyes

for efficient light-induced hydrogen production, Yuji Kubo,

4S8-09 (Special Program lecture), The 100th CSJ Annual

meeting, March 25, 2020 (in Japanese).

■Academic Meeting


13


Setaka Laboratory

■Members Wataru Setaka Professor /Dr. Sci. Physical Organic Chemistry, Functional Organic Chemistry room: 9-542 TEL: +81-42-677-1111 (Ext.4955) e-mail: [email protected] Yusuke Inagaki Assistant Professor / Dr. Sci. Main-group Chemistry, Functional Organic Chemistry room: 9-545 TEL: +81-42-677-1111 (Ext.4957) e-mail: [email protected] Doctor’s course -0 Master’s course -5 Bachelor 4 -5

■Outlines of the Research Development of Highly Designed Organic Molecules Wataru SETAKA, and Yusuke INAGAKI Development of organic molecules of which strucrure and functions are highly designed would improve our daily life with respect to energy saving and environmental consequence. Our interest lies in the design and synthesis of organic molecules with new structures that incorporate silicon to develop molecules with new functions. Specifically, we are studying the relationship between molecular structure and molecular functionalities of novel organosilicon compounds. 1. Crystalline Molecular Gyrotop A molecular machine has been defined as a discrete number of molecular components that perform mechanical─like movements in response to specific stimuli. A macrocage molecule with a bridged thiophene rotor was synthesized as a molecular gyrotop having a dipolar rotor, given that the dipole derived from the thiophene can rotate even in the crystal. The thermally induced change in the orientation of the dipolar rotors (thiophene ring) inside the crystal, i.e., order-disorder transition, and the variation in the optical properties in the crystalline state were observed.

Figure 1. molecular gyrotop. We have reported our rewiews regarding chemistry of molecular gyrotops (Review #1). In this year, following papers were published. Methylcarbazole is known as efficient fluorophore. In this study, methylcarbazole bridged macrocage was designed and synthesized. Unfortunately, the carbazole moiety shows no rotation in a crystalline state. However, highly polarized fluorescence was observed due to unidirectional alignment of the carbazolue in a crystalline state (Figure 2, paper #4).

Figure 2. Structure and Polarized fluorescence of the crystal of methylcarbazole bidged macrocage (paper #4). Carbazole nitroxide is known as labile radical species due to extended pi-electron systems. We designed carbazole nitroxide bridged macrocage as kinetically stabilized mitroxide. Actually the life time of the radical was investigated by ESR spectroscopy. Remarkablly long life-time of the radical were observed (Figure 3, paper #2).

Figure 3. Structure and ESR spectrum of carbazole nitroxide bridged macrocage (paper #2). 2. Novel Molecular Bevel Gears Ditriptycilmethanes are known as molecular bevel gears because the two triptycil groups show correlated rotation. In this report, molecular bevel gears bridged with a group 14 element, bis(methyltriptycil)X (X = SiH2, GeH2, GeF2), were synthesized, and their gearing properties were investigated. Gear slippage, that is an error in gear rotation, is observed in high-temperature solutions of molecular bevel gears. Heavy atom derivatives undergo gear slippage more easily due to the long bond lengths and wide angles between the two triptycil units and the bridging group 14 element. Activation energies of gear slippages were estimated by temperature-dependent NMR spectroscopy and DFT calculations, and theoretical thermodynamic parameters for gear slippage were found to be in excellent agreement with experimental values. The results indicate that theoretical calculations for gear rotation in molecular bevel gears can accurately reproduce experimental phenomena. (Figure 4, paper #2).

Figure4. Gear slippage in a germanium-bridged molecular gears.

14


Construction of hydrogen-bonded networks among hydroxyl groups has often been utilized to synthesize specific structures on the basis of supramolecular chemistry. In this study, resorcyltriptycene was designed as a possible component of a crystalline molecular gear, because the molecule has a triptycyl wheel and a resorcyl linker which can be involved in intermolecular alignments in a crystal, as mediated by hydrogen-bonded networks. The synthesis and crystal structure of resorcyltriptycene are reported here. The gear alignment among triptycyls in a crystalline state was achieved in a crystal structure of resorcyltriptycene containing water in the intermolecular spaces. However, rotations of triptycyls in the crystalline state was suppressed by steric interaction with the water molecules. This crystal structure was stabilized by O–HꞏꞏꞏCπ(phenyl) interactions between triptycyl and the hydrated water. Moreover, single crystals without solvent and with methanol were obtained from a dry toluene solution and a methanol solution, respectively. Transformations among the single crystals were observed by heating or drying or soaking in a solvent. It is significant that various crystal structures dependent on the condition were observed. The observed phenomena should aid the design of functional crystals. (Figure 5, paper #1).

Figure 5. Crystal structure of resolcyltriptycene hydrate.

■Papers with Peer Review 1. Gear Alignments due to Hydrogen-Bonded Networks in a

Crystal Structure of Resorcyltriptycene Hydrate and its Transformation to a non-Gearing Anhydrate Crystal by Heating, N. Tanaka, Y. Inagaki, K. Yamaguchi, and W. Setaka, Cryst. Growth Des., 20(2), 1097-1102 (2020). DOI:10.1021/acs.cgd.9b01424

2. Gear Slippage in Molecular Bevel Gears Bridged with a

Group 14 Element, K. Okamura, Y. Inagaki, H. Momma, E. Kwon, and W. Setaka, J. Org. Chem., 84(18), 14636-14643 (2019). DOI:10.1021/acs.joc.9b02214

3. Kinetic Stabilization of Carbazole Nitroxides by Inclusion

in a Macrocage and their ESR Characterization, H. Hashimoto, Y. Inagaki, H. Mommma, E. Kwon, and W. Setaka, J. Org. Chem., 84(18), 11783-11789 (2019). DOI:10.1021/acs.joc.9b01686

4. Polarized Fluorescence of a Crystal having Uniaxially

Oriented Molecules by a Carbazole-diyl-bridged Macrocage, H. Hashimoto, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi, and W. Setaka, CrystEngComm, 21, 3910-3914 (2019). DOI: 10.1039/C9CE00706G

■Review 1. Chemistry of Macrocage Molecules with a Bridged

pi-Electron System as Crystalline Molecular Gyrotops, Wataru Setaka, Yusuke Inagaki, and Kentaro Yamaguchi, J. Synth. Org. Chem., J., 77(8), 813-822 (2019). DOI: 10.5059/yukigoseikyokaishi.77.813

■Invited Lecture 1. Chemistry of Molecular Gyrotops

W. Setaka Molecular Rotor Workshop 2019 , 2019.11.21-22, the Institute of Organic Chemistry and Biochemistry of the CAS(Prague, Czech Republic)(invited)

■Awards 1. Daiki Hayash, 46th onferenceof Main Group Element

Chemistry, ChemCommPresentationPrize、2019.12.. ■Academic Meeting *International 1. Facile Synthesis of Tetrasilyl[2]acediyne

Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka The 4th International Symposium on Hydrogen Energy-based Society, 2019.8.22-23, Tokyo Metropolitan University(Tokyo, Japan) (8/22, P-22) (poster)

2. Thiophene-Dioxide Bridged Macrocages as Crystalline

Fluorescent Molecular Gyrotops Wataru Setaka, Daiki Hayashi, Miyako Tsurunaga, Yusuke Inagaki, and Kentaro Yamaguchi 18th International Symposium on Novel Aromatic Compounds (ISNA-18), Sapporo Convention Center, 2019.7.21-26, (Sapporo, Japan)(7/22, 317) (poster)

*Domestic 1. Synthesis and Crystal Structures of Isophthalyltriptycene

Syuuto Ohyama, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/25 4B7-34)(oral)

2. Synthesis of Acediynes by Utilizing Bulkiness of Silyl

Groups Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/22 1C4-37)(oral)

3. Synthesis and Fluorescence Properties of Silyl-substituted

Benzo[b]thiophene-1,1-dioxides Keita Nobuhara, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/22 1B7-43)(oral)

4. Relation between Solid-state Fluorescence Intensity and

Motion of a Fluorophore in Thienothiophene-dioxide Bridged Molecular Gyrotops Daiki Hayashi, Yusuke Inagaki, Wataru Setaka 46th Main Group Element Chemistry , Matsuyama University, 2019.12.5-7 (Ehime, Japan). (12/5 O-21)(oral)

5. Facile Synthesis of Tetrasilyl[2]acediyne due to bulky silyl

groups Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka 9th CSJ Chemistry Festa, Tower Hall of Fenabori, 2019.10.15-17 (Tokyo, Japan).(10/16 P4-029)(poster)

15


Kanamura Laboratory

■Members

Kiyoshi KANAMURA

Professor /Dr. Eng.

Inorganic Industrial Chemistry, Energy Chemistry,

Electrochemistry

room:9-247 TEL: +81-42-677-2828


Hirokazu MUNAKATA

Assistant Professor /Ph.D.

Electrochemistry, Inorganic Material Chemistry,

Batteries and Fuel Cells

room:9-246 TEL: +81-42-677-2826




Bachelor 4 -7


1. Research on rechargeable magnesium batteries

Kiyoshi KANAMURA

Rechargeable magnesium batteries are attracting much attention

as next generation batteries to replace current lithium ion

batteries due to its abundant resources on the earth. In this FY,

we made and evaluated rechargeable magnesium batteries with

practical laminated-forms in addition to the exploration of new

materials to improve the batteriy performance.

Fig. 1 The charge and discharge curves of a rechargeable

magnesium battery with a practical laminated-form (cathode:

NiCo2O4, anode: Mg alloy).

2. Research on safe and high capacity rechargeable lithium

batteries

Kiyoshi KANAMURA, Hirokazu MUNAKATA

The development of rechargeable lithium batteries with lithium-

metal anode was carrired out in order to realize high energy

density. Lithium-metal anode has about ten times larger

gravimetric capacity than currently-used graphite anode.

However, its practical use requires the improvement of cycle

performance in addition to the suppression of needle-like

deposition of lithium metal. In this FY, we focused on the effects

of kind and concentration of Li salt in electrolyte solutions on

the cycle performance of lithium-metal anode (Fig. 2) and also

the formation of artificial ion conducting layers for smooth

deposition/dissolution of lithium-metal (Fig. 3). The

development of flexible quasi-solid electrolyte membranes

including Li+-ion conducting ceramic electrolyte is also

continuously performed as in the previous FY as another

approach to improve the safety of rechargeable lithium-metal

batteries.

Fig.2 Comparison of coulombic efficiencies of lithium-metal

anode in 1 mol dm-3 LiPF6 / EC and 4.5 mol dm-3 LiFSI / EC.

Fig.3 Improvement of deposition flatness of lithium metal by

the formation of an artificial ion-conducting layer.

3. Research on fuel cells

Kiyoshi KANAMURA, Hirokazu MUNAKATA

Toward the realization of a hydrogen society, the development

of a new fuel cell system that works at intermediate temperatures

over 100 °C under non-humidified conditions was promoted

continuously in this FY based on the use of phosphoric acid /

ionic liquid mixed electrolytes that have high proton

conductivity and thermal stability. As increasing the operating

temperature, the energy conversion efficiency of fuel cells can

be increased but the dissolution of platinum catalysts also is

enhanced. In this FY, we focused on the dissolution behavior of

platinum catalysts and found that high durability can be achieved

for platinum catalysts in the phosphoric acid / ionic liquid mixed

electrolytes (Fig. 4). For the reduction of fuel cell cost, non-

platinum carbon-based catalysts were also studied.

Fig. 4 Transmission electronic microscope images of platinum

catalysts before (upper image) and after the durability test in

phosphoric acid (lower-left image) and in the phosphoric acid /

ionic liquid mixed electrolyte (lower-right image).

1 mol dm-3

LiPF6 / EC4.5 mol dm-3

LiFSI / EC

16



1. Koki Nakano, Yusuke Noda, Naoto Tanibata, Masanobu

Nakayama, Koichi Kajihara, Kiyoshi Kanamura,

Computational investigation of the Mg-ion conductivity

and phase stability of MgZr4(PO4)6, RSC Adv., 9,12590-

12595 (2019).

2. Yuto Shimizu, Kiyoshi Kanamura, Three Dimensionally

Ordered Macroporous Polybenzimidazole Separator for

Li Metal Battery, Chem. Lett., 48, 429–432 (2019).

3. Kohei Shimokawa, Taruto Atsumi, Maho Harada, Robyn

E. Ward, Masanobu Nakayama, Yu Kumagai, Fumiyasu

Oba, Norihiko L. Okamoto, Kiyoshi Kanamura, Tetsu

Ichitsubo, Zinc-based spinel cathode materials for

magnesium rechargeable batteries: toward the reversible

spinel–rocksalt transition, J. Mater. Chem. A, 7, 12225-

12235 (2019).

4. Motoko Nagasaki, Kiyoshi Kanamura, High-Performance

Lithium Metal Rechargeable Battery Using an Ultrafine

Porous Polyimide Separator with Three-Dimensionally

Ordered Macroporous Structure, ACS Applied Energy

Materials, 2, 3896-3903 (2019).

5. Jihun Song, Williams Agyei Appiah, Kim Sung-Soo,

Hirokazu Munakata, Kiyoshi Kanamura, Myung-Hyun

Ryou, Yong Min Lee, 3D electrochemical model for a

Single Secondary Particle and its application for

operando analysis, Nano Energy, 62, 810-817 (2019).

6. Toshihiko Mandai, Kenji Tatesaka, Kenya Soh, Hyuma

Masu, Ashu Choudhary, Yoshitaka Tateyama, Ryuta Ise,

Hiroaki Imai, Tatsuya Takeguchi, Kiyoshi Kanamura,

Modifications in coordination structure of Mg[TFSA]2-

based supporting salts for high-voltage magnesium

rechargeable batteries, Physical Chemistry Chemical

Physics, 21, 12100-12111 (2019).

7. Yuta Maeyoshi, Dong Ding, Masaaki Kubota, Hiroshi Ueda,

Koji Abe, Kiyoshi Kanamura, Hidetoshi Abe, Long-Term

Stable Lithium Metal Anode in Highly Concentrated

Sulfolane-Based Electrolytes with Ultrafine Porous

Polyimide Separator, ACS Appl. Mater. Interfaces, 11,

25833-25843 (2019).

8. Yong Zhang, Masashi Konya, Ayaka Kutsuma,

Seonghyeon Lim, Toshihiko Mandai, Hirokazu Munakata,

Kiyoshi Kanamura, Magnesium Storage Performance and

Mechanism of 2D ‐ Ultrathin Nanosheet ‐ Assembled

Spinel MgIn2S4 Cathode for High ‐ Temperature Mg

Batteries, Nano Micro Small, 15, 1902236 (2019).

9. Motoko Nagasaki, Kei Nishikawa, Kiyoshi Kanamura,

Deterioration Analysis of Lithium Metal Anode in Full

Cell during Long-Term Cycles, J. Electrochem. Soc., 166,

A2618-A2628 (2019).

10. Nurzhan Umirov, Yuto Yamada, Hirokazu Munakata,

Sung-Soo Kim, Kiyoshi Kanamura, Analysis of intrinsic

properties of Li4Ti5O12 using single-particle technique, J.

Electroanal. Chem., 855, 113514 (2019).

11. Seonghyeon LIM, Hirokazu MUNAKATA, Kiyoshi

KANAMURA, Carbon Coating for Improvements of

Electrochemical Properties of Li1.1V0.9O2 Anode Active

Materials for Li Secondary Batteries, Electrochemistry,

88, 22-27 (2020).

12. Eric Jianfeng Cheng, Takeshi Kimura, Mao Shoji, Hiroshi

Ueda, Hirokazu Munakata, Kiyoshi Kanamura, Ceramic-

Based Flexible Sheet Electrolyte for Li Batteries, ACS

Appl. Mater. Interfaces, doi.org/10.1021/acsami.9b21251

(2020).

■Books and reviews


■Invited Lectures

＊International

1. Kiyoshi Kanamura, Lithium Metal Electrode 3D Separator,

LBIS 2019 4th Lithium Battery International Summit,

2019年5月, Hyatt Regency Shenzhen Airport, Shenzhen,

China.

2. Kiyoshi Kanamura, All Solid State Battery Prepared by

Composite Type Solid Electrolyte, INESS 2019 The 7th

International Conference on Nanomaterials and

Advanced Energy Storage Systems, 2019 年 8 月, Al-

Farabi Kazakh National university, Almaty, Kazakhstan.

3. H. Munakata, H. Inoue, T. Kimura, E.J. Cheng, K. Kanamura,

Development of Flexible Composite Electrolyte Sheets

for Next-Generation Batteries, 2nd World Conference on

Solid Electrolytes for Advanced Applications: Garnets

and Competitors, 2019年9月, Granship, Shizuoka, Japan.

4. Kiyoshi Kanamura, Direct Fabrication of Cathode Layer

Onto Oxide-Based Solid Electrolyte with Good Interface,

236th ECS Meeting, 2019年 10月, Hilton Atlanta, Atlanta,

USA.

5. Hirokazu Munakata, Jungo Wakasugi, Kyoko Kozuka,

Katsuya Honmou, Mao Shoji, Takeshi Kimura and Kiyoshi

Kanamura, Cathode design for rechargeable lithium-metal

batteries with Li6.25Al0.25La3Zr2O12 solid electrolyte,

PACRIM13, 2019 年 10 月, Okinawa Convention Center,

Okinawa, Japan

6. Hirokazu Munakata, Yamato Nagahori, Kiyoshi Kanamura,

Electrochemical evaluation of electrode active materials

by using μ-cavity current collector, WSLIBNGB 2019

The 3rd Work Shop on Lithium Ion Battery and Next

Generation Batteries 2019, 2019 年 11 月, Chungnam

National University, Daejeon, Korea.

＊Domestic

See the annual report in Japanese (3 articles including 1

requested lecture)

■Academic Meeting

＊International

1. Dong Ding, Yuta Maeyoshi, Masaaki Kubota, Jungo

Wakasugi, Kiyoshi Kanamura, Hidetoshi Abe, A Facile Way

to Synthesize Carbon-Coated LiMn0.7Fe0.3PO4/Reduced

Graphene Oxide Sandwich-Structured Composite for

Lithium Ion Batteries, 235th ECS Meeting, 2019 年 5 月,

Sheraton Dallas, Dallas, USA.

2. Feilure Tuerxun, Masashi Hattori, Kentaro Yamamoto,

Toshihiko Mandai, Masaki Matsui, Yoshitaka Tateyama,

Tomoki Uchiyama, Tatsuya Takeguchi, Kiyoshi Kanamura,

Yoshiharu Uchimoto, Interfacial Behavior of Magnesium

Ions at Electrode/Electrolyte Interface during Magnesium

Deposition Reaction, 235th ECS Meeting, 2019 年 5 月,

Sheraton Dallas, Dallas, USA.

3. Yuta Maeyoshi, Masaaki Kubota, Hidetoshi Abe, Koji Abe,

Kiyoshi Kanamura, Effect of Salt Concentration in

Sulfolane-Based Electrolyte on Long-Term Li

17


Plating/Stripping Behavior, 235th ECS Meeting, 2019 年

5 月, Sheraton Dallas, Dallas, USA.

4. Jie. Yu, H. Miura, H. Munakata, T. Shishido, K. Kanamura,

Development of membrane electrode assembly applying

on methanol-reforming-hydrogen/ oxygen intermediate

temperature fuel cell system, The World Hydrogen

Technologies Convention 2019, 2019 年 6 月 , Tokyo

International Forum, Tokyo, Japan.

5. K. Kanamura, M. Shoji, E. Cheng, Development of Flexible

Composite Solid Electrolyte and Quasi-solid Composite

Cathode for Practical Realization of Solid-state Lithium-

ion Batteries, GFMAT-2, 2019 年 7 月, Toronto Marriott

Downtown at CF Eaton Centre Hotel, Toronto, Canada.

6. Yong Zhang, Eric Jianfeng Cheng, Yuto Yamada, Yukihiro

Nakabayashi, Mao shoji, Jin Niu, Jae-sang Park, Hirokazu

Munakata, Kiyoshi Kanamura, Innovative Next Generation

Batteries for Low Carbon Society, The 4th International

Symposium on Hydrogen Energy-based Society, 2019 年

8 月, Tokyo Metropolitan University, Tokyo, Japan.

7. Jie. Yu, H. Miura, H. Munakata, T. Shishido, K. Kanamura,

Development of non-humidified intermediate

temperature methanol-reforming-hydrogen/ oxygen fuel

cell system, The 4th International Symposium on

Hydrogen Energy-based Society, 2019 年 8 月, Tokyo

Metropolitan University, Tokyo, Japan.

8. Koichi Kajihara, Mayu Suda, Ryosui Nakagawa, Kiyoshi

Kanamura, Highly-transparent efficient sol–gel-derived

silica – (Gd,Pr)PO4 glass-ceramic narrow-band UVB

phosphors, Photoluminescence in Rare Earths 2019

(PRE19), 2019年9月, Hotel Aston La Scala, Nice, France.

9. E. Cheng, T. Kimura, M. Shoji, H. Munakata, K. Kanamura,

Flexible Al-Li7La3Zr2O12 Composite Sheet Electrolyte for

Li Metal Batteries, 2nd World Conference on Solid

Electrolytes for Advanced Applications: Garnets and

Competitors, 2019 年 9 月, Granship, Shizuoka, Japan.

10. K. Hommo, M. Shoji, H. Munakata, K. Kanamura, Interfacial

Formation between LiCoO2 and Li6.25Al0.25La3Zr2O12 using

Lithium-ion Conductive Liquid, 2nd World Conference on

Solid Electrolytes for Advanced Applications: Garnets

and Competitors, 2019年9月, Granship, Shizuoka, Japan.

11. Eric Jianfeng Cheng, Takeshi Kimura, Hirokazu Munakata,

Kiyoshi Kanamura, Garnet-Based Flexible Composite

Sheet Electrolyte, 236th ECS Meeting, 2019 年 10 月,

Hilton Atlanta, Atlanta, USA.

12. Jie Yu, Hirokazu Munakata, Kiyoshi Kanamura,

Development of 3-Dimensionally Ordered Microporous

Polyimide Based Composite Membranes Apply on Non-

Humidified Intermediate Temperature Fuel Cells, 236th

ECS Meeting, 2019 年 10 月, Hilton Atlanta, Atlanta, USA.

13. Tsutomu Hashimoto, Kiyoshi Kanamura, Life Prediction of

Lithium Ion Battery for Grid Scale Energy Storage

System, 236th ECS Meeting, 2019年10月, Hilton Atlanta,

Atlanta, USA.

14. Yuto Yamada, Takeshi Kimura, Yosuke Kushida, Mao Shoji,

Kiyoshi Kanamura, Electrochemical Analysis Using

Microelectrode for Cathode Materials Deposited on a

Solid Electrolyte Pellet By Using Aerosol Deposition

Method, 236th ECS Meeting, 2019年10月, Hilton Atlanta,

Atlanta, USA.

15. Koki NAKANO, Yusuke NODA, Naoto TANIBATA,

Masanobu NAKAYAMA, Koichi KAJIHARA, Kiyoshi

KANAMURA, Evaluation of the Mg-ion conductivity and

phase stability of Mg-ion conductor MgZr4(PO4)6 by DFT

method, PACRIM13, 2019 年 10 月, Okinawa Convention

Center, Okinawa, Japan.

16. Ryosuke SETO, Koichi KAJIHARA, Kiyoshi KANAMURA,

Cosolvent-free synthesis and characterization of

poly(Ph-co-R-SQ) (R = Me, Et, Pr, and Vi) glasses with

low melting temperatures, PACRIM13, 2019 年 10 月,

Okinawa Convention Center, Okinawa, Japan.

17. Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei

Onodera, Shinji Kohara, Microscopic ordering in

amorphous poly(n-alkylsilsesquioxane) liquids and solids

synthesized by a cosolvent-free hydrolytic

polycondensation via aging, PACRIM13, 2019 年 10 月,


18. Jae-sang, PARK, YOSUKE Kushida, KYOSHI Kanamura,

Effect of heat treatment on electrochemical properties

of interface between LiCoO2-Li3BO3 composite and

ceramic type solid electrolyte formed by aerosol

deposition method, PACRIM13, 2019 年 10 月, Okinawa

Convention Center, Okinawa, Japan.

19. Hiroki Yamashita, Jun Ikegami, Yuko Hirayama, Takaaki

Ogami, Yuto Yamada, Kiyoshi Kanamura, Synthesis and

electrochemical properties of LiMn1-xFexPO4/C

secondary particles, PACRIM13, 2019 年 10 月, Okinawa

Convention Center, Okinawa, Japan.

20. Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei

Onodera, Shinji Kohara, Microscopic ordering in

amorphous poly(n-alkylsilsesquioxane) liquids and solids

synthesized by a cosolvent-free hydrolytic

polycondensation via aging, PACRIM13, 2019 年 10 月,


21. Eric Jianfeng Cheng, Takeshi Kimura, Hirokazu Munakata,

Kiyoshi Kanamura, Ceramic-based Flexible Composite

Sheet Electrolyte for Li-metal Batteries, PACRIM13,

2019 年 10 月, Okinawa Convention Center, Okinawa,

Japan.

22. Yusuke Uetake, Shunsuke Asahina, Natasha Erdman,

Tamae Omoto, Hirokazu Munakata, Direct Analysis of

Lithium in LIB Cathode Using Soft X-Ray Emission

Spectrometer, 2019 MRS Fall Meeting & Exhibit, 2019 年

12 月, Hynes Convention Center, Boston, USA.

＊Domestic


18


Kajihara Laboratory

■Member Koichi KAJIHARA Associate Professor /Ph.D. Inorganic Chemistry, Functional Material Chemistry, Inorganic Materials/Physical Properties room:9-336 TEL: +81-42-677-2827 e-mail: [email protected] Master’s course -4 Bachelor 4 -3

■Outlines of the Research 1. Studies on silica-based materials Koichi KAJIHARA Silica is a ubiquitous material and its utilization is in accordance with SDGs. Silsesquioxanes (SQs) are silica-based organic-inorganic hybrids with a general formula RSiO3/2. We have developed cosolvent-free synthesis method of SQ polymers, an environmental-friendy synthesis method of SQ polymers, and are trying to utilize them. This FY we focused on poly(phenylsilsesquoxane)-based glasses with low melting temperatures. The cosolvent-free method provided a facile way to form these glasses with low melting temperatures. The resultant glasses exhibited several unique properties, including strong adhesion to glass plates as a result of the presence of many SiOH groups, and high fragility corresponding to a rapid viscosity decrease above the glass transition temperature. The brittleness of poly(phenylsilsesquioxane)s, which is well known for this type of glasses, was found to be suppressed by copolymerization with SQ units of aliphatic functional groups. These glasses are attractive as glasses with low melting temperatures. In addition, the presence of CH/ bondings, which probably works as cohesive forces, were confirmed.

Fig. 1 Poly(phenylsilsesquioxane) glasses melted at various temperatures (top), poly(phenyl-co-ethylsilsesquioxane) glasses melted on a glass plate (bottom left), and two glass plates bonded with this type of glass (bottom right). 2. Studies on battery-related materials Koichi KAJIHARA Abstract Studies of oxide-based battery-related materials were conducted. This FY we performed theoretical studies on Mg2+-ion-conducting oxide MgZr4(PO4)6. In corroboration with Nagoya Institute of Technology. Our group has succeded the high-temperature direct-current conductivity measurement of this compound using Mg metal electrodes. Ab-initio DFT calculations indicated that real MgZr4(PO4)6 crystals have monoclinic crystal structure, whereas its hexagonal polymorph with higher symmetry should have lower activation barriers for Mg2+ ion conduction and thus should exhibit higher Mg2+ ion conductivity.

Fig. 2 Schematic illustration of crystal structures and Mg2+-ion conduction paths derived by ab-initio theoretical calculations for Mg2+-ion-conducting ceramics MgZr4(PO4)6.

■Papers with Peer Review 1. K. Nakano, Y. Noda, N. Tanibata, M. Nakayama, K. Kajihara,

K. Kanamura, Computational investigation of the Mg-ion conductivity and phase stability of MgZr4(PO4)6, RSC Adv. 9, 12590-12595 (2019)

2. R. Seto, K. Kanamura, S. Yoshida, K. Kajihara, Cosolvent-free synthesis and characterisation of poly(phenyl-co-n-alkylsilsesquioxane) and poly(phenyl-co-vinylsilses-quioxane) glasses with low melting temperatures, Dalton Trans. 49, 2487-2495 (2020).

■Reviews ＊Domestic

See the annual report in Japanese (1 article)

■Academic Meeting ＊International 1. M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K.

Kanamura, A solid-state lithium secondary battery using a chloroboracite-based glass-ceramic solid electrolyte, The 4th International Symposium on Hydrogen Energy-Based Society, Tokyo, Japan, 2019/8/22

2. L. Skuja, N. Ollier, K. Kajihara, K. Smits, Zero-phonon line and vibrionic structures in the green luminescence band in irradiated pure alpha-quartz, The 20th International conference on Radiation Effects in Insulators (REI-20), Astana, Kazakhstan, 2019/8/22

3. K. Kajihara, M. Suda, R. Nakagawa, K. Kajihara, Highly-transparent efficient sol–gel-derived silica–(Gd,Pr)PO4 glass-ceramic narrow-band UVB phosphors, The 8th International Workshop on Photoluminescence in Rare Earths: Photonic Materials and Devices (PRE19), Nice, France, 2019/9/6

4. L. Skuja, N. Ollier, K. Kajihara, Luminescence of non-bridging hole centers as a marker of particle irradiation of -quartz, The 19th International Conference on Solid State Dosimetry (SSD19), Hiroshima, Japan, 2019/9/17

5. R. Iwasaki, K. Kajihara, Photoluminescence of sol−gel-derived transparent silica−(Tb,Ce)PO4 glass-ceramics, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/28

6. R. Nakagawa, K. Kajihara, Photoluminescence of sol−gel- derived transparent silica−(Gd,Pr)PO4 glass-ceramics under excitation with a KrCl excimer lamp, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/28

7. R. Seto, K. Kajihara, K. Kanamura, Cosolvent-free synthesis and characterization of poly(Ph-co-R-SQ) (R = Me, Et, Pr, and Vi) glasses with low melting temperatures, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29

19


8. M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K. Kanamura, Fabrication of a solid-state lithium secondary battery using a lithium-ion-conducting Li4B4Al3O12Cl-based glass-ceramic, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29

9. K. Nakano, Y. Noda, N. Tanibata, M. Nakayama, K. Kajihara, K. Kanamura, Evaluation of the Mg-ion conductivity and phase stability of Mg-ion conductor MgZr4(PO4)6 by DFT method, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29

10. K. Kajihara, R. Seto, K. Kanamura, Y. Onodera, S. Kohara, Microscopic ordering in amorphous poly(n- alkylsilsesquioxane) liquids and solids synthesized by a cosolvent-free hydrolytic polycondensation via aging, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/30

＊Domestic See the annual report in Japanese (5 articles)

■Patents ＊Domestic See the annual report in Japanese (1 article)

■Awards 1. M. Saito, Best Poster Award in Symposium 20: Ceramics for

Rechargeable Energy Storage at the 13th Pacific Rim Conference of Ceramic Societies (PACRIM13) M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K. Kanamura, Fabrication of a solid-state lithium secondary battery using a lithium-ion-conducting Li4B4Al3O12Cl-based glass-ceramic

2. K. Kajihara, 2019 Leading Professor in Faculty of Urban Environmental Sciences, Tokyo Metropolitan University

20


Takagi Laboratory

■Members Shinsuke TAKAGI Professor /Ph.D Photochemistry, Photo-functional Materials Chemistry, Porphyrin Chemistry, Clay Science Room: 9－446 TEL: +81-42-677-2839 e-mail: [email protected] Tamao ISHIDA Associate Professor/Ph. D. Catalysis Chemsitry Room: 9-447 TEL：+8142-677-2845 e-mail: [email protected] Tetsuya SHIMADA Assistant Prof. / Ph.D. Physical Chemistry, Spectroscopy Room: 9-445 TEL: +81-42-677-1111 (Ext.4897) e-mail: [email protected] Visiting researcher 4 Doctor’s course 4 Master’s course 11 Bachelor 8

■Outlines of the Research Our group challenges to control photochemical reactions such as electron and energy transfer, by controlling the orientation and alignment of dyes on the inorganic surfaces. Recently, organic/inorganic hybrids composed of porphyrins and layered materials have been the subject of intensive investigations to explore their novel properties and functionalities. We found out that a precise matching of distances between the negatively charged sites on the clay mineral layers and that between the positively charged sites in the dye molecule is one of the most important factors to determine the structure of the clay–dye complex. We have termed this the “Size-Matching Rule” Our goal is finding out a new methodology to control molecular assembly structure and realizing functionalized photochemical reaction systems such as an artificial light harvesting system. 1. Research on Artificial light harvesting system Shinsuke TAKAGI, Tetsuya SHIMADA The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the “Size- Matching Rule” that is our original technique. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system. Especially when phthalocyanine was used as energy acceptor, light harvesting type energy transfer was realized. In addition to these, hydrogen evlution systems using sunlight as an energy source has been developed. Especially, photochemical hydrogen and hydroperoxide formation were examined as an energy related subject this year.

Fig. 1. Artificial light harvesting model on the nanosheet. 2. Research on Novel Methodology to Control the Adsorption Structure of Dyes on the Clay Surface Shinsuke TAKAGI, Tetsuya SHIMADA Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, 27Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported “size-matching rule”. This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes. In this year, the glass substrate was examined as a novel host material to control the nano-structure of dye assembly.

Fig. 2. An example of our methodology to control the adsorption structure of dyes on the clay surface by using a suitable clay species.

Fig. 3. Adsorption of protein on nanosheets and formation of apoprotein.. 3. Surface – Fixation Induced Emission on the nanosheets Shinsuke TAKAGI, Tetsuya SHIMADA We investigated the fluorescence enhancement behavior of AIE (Aggregation Induced Emission) – active dyes on the clay nanosheet. Judging from their adsorption observation on the clay in water, the factor for the fluorescence enhancement is turned

21


out not to be AIE, but is to be Surface - Fixation Induced Emission (S - FIE) mechanism. While the effect of AIE depended on the molecular structure of dye in water-dioxane, S - FIE worked even for the dye that has bulky substituent. In this year, not only fluorescence but also phosphorescence was examined as a photochemical behavior. As a result, the enhancement of phosphorescence on clay surface was found put.

Fig. 4. Surface – Induced Emission on the nanosheets. Left: without nanosheet, Right: with nanosheet.. 4. Research on Novel Hybrid Complex of Semiconductor Nano-Sheet and Dye Shinsuke TAKAGI, Tetsuya SHIMADA A semiconductor nano-sheet was focused as our new research target in addition to the "insulator" clay nano-sheet. We expected we effectively extend our distinctive research about clay-dye hybridization methodology in order to create new materials with good electron transfer property for artificial photosynthesis system. We synthesized a novel TiO2 nano-sheet (TNS) and characterized it in detail. We observed adsorption behavior of porphyrin dyes on the TNS and photochemical interaction between the dyes and the TNS.

Fig. 5. Electron injection from Dye to semiconductor nanosheet. 5. Research on Gold Nanoparticle-Catalyzed Organic Reactions Tamao, ISHIDA Nanosheet materals, such as titania nanosheet (TNS) and clay (Sumecton SA, SSA), are regarded as potential supports for metal nanoparticles because of high surface area and ordered anioninc charges on the surfaces. In this year gold nanoparticles (Au NPs) were deposited on TNS and SSA by deposition-reduction method using Au(en)2Cl3 as a precursor. Catalytic activities of Au/TNS and Au/SSA were evaluated by aerobic oxidation of 4-hydroxybenzyl alcohol. Yields of 4-hydroxybenzaldehyde were calculated to be 24 and 60% for Au/TNS and Au/SSA, respectively. Although larger Au NPs were deposited on SSA, Au/SSA showed higher catalytic activity than did Au/TNS. Mean diameters of Au NPs on TNS and SSA were estimated to be 1.7 and 6.7 nm, respectively, by transmission electron microscopy. These findings will contribute to devlop new Au catalysts using nanosheet materials. Hydroxyapatite (HAP) supported Au catalysts have been known to show inverse strong metal-support interaction (SMSI)

in which Au NPs are covered by HAP under oxidative conditions, reported by J. Wang et al. Au atoms at the perimeter interface became cationic under inverse SMSI. Therefore, Au/HAPs seem to be a promising candidate as soft Lewis acid catalysts for alkene activation. Au/HAPs were prepared under oxidative and reductive conditions and were abbreviated as Au/HAP_O2 and Au/HAP_H2, respectively. Although the mean diameters of Au NPs were almost similar (ca. 2 nm), Au/HAP_O2 exhibited higher catalytic activity for alkene isomerization reation than did Au/HAP_H2. This result suggests that the electronic interaction between Au and HAP thin layer of Au/HAP_O2 with SMSI enhaces the soft Lewis acidity, resulting in high catalytic activity.

■Papers with Peer Review 1. Which Type of Clay Minerals Fix Cesium Ion Effectively?

-Cavity-Charge Matching Effect-, T. Yamamoto, T. Takigawa, T. Fujimura, T. Shimada, T. Ishida, H. Inoue, S. Takagi, Phys. Chem. Chem. Phys., 21, 9352-9356 (2019).

2. Reversed Micelles Formed by Polyfluorinated Surfactant II; the Properties of Core Water Phase in Reversed Micelle, S. Takagi, K. Arakawa, T. Shimada, H. Inoue, Bull. Chem. Soc. Jpn., 92, 1200-1204 (2019).

3. Factors for the emission enhancement of dimidium in specific media such as in DNA and on a clay surface, R. Nakazato, K. Sano, H. Ichihara, T. Ishida, T. Shimada, S. Takagi, Phys. Chem. Chem. Phys., 21, 22732-22739 (2019). Selected as “Cover paper”

4. Effect of clay surface on aldehyde-diol equilibrium, K. Arakawa, R. Nakazato, T. Shimada, T. Ishida, M. Eguchi, S. Takagi, Tetrahedron Lett., 60, 150986-150989 (2019).

5. Pd-catalyzed decarbonylation of furfural: Elucidation of support effect on Pd size and catalytic activity using in-situ XAFS, T. Ishida, T. Honma, K. Nakada, H. Murayama, T. Mamba, K. Kume, Y. Izawa, M. Utsunomiya, M. Tokunaga, J. Catal., 374, 320–327 (2019).

6. CO Oxidation over Au/ZnO: Unprecedented Change of the Reaction Mechanism at Low Temperature Caused by a Different O2 Activation Process, T. Fujita, T. Ishida, K. Shibamoto, T. Honma, H. Ohashi, T. Murayama, M. Haruta, ACS Catal., 9, 8364–8372 (2019).

7. Oxidative esterification of aliphatic aldehydes and alcohols with ethanol over gold nanoparticle catalysts in batch and continuous flow reactors, A. Taketoshi, T. Ishida, T. Murayama, T. Honma, M. Haruta, Appl. Catal. A: Gen., 585, 117169 (2019).

8. Imporatance of Size and Contact Structure of Gold Nanoparticles for the Genesis of Unique Catalytic Processes, T. Ishida, T. Murayama, A. Taketoshi, M. Haruta, Chem. Rev., 120, 464–525 (2020). “Inside cover“

9. CO2 Reduction to Methanol on Au/CeO2 Catalysts: Mechanistic Insights from De-Activation and SSITKA Measurements, A. Rezvani, A. M. Abdel-Mageed, T. Ishida, T. Murayama, M. Parlinska-Wojtan, R. J. Behm, ACS Catal., in press.

■Review articles and books 1. Gold Nanoparticles for Oxidation Reactions: Critical Role

of Supports and Au Particle Size, T. Ishida, A. Taketoshi, M. Haruta, Topics in Organometallic Chemistry, “Nanoparticles in Catalysis”, Springer, S. Kobayashi, Ed., in press (2020).

22


2. Tuning emission properties by dye encapsulation into layered silicates, Y. Ishida, S. Takagi, Springer, “Dyes and Photoactive Molecules in Microporous Systems”, (Virginia Martínez-Martínez, Ed.), in press. See the annual report in Japanese (6 articles)

■Academic Meeting ＊International 1. Anti-inflammatory effect of metal oxide supported Au

catalysts, T. Ishida, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019 (Invited).

2. Evaluation of organic-inorganic complexes for hydrogen evolution on clay nanosheets, S. Nagaoka, Y. Ohsaki, M. Kumasaka, T. Shimada, T. Ishida, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.

3. Novel oxidation reaction sensitized by Sn(IV)Porphyrin aiming at artificial photosynthesis, Y. Ohsaki, H. Tachibana, H. Inoue, T. Shimada, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.

4. Photochemical properties of water-soluble porphyrin on titania nanosheets aiming at artificial photosynthesis, J. Hara, T. Shimada, T. Ishihda, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.

5. Adsorption behavior and photochemical property of divalent cationic porphyrin on titania nanosheet, S. Tominaga, K. Sano, T. Shimada, T. Ishida, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.

6. Selective Catalytic Oxidation of NH3 with High N2 Selectivity over Au/Nb2O5, M. Lin, B. An, N. Niimi, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, The 4th International Symposium on Hydrogen Energy‒ based Society, Tokyo (Japan), August, 2019.

7. Effect of the deposition of gold to Nb2O5 for photocatalytic oxidation of 5-hydroxymethylfurfural, C. Mochizuki, T. Shishido, T. Ishida, H. Masatake, T. Murayama, The 4th International Symposium on Hydrogen Energy‒ based Society, Tokyo (Japan), August, 2019.

8. Effects of the size of nanoparticulate gold and their support on selective oxidation of furfural to furoic acid, C. Mochizuki, M. Lin, A. Taketoshi, T. Ishida, M. Haruta, T. Murayama, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.

9. Selective catalytic oxidation of ammonia using nanoparticulate noble metal deposited on Nb2O5, B. An, M. Lin, N. Niimi, Y. Jikihara, T. Nakayama, T. Ishida, M. Haruta, T. Murayama, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.

10. Mutual Redox Conversion of NAD+ and NADH by Gold Catalysts, J.-i. Nishigaki, T. Ishida, M. Haruta, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.

11. Efficient removal of ammonia by using niobium oxide supported gold catalyst with high nitrogen selectivity, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, The 8th

Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.

12. Selective Catalytic Oxidation of NH3 by using Au/Nb2O5, The 10th National Conference on Environmental Chemistry, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, The 10th National Conference on Environmental Chemistry, Tianjin (China), August, 2019.

13. Effect of the deposition of gold nanoparticle on Nb2O5 for photocatalytic selective oxidation of 5-hydroxymethylfurfural, C. Mochizuki, T. Shishido, T. Ishida, H. Masatake, T. Murayama, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019.

14. High catalytic activity for CO oxidation below room temperature over Au/Ta2O5, M. Lin, C. Mochizuki, B. An, Y. Inomata, T. Ishida, M. Haruta, T. Murayama, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019.

15. Role of acid sites in selective catalytic oxidation of NH3 with high N2 selectivity, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, 9th East Asia Joint Symposium on Environmental Catalysis and Eco-materials, Yancheng (China), November, 2019.

16. Synthesis and Identification of Titanium Oxide Nanoparticle for Molecular Catalyst Sensitized Artificial Photosynthesis Systems, K. Sano, F. Kuttassery, A. Yamakata, B. Ohtani, T. Shimada, H. Tachibana, T. Ishida, S. Takagi, H. Inoue, The 3rd International Conference on Solar Fuels (ISF-3)and International Conference on Artificial Photosynthesis2019 (ICARP2019), Hiroshima (Japan), November, 2019.

17. Emission enhancement of dyes on the inorganic nanosheets, S. Takagi, K. Arakawa, Y. Ishida, T. Ishida, T. Shimada, The 18th Asian Chemical Congress (18th ACC) and The 20th General Assembly of the Federation of Asian Chemical Societies (FACS), Taipei (Taiwan), December, 2019.

18. The Flat Effect of Clay Surface on the Aldehyde-diol Equilibrium, K. Arakawa, T. Ishida, T. Shimada, S. Takagi, The 18th Asian Chemical Congress (18th ACC) and The 20th General Assembly of the Federation of Asian Chemical Societies (FACS), Taipei (Taiwan), December, 2019.

＊Domestic See the annual report in Japanese (28 articles)

■Patents See the annual report in Japanese (1 articles)

■Awards 1. The Best Presentation Award for Students, Annual

Meeting on Photochemistry 2019, Yugo HIRADE (M1), September, 2019.

2. Excellent Poster Awards, The 9th CSJ Chemistry Festa, Keito SANO (D1), October, 2019.

3. Sustainable Energy and Fuels (SEF) Award, The 3rd International Conference on Solar Fuels and International Conference on Artificial Photosynthesis2019, Keito SANO (D1), November, 2019.

4. Poster Presentation Awards for Students, The 3rd International Conference on Solar Fuels and International

23


Conference on Artificial Photosynthesis2019, Keito SANO (D1), November, 2019.

24


Uchiyama Laboratory

■Members

Katsumi UCHIYAMA

Professor / Dr. Pharmacol.

Analytical Chemistry, Nano/Micro Chemical Fabrication,

Micro Droplet

room: 9-339 TEL: +81-42-677-1111 Ext.4877


Hizuru NAKAJIMA

Associate Prof. / Dr.Eng.

Analytical Chemistry, Micro-TAS, Chromatography,

Electrophoresis, Chemical sensor, Bio sensor

room: 9-343 TEL: +81-42-677-1111 Ext.4882

e-mail: nakajima-hizuru @tmu.ac.jp

Shungo KATO

Associate Prof. / Dr.Eng.

Atmospheric Chemistry, Analytical Chemistry, Geochemistry

room: 9-338 TEL: +81-42-677-1111 Ext.4875

e-mail: shungo @tmu.ac.jp

Sifeng MAO

Assistant Prof. / Dr.Eng

Analytical Chemistry, Micro-TAS

room: 9-344 TEL: +81-42-677-1111 Ext.4883

e-mail: maosifeng @tmu.ac.jp

Hidetaka NORITOMI

Assistant Prof. / Dr.Eng.

Enzyme Technology, Nanomaterial，Bioprocess

room: 9-148 TEL: +81-42-677-1111 Ext.4838

e-mail: noritomi @tmu.ac.jp

Sueo KAGAWA

Tech. Assistant

room: 9-290 TEL: +81-42-677-1111 Ext.4872

e-mail: kagawa @tmu.ac.jp

Haruko MIYAMOTO

Tech. Assistant

room: 9-291 TEL: +81-42-677-1111 Ext.4873

e-mail: miyamoto-haruko @jmj.tmu.ac.jp



Bachelor 4 -8

Dissertion Ph.D. supporting by JSPS-1(Tsinghua University)


1. Development of Small Droplets and Applications

Katsumi UCHIYAMA, Sifeng MAO

Monodispersive micro liquid droplets not only act as ultra

small reaction place with unique characteristics but also enhance

fluorescence intensity of surrounding media. We utilized inkjet,

which is widely used for the inkjet printer, micro dispensing tool

for analytical chemistry and many other fields, as a generation

tool for monodispersive liquid dorplets. In this study we have

developed on-line digital PCR system, new sample introduction

method for capillary electrophoresis, dispensing system for ultra

small amount of liquid for enzyme linked immune sorbent assay,

generation of mono-dispersive polymer particles for drug

delivery system.

1-1 Development of on-line digital PCR system

At first, a certain number of mono-dispersive droplets with

PCR mixture and target DNA were ejected into oil phase.

Concentration of the target DNA was adjusted by diluting until

each droplet has one or zero target DNA. Droplets ejected were

introduced into capillary (id200- 500 μm), then were flown to

the downstream. The capillary was wrapped 30~40 times around

three heating blocks, each of which has same temperatue as PCR

amplification. As a result, PCR amplification was carried out

during the flow through the capillary. Finally, determination was

made by counting fluorescent droplets. We have realized new

on-line digitial PCR system for the first time.

1-2 Droplet enhanced fluorescence, principle and application

We found the the droplet with later refractive index than

surrounding media showed drastic increase of fluorescence

intensity and we named the phenomena DEF (droplet enhanced

fluorescence). The phenomena is based upon the multiple

reflection of incident light at the interface between the droplet

and surrounding media.

We have confirmed the phenomenon by using droplets

ejectedfrom inkjet, then applied the method to ultra sensitive

determination of single strand DNA, ELISA. The method

showed 5~10 times increase in the sensitivity than conventional

methods.

1-3 Application to Capillary electrophoresis

We have developed a new quantitative sample introduction

method for capillary electrophoresis. Inkjet was used for it. And

new method of sample deribatization was developed by using

inkjet. Sample solution and reagent solution was alternately

introduced into the capillary, then these zones were overlapped

for reaction. Finally, delivatized sample was quantitatively

detected.

25


2. Development of nano/micro chemical pen and its

applications


We have developed micro chemical pen, which enabled

position selective micro chemical fabrication on the suface of

material. The chemical pen enabled the fabrication of silver

nano-wires, metal oxide nano-wires and polymer nano wires.

The device will be used for the assembling tool for chemical

machine, fabrication of chemical device and functionalization of

micro machine etcs in the future.

3. Single cell operation


One single tumor cell in large tissue was difficult to be

detected when whole tissue was analysed. However, the tumor

would spred to whole tissue in the end. If we can characterize

cell in single cell level, tumor cell will be easily detected and it

leads to the ultra fast diagnosis of tumor and precise study on the

mechanism of metastasis. In this study, we develop tools for the

characterization of single cell, extraction of single cell fluid,

measurement of chemicals exposed from a cell by using the

principle of chemical pen.

4. Development of Micro Total Analysis System Using a

Compact Disk-type Microfluidic Device

Hizuru NAKAJIMA

We have developed a flow-based ELISA system using a

microfluidic device. However, many pumps and valves are

required for multiple immunoassays, which affect total size of

the analytical system. In this study, we developed a solution

sending method based on the centrifugal force generated by

rotating a compact disk-type microfluidic device. A portable

fluorescence detection system, electrochemical detection system

and surface plasmon resonance sensor using the compact disk-

type microfluidic device were developed. Since these systems do

not need pumps and valves, these systems would be useful for

on-site analysis, such as environmental monitoring, food safety

testing and point-of-care testing.

5. Development of Portable ELISA System Using Pipette

Tips

Hizuru NAKAJIMA

Enzyme-linked immunosorbent assay (ELISA) is an

immunological assay commonly used to measure antibodies,

antigens, proteins and glycoproteins in biological samples.

However, the conventional ELISA method relatively needs a

long analysis time and many expensive reagents. In addition,

commercially available microplate readers are large-size and

very expensive. Therefore, it is not possible to measure

biological samples and environmental samples in the field by

ELISA. To overcome these drawbacks, we developed an ELISA

method using pipette tips (PT-ELISA) and the palm-sized

fluorescence detector for PT-ELISA. This PT-ELISA system was

successfully used in the determination of IgA in human saliva, a

marker of stress.

6. Development of Portable Genetic Testing System Based on

LAMP

Hizuru NAKAJIMA

A genetic amplification method using polymerase chain

reaction (PCR) is commonly used in the genetic test. However,

the PCR method is not suitable for on-site genetic test since the

method needs large-sized and expensive assay devices such as a

thermal cycler, an electrophoresis equipment and an absorption

/ fluorescence detector. To overcome these drawbacks, a portable

genetic testing system based on LAMP was developed using

LEDs, photodiodes a transparent glass heater and so on. The

genetic testing system was successfully used in the variety

identification of rice.

7. Development of Multichannel ISFET Sensor for

Measuring pH Distribution of Interstitial Water in

Marine Sediment

Hizuru NAKAJIMA

Recentry, marine acidification is progressing with increasing

the concentration of CO2 in atmosphere. Since the marine

acidification causes the dissolution of sandy soil in coral reef

area, the effect of ocean acidification on marine organisms living

in there is apprehended. Therefore, the measurement of pH

distribution of interstitial water in marine sediment is important

task for evaluating the effect of marine acidification on

ecosystem. In general, the pH value of interstitial water in marine

sediment is measured by diver using the pH meter with glass

electrode. However, the measurement work is very hard, the

glass electrode is fragile, and the pH distribution of interstitial

water could not be measured at same time. To overcome these

drawbacks, a novel multichannel ISFET sensor using Ta2O5 as

an ion sensitive membrane was developed for measureing the pH

distribution of interstitial water in marine sediment.

26


8. Measurements of VOCs at urban and suburban sites

Shungo KATO

Volatile Organic Compounds (VOCs) were observed at

uburban site (Minamiosawa, Koto-ku, Yokohama). Emission

sources, contribution to ozone formation of each VOC were

estimated.

9. Atmospheric trace species measurements at remote sites

Shungo KATO

Atmospheric carbon monoxide, ozone, and various volatile

organic compounds were continuously observed at remote

sites: cape Hedo in Okinawa, Suzu in Ishikawa.

10. Measurements of atmospheric pollutants at mountain

sites

Shungo KATO

Carbon monoxide, ozone, and sulferdioxide were observed at

summit of Mt. Fuji during summer. There was no influence from

local pollution source and typical air at remote site during

summer was observed. Plume from volcano was observed at Mt.

Fuji. Realtime measurement of gas at the top of Mt. Fuji during

winter without commercial electric power was donducted with

low power gase sensor and LPWA ELTRES (SONY).

11. Atmospheric trace gas measurements using small gas

sensor

Shungo KATO

Atmospheric trace gases and PM2.5 were measeured by

small gas sensors at urban area and clean remote site at the top

of Mt. Fuji. Also, portable system working by battely was

constructed.

12. Hydrogen measurement in ambient aire

Shungo KATO

Gas chromatgrapy/Redection gas detector system was

constructed for low level hydrogen measuremtns. Atmospheric

hydrogen concentration in suburban, urban, and remote sites

were observed.

13. Application of biochar to stress tolerance of proteins

Hidetaka NORITOMI

To reduce greenhouse gas emissions, biochar was prepared

from forestry residues, which are carbon neutral, and was used

as a protein carrier. We found that biochar imparts high heat

stress tolerance and organic solvent stress tolerance to proteins.

This result would be expected to the applications to

bioprocesses such as bioreactors, biosensors, and biofuel cells.


1. Syed Niaz Ali Shah, Xiangnan Dou, Mashooq Khan,

Katsumi Uchiyama, Jin-Ming Lin

N-doped carbon dots/H2O2 chemiluminescence system for

selective detection of Fe2+ ion in environmental samples

Talanta, 196, 370–375, (2019)

2. Tsuguhiro Kaneko, Yue Sun, Hizuru Nakajima, Katsumi

Uchiyama, Hulie Zeng

Droplet Sensitized Fluorescence Detection for Enzyme-

Linked Immune Sorbent Assays on Microwell Plate

Anal. Chem. 91(9), 5685-5689, (2019)

3. Haifeng Lin, Sifeng Mao, Hulie Zeng, Yong Zhang, Masato

Kawaguchi, Yumi Tanaka, Jin-Ming Lin, Katsumi Uchiyama

Selective Fabrication of Nanowires with High Aspect Ratios

Using a Diffusion Mixing Reaction System for Applications

in Temperature Sensing

Anal. Chem. 91(11), 7346-7352, (2019)

4. Hidetaka Noritomi, Ryotaro Kai, Nobuyuki Endo, Satoru

Kato, Katsumi Uchiyama

Thermal Stabilization of HEWL by Adsorption on Biochar

Journal of Materials Science Research, 8(4), 30-36, (2019)

5. A. Yamakawa, A. Takami, Y. Takeda, S. Kato, and Y. Kajii,

Investigation of Mercury Emission Sources Using Hg

Isotopic Compositions of Atmospheric Mercury at the Cape

Hedo Atmosphere and Aerosol Monitoring Station

(CHAAMS), Japan,

Environmental Science: Processes & Impacts, 21, 809-818,

(2019)

6. R. Wada, Y. Sadanaga, S. Kato, N. Katsumi, H. Okochi, Y.

Iwamoto, K. Miura, H. Kobayashi, M. Kamogawa, J.

Matsumoto, S. Yonemura, Y. Matsumi, M. Kajino, S.

Hatakeyama,

Ground-based observation of lightning-induced nitrogen

oxides at a mountaintop in free troposphere,

Journal of Atmospheric Chemistry, 76(2), 133-150, (2019)

7. Kohji Marumoto, Noriyuki Suzuki, Yasuyuki Shibata, Akinori

Takeuchi, Akinori Takami, Norio Fukuzaki, Kazuaki

Kawamoto, Akira Mizohata, Shungo Kato, Takashi

Yamamoto, Jingyang Chen, Tatsuya Hattori, Hiromitsu

Nagasaka, Mitsugu Saito,

Long-term observation of atmospheric speciated mercury

during 2007-2018 at Cape Hedo, Okinawa, Japan,

Atmosphere, 10, 362, (2019)

8. Momoka Yoshizue, Yoko Iwamoto, Kouji Adachi, Shungo

Kato, Siyi Sun, Kazuhiko Miura, Mitsuo Uematsu,

Individual particle analysis of marine aerosols collected

during the North-South transect cruise in the Pacific Ocean

and its marginal seas,

Journal of Oceanography, 75, 513-524, (2019)

9. Kojiro Shimda, Masayuki Nohchi, Taichi Sugiyama, Kaori

Miura, Akinori Takami, Kei Sato, Xuan Chen, Shungo Kato,

Yoshizumi Kajii, Fan Meng, Shiro Hatakeyama,

Degradation of PAHs during long range transport based on

simultaneous measurements at Tuoji Island, China, and at

Fukue Island and Cape Hedo, Japan,

Environmental Pollution, 260, 113906, (2020)


■Invited Lectures

1. Katsumi Uchiyama

Possible application of push-pull nozzle system for single

cell analyses and manipulation

The Second Symposium for Cell Analysis on

Micro/Nanofluidics, Xijiao Hotel Beijing, Beijing, China

2. Katsumi Uchiyama

Selective Fabrication of Nanowires with High Aspect Ratios

27


Using a Diffusion Mixing Reaction System for Applications

in Temperature Sensing

2019 China-Japan-Korea Symposium on Analytical Science

（ 2019CJK ） , Kyung Hee University (Global Campus)

Yongin, Korea

3. Katsumi Uchiyama

Analytical chemistry in Japan

the 18th Beijing Conference and Exhibition on Instrumental

Analysis (BCEIA 2019), China National Convention Center,

Beijing, China

4. Katsumi Uchiyama

Push-pull nozzle system for the biochemical study



Beijing, China

5. Katsumi Uchiyama

Droplet enhanced fluorescence and itsa application to bio-

analysis



Beijing, China

■Academic Meeting

＊International

1. Hidetaka Noritomi, Ryotaro Kai, Nobuyuki Endo, Satoru

Kato, Katsumi Uchiyama

Thermal Stabilization of Enzymes by Adsorption on Biochar

OKINAWA COLLOIDS 2019(the 70th Anniversary of the

Divisional Meeting of Division of Colloid and Surface

Chemistry), Bankoku Shinryoukan, OKINAWA

＊Domestic

See the annual report in Japanese (16articles)

■Books

1. Hidetaka Noritomi

Application of biochar to enzyme carrier for stress tolerance

of enzymes, Biochar-An Imperative Amendment for Soil and

the Environment (ISBN: 978-1-83881-987-3), Ed by Vikas

Abrol, InTech, London, United Kingdom, Chapter 5, pp.75-

95 (2019)

See the annual report in Japanese (1 book)

■Awards

28


Shishido Laboratory

■Members

Tetsuya Shishido

Professor /Dr. Eng.

Catalyst Science, Surface chemistry, Solid acid-base, Selective

oxidation, in-situ observation

room:9-551 TEL: +81-42-677-2852 (Ext. 4961)


Hiroki Miura

Assistant Professor /Dr. Eng.

Catalysis Science, Solid acid-base, Organic chemistry,

Organometallic chemistry

room:9-550 TEL: +81-42-677-2851 (Ext. 4962)




Bachelor 4 -7


1. One-pod synthesis of lactic acid from glycerol by hydrid

catalysis of solid acid-Pt nanoparticles

Lactic acid is an important compound used as various chemicals

such as foods and pharmaceuticals. Due to excess formation of

glycerol as a by-product during biodiesel production, the method

for selective conversion of glycerol to lactic acid is strongly

desired. In this study, we investigated one-step synthesis of lactic

acid from glycerol and found that Pt catalyst supported on Nb2O5

was remarkably effective. This reaction is consisted of two kinds

of reactions, ie, oxidative of glycerol to trioses and subsequent

isomerization to lactic acid. In this catalytic reaction, the

Pt/Nb2O5 functioned as "hybrid catalysts" in which Pt

nanoparticles and Nb2O5 promoted the oxidation and

isomerization, respectively.

2. Silylation of aryl chlorides by bimetallic catalysis of

palladium and gold on alloy nanoparticles

Supported palladium–gold alloy-catalyzed cross-coupling of

aryl chlorides and hydrosilanes enabled the selective formation

of aryl–silicon bonds. Whereas a monometallic palladium

catalyst predominantly promoted the hydrodechlorination of aryl

chlorides and gold nanoparticles showed no catalytic activity,

gold-rich palladium–gold alloy nanoparticles efficiently

catalyzed the title reaction to give arylsilanes with high

selectivity. A wide array of aryl chlorides and hydrosilanes

participated in the heterogeneously-catalyzed reaction to furnish

the corresponding arylsilanes. A detailed mechanistic

investigation revealed that palladium and gold atoms on the

surface of alloy nanoparticles independently functioned as active

sites for the formation of aryl nucleophiles and silyl electrophiles,

respectively, which indicates that palladium and gold atoms on

alloy nanoparticles work together to enable the selective

formation of aryl–silicon bonds.

3. Brønsted acid property of alumina-based mixed-oxides-

supported tungsten oxide

The effect of alumina-based supports on the structure and acid

properties of supported tungsten oxide catalysts was investigated.

WO3/Al2O3–TiO2 (Al2O3/TiO2 = 9, Al–Ti9) showed high activity

for reactions catalyzed by Brønsted acid sites and large Brønsted

acidity. Structural characterization revealed that Brønsted acid

sites on WO3/Al–Ti9 were generated at the boundaries between

domains of amorphous monolayer WO3 and Al2O3–TiO2 support,

and that Al–Ti9 with a high density of Lewis acid and surface

hydroxyl groups resulted in the formation of Brønsted acid sites.

These results suggested that a high density of Lewis acid sites

and surface hydroxyl groups are important factors to form

amorphous WO3 monolayer domains and to generate Brønsted

acid sites on alumina-based supports.


1. “Silylation of Aryl Chlorides by Bimetallic Catalysis of

Palladium and Gold on Alloy Nanoparticles” Miura, H.;

Masaki, Y.; Fukuta, Y.; Shishido, T. Adv. Synth. Catal.

2020, in press.【Selected as a Very Important Publication】 2. “Acid Property of Alumina-Based Mixed Oxides

Supported Tungsten Oxide” Saito, M.; Aihara, T.; Miura,

H.; Shishido, T. Catal. Today 2020, in press.

3. “Importance of the Pd and Surrounding Sites in

Hydrosilylation of Internal Alkynes by Palladium-Gold

Alloy Catalyst” Sadhukhan, T.; Junkaew, A.; Zhao, P.;

Miura, H.; Shishido, T.; Ehara, M. Organometallics 2020,

39, 528–537.【Featured as a Supplementary Cover】

4. “Investigation of the mechanism of the selective

hydrogenolysis of C-O bonds over a Pt/WO3/Al2O3

catalyst” Aihara, T.; Miura, H.; Shishido, T. Catal. Today

2020, in press.

5. “One-pot synthesis of lactic acid from glycerol over Pt/L-

29


Nb2O5 catalyst under base-free conditions” Shixiang, F.;

Takahashi, K.; Miura, H.; Shishido, T. Fuel Process.

Technol. 2020, 197, 106202

6. “Reductive Cycloisomerization of Diynes by Supported

Palladium Catalysts and Subsequent [4+2] Cycloaddition

Leading to Cyclohexene Derivatives” Miura, H.; Tanaka

Y.; Nakahara, K.; Shishido, T. ChemCatChem 2019, 12,

455–458.

7. “Effect of Perimeter Interface Length between 2D WO3

Monolayer Domain and γ-Al2O3 on Selective

Hydrogenolysis of Glycerol to 1,3-Propanediol” Aihara,

T.; Miura, H.; Shishido, T. Catal. Sci. Technol. 2019, 9,

5359–5367.

8. “Supported Gold-Palladium Alloy Catalysts for Highly

Efficient Hydrogen Storage System based on Ammonium

Bicarbonate/Formate Redox Equilibrium” Nakajima, K.;

Tominaga, M.; Waseda, M.; Miura, H.; Shishido, T. ACS

Sustainable Chem. Eng. 2019, 7, 6522–6530.

9. “The importance of direct reduction in synthesizing highly

active Pt-Sn/SBA-15 for n-butane dehydrogenation” Deng,

L.; Miura, H.; Ohkubo, T.; Shishido, T.; Zheng, W.;

Hosokawa, S.; Teramura, K.; Tanaka, T. Catal. Sci.

Technol. 2019, 9, 947–956. 【Featured as a Front Cover】 10. “Catalysis of Cu Cluster for NO Reduction by CO:

Theoretical Insight into Reaction Mechanism and

Experimental Evidence” Takagi, N.; Ishimura, K.; Miura,

H.; Shishido, T.; Fukuda, R.; Ehara, M.; Sakaki, S.ACS

Omega 2019, 4, 2596–2609.

11. “Role of the Acid Site for Selective Catalytic Oxidation of

NH3 over Au/Nb2O5” Lin, M.; An, Baoxiang; Niimi, N.;

Jikihara, Y.; Nakayama, T.; Honma, T; Takei, T.; Shishido,

T.; Ishida, T.; Haruta, M.; Murayama, T., ACS Catal., 2019,

9, 1753-1756.

■Invited Lectures

1. 124th CatSJ Meeting “Design of Brensted acid sites with

high hydrophobicity and their catalysis toward hydrolysis

of organic molecules” 2019/9/19 Nagasaki University

2. Design of High-Performance Alloy catalysts: Enhancing

Activity and Switching Selectivity by the Incorporation of

Palladium into Gold Nanoparticles,

T. Shishido, (Jan. 4th (Fri)), National Taiwan University,

Taipei, Taiwan.

3. Supported Palladium-Gold Alloy Catalysts for Highly

Efficient Hydrogen Storage System, (Invited Lecture), T.

Shishido, PACCON2020 (Pure and Applied Chemistry

International Conference 2020) (13-14th February 2020),

Bangkok

4. 141th Meeting of the surface finishing society of japan

“Highly efficient hydrogen evolution-storage by PdAu

alloy nanoparticle catalysts” T. Shishido 2020/3/3, Tokyo

Metropolitan University.

5. 100th annual meeting of CSJ “Hydrogen production by

supported alloy nanoparticle catalysts” T. Shishido,

2020/3/22-26, Tokyo University of Science.

■Academic Meeting

＊International

1. Selective Catalytic Reduction of NO over Delafossite-type

Oxide

Shengyan Piao, Shinsuke Imai, Hiroki Miura, Tetsuya

Shishido，The 17th Korea-Japan Symposium on Catalysis，

May 20-22, 2019, Jeju, Korea

2. Silylation of aryl chlorides by supported Pd-Au alloy

catalysts

Y. Masaki, H. Miura, T. Shishido, The 1st International

Symposium on Hybrid Catalysis for Enabling Molecular

Synthesis on Demand, May 30-31, 2019, Tokyo, Japan

3. Development of perovskite type catalyst for oxidative

coupling of methane

A. Nishida, H. Miura, T. Shishido, The 8th Asia Pacific

Congress on Catalysis (APCAT-8) August 4-7, 2019,

Bangkok, Thailand

4. One pot conversion of glycerol to lactic acid over

supported platinum catalyst

K. Takahashi, S. Feng, H. Miura, T. Shishido, The 8th

Asia-Pacific Congress on Catalysis (APCAT-8) August 4-

7, 2019, Bangkok, Thailand

5. Acid property of alumina-based mixed oxides supported

tungsten oxide

Mizuki Saito, Hiroki Miura, Tetsuya Shishido, The 8th

Asia-Pacific Congress on Catalysis(APCAT-8), August 4-

7, 2019, Bangkok, Thailand

6. Interconversion between bicarbonate and formate over

supported palladium-gold alloy catalysts

M. Waseda, K. Nakajima, M. Tominaga, H. Miura, T.

Shishido, The eightth Asia Pacific Congress on Catalysis

(APCAT-8) August 4-7, 2019, Bangkok, Thailand

7. [2+2+2] Cycloaddition of Alkynes by Concerted Catalysis

of Adjacent Pd–Au in Alloy Nanoparticles

H. Miura, T. Shishido, 14th European Congress on

Catalysis 2019 (EuropaCat2019), August 18-23, 2019,

Aachen, Germany

8. Selective Silylation of Aryl halides by Supported

Palladium-Gold Alloy Catalysts

Y. Masaki, H. Miura, T. Shishido, 14th European Congress

on Catalysis 2019 (EuropaCat2019), August 18-23, 2019,

Aachen, Germany

9. Kinetic study on reaction mechanism of hydrogenolysis

over Pt/WO3/Al2O3 catalysts

T. Aihara, H. Miura, T. Shishido, EuropaCat2019 August

18–23, 2019, Aachen, Germany

10. Selective CO2 hydrogenation over supported Rh catalysts

J. Suzuki, H. Miura, T. Shishido, 14th European Congress

on Catalysis (EuropaCat 2019, Aachen) August 18-23,

2019, Aachen, Germany

11. Supported Pd-based alloy catalysts for highly efficient

hydrogen storage system based on carbon dioxide/formic

acid cycle

M. Waseda, E. Kawai, H. Miura, T. Shishido, The fourth

International Symposium on Hydrogen Energy-based

Society August 22-23, 2019, Tokyo, Japan

12. Selective catalytic reduction of NO over Cu-Cr/Al2O3

catalysts

Shengyan Piao, Hiroki Miura, Tetsuya Shishido, The 9th

East Asia Joint Symposium on Environmental Catalysis

and Eco-materials, November 5-8, 2019, Yancheng, China

13. Selective catalytic reduction of NO with CO and C3H6

over Rh/HAP

S. Doi, S. Hayashi, H. Miura, T. Shishido, The 9th East

Asia Joint Symposium on Environmental Catalysis and

Eco-materials, November 5-8, 2019, Yancheng, China

＊Domestic


■Awards

30


1. Poster Award "Alloying effect of Pd and Au on selective

hydrosilylation of allenes" Suguru Sasaki 121th CatSJ

Meeting (22-23 March 2018, The University of Tokyo).

2. Poster Award "Hydrolytic desilylation of silyl ethers by

Brønsted acid gel catalysts with highly hydrophobic

surface" Syutaro Kameyama 121th CatSJ Meeting (22-23

March 2018, The University of Tokyo).

3. Poster Award ‘‘Structural characterization of supported

PdTe catalysts for oxidative diacetoxylation of olefines”

Yuta Homae 40th summer seminar of junior society of

CatSJ in Hamamatsu, August 3, 2019, Aichi.

4. Best Poster Award “Sillylation of sp2 C-H bonds in

heteroaromatics by supported Au catalysts” Ryuji Hirata

17th catalysts chemistry workshop at Himeji, July 25,

2019, Hyogo

5. Excellent Poster Award ‘‘Sillylation of sp2 C-H bonds in

heteroaromatics by supported Au catalysts” Ryuji Hirata

9th CSJ chemistry festa, Funabori. 23-25 October 2019,

Tower Hall Funabori

6. Excellent Poster Award ‘‘Supported NiAu catalysts

effective for hydrosilaytion of alkynes” Yohei Fukuta 9th

CSJ chemistry festa, Funabori. 23-25 October 2019,

Tower Hall Funabori

7. Catalysis Society of Japan Award for Young Researchers

2019 “Transformation of organic molecules by concerted

catalysis of different elements on the surface of PdAu alloy

nanoparticles” Hiroki Miura, January 6th 2020,

8. Best poster award “Selective catalytic reduction of NO

over Cu-Cr/Al2O3 catalysts”

Shengyan Piao, Hiroki Miura, Tetsuya Shishido, The 9th

East Asia Joint Symposium on Environmental Catalysis

and Eco-materials, November 5-8, 2019 Yancheng, China

9. Best poster award Selective catalytic reduction of NO

with CO and C3H6 over Rh/HAP

S. Doi, S. Hayashi, H. Miura, T. Shishido, The 9th East

Asia Joint Symposium on Environmental Catalysis and

Eco-materials, November 5-8, 2019, Yancheng, China

31


Shudo Laboratory

■Members Toshio Shudo Professor /Dr. Eng. Energy Engineering, room: 9-455 TEL: +81-42-677-2715 e-mail: [email protected] Doctor’s course -0 Master’s course -3 Bachelor 4 -3

■Outlines of the Research 1. Performance improvement in polymer electrolyte fuel cell, Toshio Shudo Because polymer electrolyte fuel cell has higher energy efficiency and lower power density compared to internal combustion engine, it is important to improve the performance of polymer electrolyte fuel cell. This research investigates the effect of porous metal flow field for even supply of reactants to the whole area of electrodes. 2. Performance improvement in direct methanol fuel cell. Toshio Shudo Direct methanol fuel cell system has higher energy density and lower power density compared to polymer electrolyte fuel cell system. This research investigates the effect of porous metal flow field for enhancing the reactant supply and product removal at the electrodes. 3. Ignition control in homogeneous charge compression ignition combustion. Toshio Shudo Internal combustion engine has higher power density and lower energy efficiency compared to fuel cell system. This research investigates a new combustion system by the compression ignition of homogeneous fuel-air mixture for achieving higher thermal efficiency in internal combustion engines.

■Papers with Peer Review See the annual report in Japanese (2 article)

■Reviews See the annual report in Japanese (2 article)

■Academic Meeting ＊Domestic See the annual report in Japanese (4 articles)

■Awards See the annual report in Japanese (1 award)

32

Applied Chemistry Colloquium

383th 2019/5/16

Katsuhiko Ariga (National Institute for Materials Science & The

University of Tokyo)

”How do you control molecular machines and nanocars by top-science

instruments or your own hands?”

384th 2019/5/22

Yoichi TOMINAGA (Tokyo University of Agriculture and Technology,

Institute of Engineering, Division of Applied Chemistry)

”Development of Li ion-conductive solid polymers”

385th 2019/7/10

Ziyi Zhong (Guangdong Technion Israel Institute of Technology)

”Heterogeneous catalysts: preparation or synthesis?”

386th 2019/8/27

Kazuo Tanaka (Department of Polymer Chemistry, Graduate School of

Engineering, Kyoto University)

”Development of functional luminescent materials based on non-

luminescent molecules”

387th 2019/9/10

Hiroyasu Furukawa (University of California, Berkeley)

”Design and Synthesis of Metal–Organic Frameworks for Hydrogen

Storage Applications”

388th 2019/9/13

Atsushi Maruyama (Tokyo Institute of Technology: School and Graduate

School of Bioscience and Biotechnology)

”Flexible Polyelectrolyte Complexes for Enhancement and

Development of Biomolecular Functions”

389th 2019/10/16

33

Applied Chemistry Colloquium

Eric Apel (National Center for Atmospheric Research, USA)

”Volatile Organic Compounds and Atmospheric Chemistry”

390th 2019/12/12

Wen-Yueh Yu (National Taiwan University)

”Surface Engineering of Ceria-Based Catalysts forNon-Reductive

Conversion of Carbon Dioxide”

Kevin Chia-Wen Wu (National Taiwan University)

”Water-based Synthesis of Metal-Organic Frameworks (MOFs) for

Energy Applications”

391th 2019/12/21

Sung-Soo Kim (Chungnam National University)

”Thermal and structural stabilities of LixCoO2 cathode for Li secondary

battery studied by a temperature programmed reduction”

34

Annual Report 2019 Published by Tokyo Metropolitan University Faculty of Environmental Sciences Department of Applied Chemistry for Environmental Sciences

April 1, 2019

annual report 2019 · 2020. 3. 19. · 7. processing of feeble magnetic materials under a magnetic...

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