Faculty of Environmental Sciences
Department of Applied Chemistry for Environment
Graduate School of Environmental Sciences
Department of Applied Chemistry for Environment

Annual Report 2019

IndexReports from Research Groups
Kawakami Laboratory

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1

Masuda Laboratory

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7

Asayama Laboratory

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9

Kubo Laboratory

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11

Setaka Laboratory

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14

Kanamura Laboratory

▪▪▪▪▪

16

Kajiwara Laboratory

▪▪▪▪▪

19

Takagi Laboratory

▪▪▪▪▪

21

Uchiyama Laboratory

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25

Shishido Laboratory

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29

Shudo Laboratory

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32

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33

ColloquiumReports from Research Groups
Kawakami Laboratory■Members
Hiroyoshi KAWAKAMI
Professor / Dr. Eng.
Polymer Chemistry, Functional Polymers, Nanofiber
Engineering, Biomaterials, Epigenetics Engineering, Free
Radical ScienceRm. 9-638, +81-42-677-1111 Ext. 4972
kawakami-hiroyoshi@tmu.ac.jp

2. Study of Polymer Electrolyte Membrane
Hiroyoshi 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 haveproton conductivity inside nanofibers, inter-connected structures
to construct continuous proton conductive pathway, and surfacemodified 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.

Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-ScienceRm. 9-137, +81-42-677-1111 Ext. 4837
yamato-masafumi@tmu.ac.jp
Kiyoshi SATO
Associate Professor / Dr. Eng.
Synthetic Organic Chemistry, Molecular Recognition,
Heterocyclic Chemistry, Physical Organic ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
sato-kiyoshi@tmu.ac.jp①
Utilization of① NF内部もプロトン
insidenanofiber
伝導に活用

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
tanaka-manabu@tmu.ac.jp③ Surface-③ 表面プロトン
modification
伝導層の拡大②②NF連結性向上
Connected

Figure 2. Approaches to improve proton conductivity on thenanofiber composite membranes.

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

3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA■Outlines of the Research

Recently, nano-scale fibers prepared through an electricallycharged jet of polymer solution/melt (electrospinning) havereceived a lot of attention. Nanofibers have several inherent
characteristics including high surface area, unique optical andphysicochemical properties originated from the nano-size, andalignment of polymer chains in the nanofibers. The diameter ofnanofiber 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 thepolymer 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 andgood charge-discharge properties.

1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO,
Manabu TANAKA
Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO2). Recently, we
have reported that novel composite membranes composed of thefluorinated 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 toan 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 3. Schematic illustration of the lithium ion battery using
the lithium ion conductive polymer nanofiber composite
membrane.
4. Design of Multi-electron Redox Catalysts
Hiroyoshi KAWAKAMI, Kiyoshi SATO

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

1

Reports from Research Groups
In this year, we have prepared a cationic manganese Nconfused porphyrin (MnNCP) as a coreductant-free catalyst for
ONOOdisproportionation.
The
pyridinium-appended
tetracationic MnNCP showed a higher ONOO- eliminating
activity than that of previous reported metal porphynoids underphysiological conditions without coreductants. Furthermore,
synthesis of MnNCP dimer, expected a multiple antioxidant
activity, is now under investigation.

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 spatiallyclosed to the metal centers. The metal complex acts as a protoncoupled multi-electron catalysis for electrochemical CO2
reduction by an efficient combination of the metal centers and
OH groups.

HO
OH

OH
N

N
N+

Fe
N

OH
HO

N
OH

Figure 4. Proton-coupled multi-electron redox catalyst forelectrocatalytic CO2 reduction.
Figure 6. Cationic-N-confused Mn-porphyrin (MnNCP) withperoxynitrite eliminating activity.

5. Study of Epigenetics Engineering
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA

7. Processing of feeble magnetic materials under a magnetic
field
Masafumi YAMATO

The development and maintenance of an organism isorchestrated by a set of chemical reactions that switch parts ofthe 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 theartificial epigenetic control of the chromatin conformations. The
anionic oligo- and poly-peptides successfully delivered tonucleus and show regulation of gene expressions. We also
prepared a liposome nanocarrier capable of induction of
mitophagy of damaged mitochondria to suppress cellularsenescence. These biomaterials will provide new treatment
strategies for acquired diseases caused by epigenomic
modifications and regenerative therapy (adoptive cellularimmunotherapy).

Controls of higher-order structure of feeble magnetic materials
by using a magnetic field have been studied in order to improvesome 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 thenano 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.
Rotating MF

Figure 7. Schematic drawing of plane orientation of clay byrotating magnetic field and stress-strain curves ofnanocomposite gels preparing in a rotating magnetic field.
Figure 5. Epigenetic gene expression control by chromatin
conformations.

■Papers with Peer Review
1. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, "Fabrication and characterizations of soft andflexible 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

6. Study of Free Radical Control by Artificial Enzyme
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTASuperoxide dismutase (SOD) or catalase (CAT) are wellknown 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.

2

Reports from Research Groups
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 magneticalignment, 2018 Annual report of high field laboratory forsuperconducting materials in institute for materials researchat Tohoku university，p.p. 158-159 (2019) (in Japanese)

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, 25162524 (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 ofPower 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-solidstate lithium ion batteries", Polymer International, 68, 684693 (2019).
7. Taku Ibaraki, Manabu Tanaka, Hiroyoshi Kawakami, "Fastsurface 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 MonoIon 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).

■Invited Lectures
1. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 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 bymagnetic 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, TokyoJapan (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 ofJapan, Jan. 2020, Tokyo Japan (in Japanese)■Academic Meeting
1. Kosuke Chikuma, Kohei Arima, Riku Kubota, Kiyoshi Sato,
Hiroyoshi Kawakami, A novel approach by ROS inhibitonand HDAC2 activation for COPD treatment, The 9th
Biennial Meeting of Society for Free Radical Research-Asia(Kyoto International Community House), P15, April 2019(inEnglish)2. M. Yamato, H. Kawakami ， Study on gas permeation insurface-modified silica nanoparticle containing composite
membrane with high gas permeability，41st annual meetingof membrane science of Japan, May 2019, Tokyo, Japan (inJapanease).
3.
Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi
Kawakami, Enhancement of proton conductivity ofcomposite electrolyte membrane by nanofiber containing
polyvinylphosphonic acid, 39 th The Membrane Society ofJapan, (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)■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 ofSurface-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 ofThermal Conductivity-(Chapter 3, Section 6, Filler

3

Reports from Research Groups
18. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi
Kawakami, Evaluation of Fuel Cell Characteristics ofComposite
Electrolyte
Membrane
with
Polyvinylphosphonic Acid Containing Nanofiber, The
Annual Meeting of the Society of Fiber Science andTechnology, Japan(Tower Hall Funabori), 2P216 (June 2019）19. Motoki Nishizawa, Takahiro Ogura, Manabu Tanaka, andHiroyoshi Kawakami, Preparation of proton conductive
nanofibers containing sulfonic acid and phosphonic acid andtheir application to fuel cells, The Annual Meeting of theSociety 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 macromolecularsymposium, P3, July 2019, Tokyo, Japan (in Japanese)
25. Takeru Yamazaki, Kohei Arima, Riku Kubota, Kiyoshi Sato,
Hiroyoshi Kwakami, Inhibition of ROS induced epithelialto-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 spiralstructure mimicking crustaceans using liquid crystal ofcellulose nanocrystal，23rd symposium on liquid-crystalline
chemistry, July 2019, Yokohama, Japan (in Japanese).
27. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, andHiroyoshi Kawakami, Preparation and evaluation of surfacemodified pearl-necklace nanoparticles containing PIM-1
composite membrane with high gas permeability, The 4thInternational 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, andHiroyoshi Kawakami, Fabrication and characteristic
evaluation of composite electrolyte membranes containing
proton conductive polymer nanofibers for fuel cells,International Seminar on Green Energy Conversion 2019,

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, Studyin 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, Fabricationand 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 (inJapanese)
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 (inJapanese)
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 (inJapanese)
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 Scienceand 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 andTechnology, Makuhari Messe, Japan, B1-02, June 2019 (inJapanese)
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 ResearchJAPAN (Hokkaido Prefectural Citizens Activity Center), P14, June 2019(in Japanese)
17. Ayano Imai, Hiroto Mikami, Manabu Tanaka, Masafumi
Yamato, and Hiroyoshi Kawakami, Influence of surfacemodified 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)4

Reports from Research Groups
Shimizu, Hiroyoshi Kawakami, Fabrication and Evaluationof 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 allsolid-state secondary batteries consisted of lithium saltcontaining 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 inJapan, 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 ofpolyimide and Aromatic polymer, Tokyo institute ofTechnology, 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) (inJapanese)
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, andHiroyoshi Kawakami, Mechanical properties of MMT-NC
gel prepared in rotating magnetic field, 14th Annual Meetingof the Magneto-Science Society of Japan (City Hall Plaza
Aore Nagaoka), P-25, November 2019.
48. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, andHiroyoshi Kawakami, Preparation and evaluation of gas
permeation properties of PIM-1 composite membranes
containing
surface-modified
pearl-necklace
silicananoparticles, The 57th Annual Meeting (Tokyo Universityof Marine Science and Technology), P-10, Dec. 201949. 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 ofMarine 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,(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,
MotokiNISHIZAWA, Moeri SHIMIZU, Hiroyoshi KAWAKAMI,
Development of Nanofiber Composite Membranes
Consisted of Non-Sulfonated Polymer Matrix for Reductionof 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 applicationof composite electrolyte membranes consisted of nanofibers
containing
lithiumsalts.
68h
SymposiumonMacromolecules (Hukui University) 1I15 (September 2019)(in Japanese)
33. Yu Matsuda, Manabu Tanaka, Masahumi Yamato, Hiroyoshi
Kawakami. Lithium ion conductive characteristics ofcomposite 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 ofJapan 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, Studyin 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 (inJapanease).
37. S. KAJIYAMA, M. NAKAYAMA, A. KUMAMOTO, M.
YAMATO, Y. IKUHARA, T. KATO, Morphological andOrientational 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 ofmagneto-birefringence of clay dispersion containing NIPAM,
12th Annual Meeting of the Magneto-Science Society ofJapan, Nov. 2019, Nagaoka, Japan (in Japanease).
39. Kosuke Chikuma, Kohei, Arima, Kiyoshi Sato, Hiroyoshi
Kawakami,
Developmentof
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

5

Reports from Research Groups
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, the16th Pacific Polymer Congress, Dec. 2019, Suntec,
Singapore,
53. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi
Kawakami, Hirota Noriyuki, Study in Adsorption behaviorof organic molecules to clay using *in-situ* magnetobirefringence and quantitative NMR, The 67th JSAP Spring
Meeting, (Sophia University), 14p-PA1-2 (March, 2020) (inJapanese)
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 byfunctional 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 surfacemodified pearl-necklace shaped nanoparticles, the SJEJ 85th
Annual Meeting / IChES 2020 (Kansai University), PE302(March, 2020) (in Japanese)

5.

6.

7.

8.

■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, andLithium ion battery, Hiroyoshi Kawakami, Manabu Tanaka,
Tsukasa Watanabe■Awards
1. Prize for Encouragement, H30 Fuel Cell Development
Information
Center(FCDIC),
ManabuTanaka,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
membranebynanofiber
containing
polyvinylphosphonic acid
4. Student poster award, 2019 Annual Meeting on The Society
6of 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.
Student poster award, 2019 Annual Meeting on The Societyof Fiber Science and Technology, Japan, Yu Matsuda,
Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion
conductive characteristics of composite electrolyte
membranes consisted of polymer nanofibers.
Best Poster Award, The 57th Annual Meeting of the JapaneseSociety for Artificial Organs, Kosuke Chikuma, Kohei,
Arima, Kiyoshi Sato, Hiroyoshi Kawakami, Development of
mitophagy-induced nanocarriers for the suppression ofcellular senescence
Student poster award, 27th symposium of polyimide andAromatic polymer, Wataru Murata, Yuta Inafune, Manabu
Tanaka, Hiroyoshi kawakami, Fabrication and evaluation ofcomposite polymer electrolyte membranes based on lithium
ion conductive PEO-grafted polyimide nanofibers
Student Poster Award, The 57th Annual Meeting of Polymer
and Water, Hiroki Harada, Manabu Tanaka, Hiroyoshi
Kawakami, Fabrication and fuel cell characterizations ofcomposite electrolyte membranes composed of proton
conductive nanofibers modified with zwitterion for highproton conductivity at high temperature and low humidityReports from Research Groups
Masuda Laboratory■Members

Hideki MASUDA, Takashi YANAGISHITAFor the preparation of uniform sized nanoparticles, we haveintroduced membrane emeulsification process using ordered
anodic porous alumina. The present process is simple and can beused 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.

Hideki Masuda
Professor/ Dr. Eng.
Electrochemistry, Nano Fabrication, Functional ElectrodeRm. 9-147, +81 426 77 2843
masuda-hideki@tmu.ac.jp
Takashi Takei
Associate Professor /Dr. Eng.
Solid surface chemistry, interface and colloid scienceRm. 9-136, +81 426 77 2822
takei-takashi@tmu.ac.jp(4) Study of Self-ordering Mechanism of the Cell Arrangementof Anodic Porous Alumina
Hideki MASUDA
Regularity of the holearray structure of the anodic porousalumina which is used as mother template is important toimprove the regularity of the obtained metal and semiconductor
nanohole arrays. To improve the regularity of the holearraystructure of the anodic porous alumina, anodizing conditions
were explored, and self-ordering of the anodic oxide film wasnewly discovered in sulfuric acid solution. The detailed
mechanism of the self-ordering of the anodic porous alumina iscurrently being investigated.

Takashi Yanagisita
Associate Professor/ Dr. Eng.
Electrochemistry, Functional Metal Oxide FilmRm. 9-140,+81 426 77 1111 (Ext. 4931)
yanagish@tmu.ac.jp
Master’s course -10
Bachelor 4 -6

(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.

■Outlines of the Research(1) Fabrication of Nanofilters by Electrochemical Process
Hideki MASUDA, Takashi YANAGISHITAFor the fabrication of ordered nanofilere membranes, wehave investigated anodization process of Al. The size andinterval 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 atemplate. For the replacement of the ordered hole-array structurewith other materials we developed a two-step replication process
in which formation of a replicated negative and subsequentpreparation 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■Papers with Peer Review
1. T. Yanagishita, A. Kato, T. Kondo, and H. Masuda,
Preparation of Freestanding Tubular Alumina ThroughHole 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.

SEM image of anodic porous alumina(2) Preparation of Ordered Nanostructures by Nanoimprinting
Using Ordered Anodic Porous Alumina Molds
Hideki MASUDA, Takashi YANAGISHITA
Ordered pillar array and hole array patterns were fabricatedby nanoimprinting using anodic porous alumina. Patterned
surface prepared by this process could be used for theantirefrection surface and surper hydrophobic surface.

2.

(3). Fabrication of Enagy Devices Based on Ordered Anodic
Porous Alumina
7

H. Masuda
Fabrication of Highly Ordered Anodic Porous Alumina and
Its Functional Applications
3rd International Symposium on AST 2019，2019/6，Awaji.

Reports from Research Groups
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
See the annual report in Japanese (5 articles)■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 Etchingof Al, ANZCOP 2019-SPIE, 2019/12，Australia.

＊Domestic
See the annual report in Japanese (15 articles)■Patents
See the annual report in Japanese (1 articles)■Awards
See the annual report in Japanese (2 articles)8

Asayama Laboratory■Members

to liver is applied for remote control of hypoglycemic hormone(Figure 2).

Shoichiro ASAYAMA
Associate Professor / Dr. Eng.
Biomaterials, Drug Delivery System, Biomedical Polymers,
Biomolecular Engineering, BiochemistryRm. 9-651, +81-42-677-1111 Ext. 4976
asayama-shoichiro@tmu.ac.jp

Insulinsecretion

InsulinPancreas

Liver

H
C CH2

Master’s course -5
Bachelor 4 -3

N

Protein■Outlines of the Research

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).

+

Delivery toUnexplored
Space

O
H2N

N

N

1-x-y

Zn2+

3. Biomaterials with Funtional Surface
Shoichiro ASAYAMA
As water-insoluble (splid-phase) biomaterials, to design
medical devices working in vivo or ex vivo with efficientbiocompatibility, we have recently applied cholesterol endmodified poly(ethylene glycol), that is, Chol-PEG, as DDS
carrier to the non-covalent modification of solid surface (Figure3).

Mono-Ion Complex【MIC】
C(CH2)nN

In this year, the zinc porphyrin-carbohydrate conjugate (ZnPLac) 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 therecognition of lactose with an asialoglycoprotein receptor(ASGP-R) on the HepG2 cell.

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

+

N

H
C CH2

y

Figure 2. Remote control of hypoglycemic hormone in blood.

To improve human health and quality of life (QOL), we havedesigned new biomaterials. Especially, we have designed new
drug delivery system (DDS) for advanced and homogeneous
medicine as follows:

+

H
C CH2

x

+
N
N
(CH2)nCH3

N+

Survival insulin
to whole body

Zn 2+

PEG

H3C

Mo st S im p le
No n co v a len t
P E Gyla t io n
CH3O

DiseaseCH2CH2OnCH3In 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 beensynthesized.
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 ofin vivo gene delivery by use of the MIC and DIC have been
demonstrated.

H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

Figure 1. Delivery to in vivo unexplored space by the monoion complex (MIC).

CH3

H3C

Insulin

7

8

9
10
11
Elution volume / mL

12

Figure 3. Development of novel bio-function by Chol-PEG.
In this year, the modification density of cholesterol endmodified PEG (Chol-PEG) to poly(propylene) (PP) surface, andthe 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 beensucceeded. The resulting bio-inert surface is expected to be
applied for in vivo implanted devices.

2. Bioactive Substance (Zn2+, protein) Delivery System
Shoichiro ASAYAMA
To give DDS carrier the ability for definitive treatment, wehave designed pH-sensitive polyvinylimidazole (PVIm)
derivateives as intelligent materials to change their structure andfunction in respons to external stimuli. Recently, Zn2+ delivery

9

■Papers with Peer Review
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(1vinylimidazole) for cell-specific plasmid DNA carrier, Internal
Medicine and Care, 4, 1-5 (2020).
■Academic Meeting
See the annual report in Japanese (13 articles)

10

Reports from Research Groups
Kubo Laboratory■Members
Yuji Kubo
Professor /Dr. Eng.
Organic Chemistry, Supramolecular Chemistry, Functional Dye
Room: 9-539 TEL: +81-42-677-3134
e-mail: yujik@tmu.ac.jp
Figure 2. Chemical structure of a sensitizer for application in
p-typed DSSC and EQE spectrum the dye-loaded p-type DSSC.

J. Yan Mulyana
Associate Professor / Ph.D.
Coordination Chemistry, Photochemistry
Room: 9-149 TEL: +81-42-677-2823
e-mail: ymulyana@tmu.ac.jp

3. Synthesis of selenium-containing dyes as photosensitizers
for triplet–triplet annihilation upconversion
Yuji Kubo
Abstract
A series of selenium-containing BODIPY dyes weresynthesized 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 toheavy atom effects. When TTA-UC systems comprising thesedyes as triplet donors and pelyrene as a triplet acceptor
perylene were set up, substituent-dependent TTA-UC behaviors
were observed.

Ryuhei Nishiyabu
Assistant Professor / Dr. Eng.
Supramolecular Chemistry, Organic Chemistry, Matetials
Chemistry
Room: 9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: ryuhei@tmu.ac.jp
Doctor’s course -3
Master’s course -11
Bachelor 4 -8

■Outlines of the Research
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 thesystem exhibited hydrogen generation. This study provides
important information for the development of metal-freeorganic photosensitizers with a wide spectral response up to the
NIR region for photocatalytic water-splitting hydrogenproduction.

Figure 3. Selenium-containing BODIPYs as sensitizers fortriplet–triplet annihilation upconversion.
4. Synthesis of Near Infrared (NIR) Light Absorbing Dye for
Photodetectors
Yuji Kubo
AbstractA
seriesofthieno[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. Itsapplicability as a NIR photodetector was evaluated throughfabrication of a single-component device. The ITO/3 (85nm)/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 1. Dye-sensitized photocatalytic hydrogen production
by water splitting.
2. Synthesis of photosensitizers for application indye-sensitized solar cells
Yuji Kubo
This study has been collaborated with Prof. Dr. ŞuleERTEN-ELA (Solar Energy Institute, Ege University).
Abstract
Much attention has been devoted to the synthesis of dyesthat absorb near-infrared (NIR) radiation because of numerous
demands for them as functional materials. In this work, wehave tried to propose NIR absorbing photosensitizers
applicable to dye-sensitized solar cell (DSSC) devices.

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
particles as ratiometric afterglow sensors

11boronateReports from Research Groups
Yuji Kubo and Ryuhei Nishiyabu
Abstract:
We found that boronate particles (BP), as a self-assembled
systempreparedbysequential
dehydrationofbenzene-1,4-diboronic acid with pentaerythritol, showedgreenish room-temperature phosphorescence. This emission
was observed in both solid and dispersion state in water andratiometric afterglow sensing of water content in an organic
solvent was achieved by grafting of a rhodamine onto thesurface of BP.

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 asingle chemosensor
Yuji Kubo
This study was collaborated with Tsuyoshi Minami (Institute ofIndustrial 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 onimine formation between the aldehyde group of (R)-1 andtarget 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 fromthe 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 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 photoanodesurface-modified with Rutbipy dye and CuTCPP co-catalyst.

Figure 8. Enantioselective response for optically ative
diamines by self-assembled chiral chemosensors.

7. Boronate sol–gel method for one-step fabrication of
polyvinyl alcohol hydrogel coatings by simple cast- anddip-coating techniques
Ryuhei Nishiyabu and Yuji Kubo
Abstract
The self-assembly of polyvinyl alcohol (PVA) andbenzene-1,4-diboronic acid (DBA) is employed as a sol–gel
method for one-step fabrication of hydrogel coatings withversatile 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 withhydrogel films by simple cast- and dip-coating techniques.

■Papers with Peer Review
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 asingle chemosensor. Chem. Sci., 2020, accepted. DOI:
10.1039/D0SC00194E
2. M. Hoshi, R. Nishiyabu, Y. Hayashi, S. Yagi and Y. Kubo,
Room-temperaturephosphorescence-active
boronate
particles: characterization and ratiometric afterglow-sensing
behavior via surface grafting of Rhodamine B. Chem. AsianJ., 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 alcoholhydrogel coatings by simple cast- and dip-coating
techniques. RSC Adv., 2020, 20, 86‒94. DOI:
10.1039/C9RA08208E
12

Reports from Research Groups
4 Y. Kubo, T. Shimada, K. Maeda
andY.
Hashimoto,Thieno[1,3,2]oxazaborinine-con
taining aza-BODIPYs with nearinfraredabsorption
bands:
synthesis,
photophysicalproperties,
anddeviceapplication. New J. Chem., 2020,44,
29-37.
DOI:
10.1039/C9NJ04612G
5. Y. Higashino, S. Erten-Ela andY. Kubo, π-Expanded dibenzo-BODIPY with near-infrared
light absorption: investigation of photosensitizing properties
of NiO-based p-type dye-sensitized solar cells. Dyes andPigments,
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 onnanostructured BiVO4/TiO2 modified with dye andco-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
photocatalytichydrogen production using dibenzo-BODIPY andphenothiazine conjugate as organic photosensitizer. ACS
Appl. Energy Mater., 2019, 2, 448‒458. DOI:
10.1021/acsaem.8b01474■Invited Lectures
1.

2.

3.

4.

Near-infrared absorbing dibenzo-BODIPYs; Synthesis,
properties, and applications, Yuji Kubo, Lecture at Ege
University (Izmir, Turkey), July 22, 2019.
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.
Preparation of solid catalysis and solid-based
luminescence materials based on boronate supramolecules,
Yuji Kubo, 19-2 Research group on supramolecules (TheSociety of Polymer Science), Tokyo, January 24, 2020 (inJapanese).
Synthesis of visible light and near-infrared absorbing dyesfor efficient light-induced hydrogen production, Yuji Kubo,
4S8-09 (Special Program lecture), The 100th CSJ Annual
meeting, March 25, 2020 (in Japanese).

■Academic Meeting
See the annual report in Japanese (17 articles)

13

Reports from Research Groups
Setaka Laboratory■Members
Wataru Setaka
Professor /Dr. Sci.
Physical Organic Chemistry, Functional Organic Chemistryroom: 9-542 TEL: +81-42-677-1111 (Ext.4955)
e-mail: wsetaka@tmu.ac.jp

Figure 2. Structure and Polarized fluorescence of the crystal of
methylcarbazole bidged macrocage (paper #4).

Yusuke Inagaki
Assistant Professor / Dr. Sci.
Main-group Chemistry, Functional Organic Chemistryroom: 9-545 TEL: +81-42-677-1111 (Ext.4957)
e-mail: yinagaki@tmu.ac.jp
Doctor’s course -0
Master’s course -5
Bachelor 4 -5

Carbazole nitroxide is known as labile radical species due toextended 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 wereobserved (Figure 3, paper #2).

■Outlines of the Research
Development of Highly Designed Organic Molecules
Wataru SETAKA, and Yusuke INAGAKIDevelopment of organic molecules of which strucrure andfunctions are highly designed would improve our daily life withrespect to energy saving and environmental consequence. Ourinterest lies in the design and synthesis of organic moleculeswith new structures that incorporate silicon to develop
molecules with new functions. Specifically, we are studying therelationship between molecular structure and molecularfunctionalities of novel organosilicon compounds.

Figure 3. Structure and ESR spectrum of carbazole nitroxide
bridged macrocage (paper #2).

1. Crystalline Molecular Gyrotop
A molecular machine has been defined as a discrete number ofmolecular components that perform mechanical─likemovements in response to specific stimuli. A macrocage
molecule with a bridged thiophene rotor was synthesized as amolecular 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-disordertransition, and the variation in the optical properties in the
crystalline state were observed.

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), weresynthesized, and their gearing properties were investigated.
Gear slippage, that is an error in gear rotation, is observed inhigh-temperature solutions of molecular bevel gears. Heavy
atom derivatives undergo gear slippage more easily due to thelong bond lengths and wide angles between the two triptycil
units and the bridging group 14 element. Activation energies ofgear 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 inmolecular bevel gears can accurately reproduce experimental
phenomena. (Figure 4, paper #2).

Figure 1. molecular gyrotop.
We have reported our rewiews regarding chemistry ofmolecular gyrotops (Review #1).
In this year, following papers were published.
Methylcarbazole is known as efficient fluorophore. In thisstudy, methylcarbazole bridged macrocage was designed andsynthesized. Unfortunately, the carbazole moiety shows norotation 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).

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

14

Reports from Research Groups■Invited Lecture
1. Chemistry of Molecular Gyrotops
W. Setaka
Molecular Rotor Workshop 2019 , 2019.11.21-22, theInstitute of Organic Chemistry and Biochemistry of theCAS(Prague, Czech Republic)(invited)

Construction of hydrogen-bonded networks among hydroxyl
groups has often been utilized to synthesize specific structureson the basis of supramolecular chemistry. In this study,
resorcyltriptycene was designed as a possible component of acrystalline molecular gear, because the molecule has a triptycyl
wheel and a resorcyl linker which can be involved inintermolecular alignments in a crystal, as mediated byhydrogen-bonded networks. The synthesis and crystal structureof resorcyltriptycene are reported here. The gear alignment
among triptycyls in a crystalline state was achieved in a crystal
structure of resorcyltriptycene containing water in theintermolecular spaces. However, rotations of triptycyls in the
crystalline state was suppressed by steric interaction with thewater molecules. This crystal structure was stabilized by
O–HꞏꞏꞏCπ(phenyl) interactions between triptycyl and thehydrated water. Moreover, single crystals without solvent andwith methanol were obtained from a dry toluene solution and amethanol solution, respectively. Transformations among thesingle 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).

■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)

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 aGroup 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

15

2.

Synthesis of Acediynes by Utilizing Bulkiness of SilylGroupsKazuki 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 andMotion 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 silylgroupsKazuki Komatsubara, Yusuke Inagaki, Wataru Setaka
9th CSJ Chemistry Festa, Tower Hall of Fenabori,2019.10.15-17 (Tokyo, Japan).(10/16 P4-029)(poster)Reports from Research Groups
Kanamura Laboratory
approach to improve the safety of rechargeable lithium-metal
batteries.

■Members
Kiyoshi KANAMURA
Professor /Dr. Eng.
Inorganic
Industrial
Chemistry,
Electrochemistryroom:9-247 TEL: +81-42-677-2828
e-mail: kanamura@tmu.ac.jp

EnergyChemistry,

1 mol dm-3
LiPF6 / EC

4.5 mol dm-3
LiFSI / EC

Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-246 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp
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.

Doctor’s course -3
Master’s course -13
Bachelor 4 -7

■Outlines of the Research
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 withpractical laminated-forms in addition to the exploration of newmaterials to improve the batteriy performance.

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 developmentof 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 canbe increased but the dissolution of platinum catalysts also isenhanced. In this FY, we focused on the dissolution behavior of
platinum catalysts and found that high durability can be achievedfor platinum catalysts in the phosphoric acid / ionic liquid mixed
electrolytes (Fig. 4). For the reduction of fuel cell cost, nonplatinum carbon-based catalysts were also studied.

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 lithiummetal 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 anotherFig. 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).

16

Reports from Research Groups■Papers with Peer Review
1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

Appl. Mater. Interfaces, doi.org/10.1021/acsami.9b21251(2020).

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., 9,1259012595 (2019).
Yuto Shimizu, Kiyoshi Kanamura, Three DimensionallyOrdered Macroporous Polybenzimidazole Separator for
Li Metal Battery, Chem. Lett., 48, 429–432 (2019).
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 formagnesium rechargeable batteries: toward the reversible
spinel–rocksalt transition, J. Mater. Chem. A, 7, 1222512235 (2019).
Motoko Nagasaki, Kiyoshi Kanamura, High-Performance
Lithium Metal Rechargeable Battery Using an Ultrafine
Porous Polyimide Separator with Three-DimensionallyOrdered Macroporous Structure, ACS Applied Energy
Materials, 2, 3896-3903 (2019).
Jihun Song, Williams Agyei Appiah, Kim Sung-Soo,
Hirokazu Munakata, Kiyoshi Kanamura, Myung-Hyun
Ryou, Yong Min Lee, 3D electrochemical model for aSingle Secondary Particle and its application for
operando analysis, Nano Energy, 62, 810-817 (2019).
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]2based supporting salts for high-voltage magnesium
rechargeable batteries, Physical Chemistry Chemical
Physics, 21, 12100-12111 (2019).
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).
Yong Zhang, Masashi Konya, Ayaka Kutsuma,
Seonghyeon Lim, Toshihiko Mandai, Hirokazu Munakata,
Kiyoshi Kanamura, Magnesium Storage Performance andMechanism of 2D ‐ Ultrathin Nanosheet ‐ Assembled
Spinel MgIn2S4 Cathode for High ‐ Temperature Mg
Batteries, Nano Micro Small, 15, 1902236 (2019).
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).
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).
Seonghyeon LIM, Hirokazu MUNAKATA, Kiyoshi
KANAMURA, Carbon Coating for Improvements ofElectrochemical Properties of Li1.1V0.9O2 Anode Active
Materials for Li Secondary Batteries, Electrochemistry,88, 22-27 (2020).
Eric Jianfeng Cheng, Takeshi Kimura, Mao Shoji, Hiroshi
Ueda, Hirokazu Munakata, Kiyoshi Kanamura, CeramicBased Flexible Sheet Electrolyte for Li Batteries, ACS■Books and reviews
See the annual report in Japanese (8 articles)■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 byComposite Type Solid Electrolyte, INESS 2019 The 7thInternational Conference on Nanomaterials andAdvanced Energy Storage Systems, 2019 年 8 月, AlFarabi 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

Reports from Research Groups

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

Plating/Stripping Behavior, 235th ECS Meeting, 2019 年
5 月, Sheraton Dallas, Dallas, USA.
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.
K. Kanamura, M. Shoji, E. Cheng, Development of Flexible
Composite Solid Electrolyte and Quasi-solid Composite
Cathode for Practical Realization of Solid-state Lithiumion Batteries, GFMAT-2, 2019 年 7 月, Toronto Marriott
Downtown at CF Eaton Centre Hotel, Toronto, Canada.
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.
Jie. Yu, H. Miura, H. Munakata, T. Shishido, K. Kanamura,
Developmentof
non-humidified
intermediate
temperature methanol-reforming-hydrogen/ oxygen fuelcell system, The 4th International Symposium on
Hydrogen Energy-based Society, 2019 年 8 月, Tokyo
Metropolitan University, Tokyo, Japan.
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.
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 andCompetitors, 2019 年 9 月, Granship, Shizuoka, Japan.
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.
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.
Jie Yu, Hirokazu Munakata, Kiyoshi Kanamura,
Development of 3-Dimensionally Ordered Microporous
Polyimide Based Composite Membranes Apply on NonHumidified Intermediate Temperature Fuel Cells, 236th
ECS Meeting, 2019 年 10 月, Hilton Atlanta, Atlanta, USA.
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.
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.
Koki NAKANO, Yusuke NODA, Naoto TANIBATA,
Masanobu NAKAYAMA, Koichi KAJIHARA, Kiyoshi

16.

17.

18.

19.

20.

21.

22.

KANAMURA, Evaluation of the Mg-ion conductivity andphase stability of Mg-ion conductor MgZr4(PO4)6 by DFT
method, PACRIM13, 2019 年 10 月, Okinawa Convention
Center, Okinawa, Japan.
Ryosuke SETO, Koichi KAJIHARA, Kiyoshi KANAMURA,
Cosolvent-free synthesis and characterization ofpoly(Ph-co-R-SQ) (R = Me, Et, Pr, and Vi) glasses withlow melting temperatures, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei
Onodera, Shinji Kohara, Microscopic ordering in
amorphous poly(n-alkylsilsesquioxane) liquids and solids
synthesizedbyacosolvent-freehydrolytic
polycondensation via aging, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
Jae-sang, PARK, YOSUKE Kushida, KYOSHI Kanamura,
Effect of heat treatment on electrochemical properties
of interface between LiCoO2-Li3BO3 composite andceramic type solid electrolyte formed by aerosol
deposition method, PACRIM13, 2019 年 10 月, Okinawa
Convention Center, Okinawa, Japan.
Hiroki Yamashita, Jun Ikegami, Yuko Hirayama, Takaaki
Ogami, Yuto Yamada, Kiyoshi Kanamura, Synthesis andelectrochemical
properties
ofLiMn1-xFexPO4/C
secondary particles, PACRIM13, 2019 年 10 月, Okinawa
Convention Center, Okinawa, Japan.
Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei
Onodera, Shinji Kohara, Microscopic ordering in
amorphous poly(n-alkylsilsesquioxane) liquids and solids
synthesizedbyacosolvent-freehydrolytic
polycondensation via aging, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
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.
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
See the annual report in Japanese (31 articles)

18

Reports from Research Groups
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: kkaji@tmu.ac.jp
Master’s course -4
Bachelor 4 -3

■Outlines of the Research

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.

1. Studies on silica-based materials
Koichi KAJIHARA
Silica is a ubiquitous material and its utilization is in accordancewith SDGs. Silsesquioxanes (SQs) are silica-based organicinorganic hybrids with a general formula RSiO3/2. We havedeveloped cosolvent-free synthesis method of SQ polymers, anenvironmental-friendy synthesis method of SQ polymers, andare trying to utilize them. This FY we focused onpoly(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 bycopolymerization 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.

■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, Cosolventfree synthesis and characterisation of poly(phenyl-co-nalkylsilsesquioxane)andpoly(phenyl-co-vinylsilsesquioxane) 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 achloroboracite-based glass-ceramic solid electrolyte, The 4thInternational Symposium on Hydrogen Energy-BasedSociety, 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, Highlytransparent efficient sol–gel-derived silica–(Gd,Pr)PO4 glassceramic 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 nonbridging 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−gelderived 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−gelderived 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

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 bondedwith 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+-ionconducting oxide MgZr4(PO4)6. In corroboration with Nagoya
Institute of Technology. Our group has succeded the hightemperature direct-current conductivity measurement of thiscompound using Mg metal electrodes. Ab-initio DFT
calculations indicated that real MgZr4(PO4)6 crystals havemonoclinic 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.

19

Reports from Research Groups
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 CeramicSocieties (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 andphase stability of Mg-ion conductor MgZr4(PO4)6 by DFT
method, The 13th Pacific Rim Conference of CeramicSocieties (PACRIM13), Okinawa, Japan, 2019/10/29
10.K. Kajihara, R. Seto, K. Kanamura, Y. Onodera, S. Kohara,
Microscopic
ordering
inamorphouspoly(nalkylsilsesquioxane) liquids and solids synthesized by acosolvent-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

Reports from Research Groups
Takagi Laboratory■Members
Shinsuke TAKAGIProfessor /Ph.D
Photochemistry, Photo-functional Materials
Porphyrin Chemistry, Clay Science
Room: 9－446 TEL: +81-42-677-2839
e-mail: takagi-shinsuke@tmu.ac.jp

Chemistry,

Tamao ISHIDA
Associate Professor/Ph. D.
Catalysis Chemsitry
Room: 9-447 TEL：+8142-677-2845
e-mail: tamao@tmu.ac.jp

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 hexagonalarray. The complex formation behavior between SS and cationicporphyrins was examined. It turns out that the averageintermolecular 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 canbe rationally understood by the previously reported “sizematching 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 behighly 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.

Tetsuya SHIMADA
Assistant Prof. / Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Visiting researcher 4
Doctor’s course 4
Master’s course 11
Bachelor 8■Outlines of the Research
Our group challenges to control photochemical reactions suchas electron and energy transfer, by controlling the orientation andalignment of dyes on the inorganic surfaces.
Recently,organic/inorganic hybrids composed of porphyrins and layeredmaterials have been the subject of intensive investigations to
explore their novel properties and functionalities. We foundout that a precise matching of distances between the negatively
charged sites on the clay mineral layers and that between thepositively charged sites in the dye molecule is one of the mostimportant 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 molecularassembly 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 segregatedadsorption structure of two kinds of dyes on the clay surface.
These findings indicate that the clay/porphyrin complexes arepromising and prospective candidates to be used for constructionof 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 andhydroperoxide formation were examined as an energy related
subject this year.

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 turned21

Reports from Research Groups
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, theenhancement of phosphorescence on clay surface was found put.

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 seemto be a promising candidate as soft Lewis acid catalysts foralkene activation. Au/HAPs were prepared under oxidative andreductive 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 theReaction Mechanism at Low Temperature Caused by aDifferent 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 andcontinuous 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.

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 researchtarget 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 withgood electron transfer property for artificial photosynthesis
system. We synthesized a novel TiO2 nano-sheet (TNS) andcharacterized 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 formetal nanoparticles because of high surface area and orderedanioninc charges on the surfaces. In this year gold nanoparticles(Au NPs) were deposited on TNS and SSA by depositionreduction 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 4hydroxybenzaldehyde 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, bytransmission electron microscopy. These findings will contributeto devlop new Au catalysts using nanosheet materials.
Hydroxyapatite (HAP) supported Au catalysts have been
known to show inverse strong metal-support interaction (SMSI)■Review articles and books
1. Gold Nanoparticles for Oxidation Reactions: Critical Roleof 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

Reports from Research Groups
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 forphotocatalytic
selective
oxidationof
5hydroxymethylfurfural, 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, AusdarcYTU 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)andInternational 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)

2. Tuning emission properties by dye encapsulation intolayered silicates, Y. Ishida, S. Takagi, Springer, “Dyesand 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 4thInternational 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 4thInternational 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 4thInternational Symposium on Hydrogen Energy‒based
Society, Tokyo (Japan), August, 2019.
5. Adsorption behavior and photochemical property ofdivalent 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 photocatalyticoxidation of 5-hydroxymethylfurfural, C. Mochizuki, T.
Shishido, T. Ishida, H. Masatake, T. Murayama, The 4thInternational 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■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 3rdInternational Conference on Solar Fuels and International
Conference on Artificial Photosynthesis2019, Keito SANO
(D1), November, 2019.
4. Poster Presentation Awards for Students, The 3rdInternational Conference on Solar Fuels and International

23

Reports from Research Groups
Conference on Artificial Photosynthesis2019, Keito SANO
(D1), November, 2019.

24

Reports from Research Groups
Uchiyama Laboratory■Members

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 wereintroduced into capillary (id200- 500 μm), then were flown to
the downstream. The capillary was wrapped 30~40 times aroundthree heating blocks, each of which has same temperatue as PCRamplification. As a result, PCR amplification was carried out
during the flow through the capillary. Finally, determination wasmade by counting fluorescent droplets. We have realized new
on-line digitial PCR system for the first time.

Katsumi UCHIYAMA
Professor / Dr. Pharmacol.
Analytical Chemistry, Nano/Micro Chemical Fabrication,
Micro Droplet
room: 9-339
TEL: +81-42-677-1111 Ext.4877
e-mail: uchiyama-katsumi@tmu.ac.jp
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, Geochemistryroom: 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

1-2 Droplet enhanced fluorescence, principle and application
We found the the droplet with later refractive index thansurrounding media showed drastic increase of fluorescenceintensity 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.

Hidetaka NORITOMIAssistant 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. Assistantroom: 9-290
TEL: +81-42-677-1111 Ext.4872
e-mail: kagawa @tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistantroom: 9-291
TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp
Doctor’s course -2
Master’s course -11
Bachelor 4 -8
Dissertion Ph.D. supporting by JSPS-1(Tsinghua University)

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.

■Outlines of the Research
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 havedeveloped 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 drugdelivery system.
1-1 Development of on-line digital PCR system

25

Reports from Research Groups
2. Development of nano/micro chemical pen and its
applications
Katsumi UCHIYAMA, Sifeng MAO
We have developed micro chemical pen, which enabled
position selective micro chemical fabrication on the suface ofmaterial. 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 chemicalmachine, fabrication of chemical device and functionalization of
micro machine etcs in the future.

antigens, proteins and glycoproteins in biological samples.
However, the conventional ELISA method relatively needs along analysis time and many expensive reagents. In addition,commercially available microplate readers are large-size andvery 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, amarker 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 themethod needs large-sized and expensive assay devices such as athermal 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.

3. Single cell operation
Katsumi UCHIYAMA, Sifeng MAO
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 characterizecell in single cell level, tumor cell will be easily detected and it
leads to the ultra fast diagnosis of tumor and precise study on themechanism of metastasis. In this study, we develop tools for thecharacterization of single cell, extraction of single cell fluid,
measurement of chemicals exposed from a cell by using theprinciple 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 ofthe analytical system. In this study, we developed a solution
sending method based on the centrifugal force generated byrotating a compact disk-type microfluidic device. A portable
fluorescence detection system, electrochemical detection systemand surface plasmon resonance sensor using the compact disktype microfluidic device were developed. Since these systems do
not need pumps and valves, these systems would be useful foron-site analysis, such as environmental monitoring, food safety
testing and point-of-care testing.

7.

Development of Multichannel ISFET Sensor for
Measuring pH Distribution of Interstitial Water inMarine 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 reefarea, the effect of ocean acidification on marine organisms livingin there is apprehended. Therefore, the measurement of pH
distribution of interstitial water in marine sediment is importanttask 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, theglass electrode is fragile, and the pH distribution of interstitialwater could not be measured at same time. To overcome thesedrawbacks, 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.

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,26

Reports from Research Groups
Uchiyama, Hulie Zeng
Droplet Sensitized Fluorescence Detection for EnzymeLinked 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 Applicationsin 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 nitrogenoxides 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 collectedduring 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)

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 volatileorganic compounds were continuously observed at remotesites: cape Hedo in Okinawa, Suzu in Ishikawa.
10. Measurements of atmospheric pollutants at mountainsites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide were observed atsummit of Mt. Fuji during summer. There was no influence fromlocal 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 withlow power gase sensor and LPWA ELTRES (SONY).
11. Atmospheric trace gas measurements using small gas
sensorShungo KATO
Atmospheric trace gases and PM2.5 were measeured bysmall gas sensors at urban area and clean remote site at the topof Mt. Fuji. Also, portable system working by battely wasconstructed.
12. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen 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 preparedfrom forestry residues, which are carbon neutral, and was used
as a protein carrier. We found that biochar imparts high heatstress tolerance and organic solvent stress tolerance to proteins.
This result would be expected to the applications tobioprocesses such as bioreactors, biosensors, and biofuel cells.

See the annual report in Japanese (1 articles)■Invited Lectures■Papers with Peer Review

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

1. Syed Niaz Ali Shah, Xiangnan Dou, Mashooq Khan,
Katsumi Uchiyama, Jin-Ming Lin
N-doped carbon dots/H2O2 chemiluminescence system forselective detection of Fe2+ ion in environmental samples
Talanta, 196, 370–375, (2019)
2. Tsuguhiro Kaneko, Yue Sun, Hizuru Nakajima, Katsumi

27

Reports from Research Groups
Using a Diffusion Mixing Reaction System for Applicationsin Temperature Sensing
2019 China-Japan-Korea Symposium on Analytical Science（ 2019CJK ） , Kyung Hee University (Global Campus)
Yongin, Korea
3. Katsumi Uchiyama
Analytical chemistry in Japanthe 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
the 18th Beijing Conference and Exhibition on Instrumental
Analysis (BCEIA 2019), China National Convention Center,
Beijing, China
5. Katsumi Uchiyama
Droplet enhanced fluorescence and itsa application to bioanalysis
the 18th Beijing Conference and Exhibition on Instrumental
Analysis (BCEIA 2019), China National Convention Center,
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 theDivisional 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 andthe Environment (ISBN: 978-1-83881-987-3), Ed by Vikas
Abrol, InTech, London, United Kingdom, Chapter 5, pp.7595 (2019)
See the annual report in Japanese (1 book)■Awards28

Reports from Research Groups
Shishido Laboratory■Members

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.

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)
e-mail: shishido-tetsuya@tmu.ac.jp
Hiroki Miura
Assistant Professor /Dr. Eng.
Catalysis Science, Solid acid-base, Organic
Organometallic chemistryroom:9-550 TEL: +81-42-677-2851 (Ext. 4962)
e-mail: miura-hiroki@tmu.ac.jp

chemistry,

Doctor’s course -3
Master’s course -18
Bachelor 4 -7

3. Brønsted acid property of alumina-based mixed-oxidessupported tungsten oxide■Outlines of the Research

The effect of alumina-based supports on the structure and acidproperties 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 acidsites 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 surfacehydroxyl 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 Brønstedacid sites on alumina-based supports.

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 ofglycerol 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 kindsof reactions, ie, oxidative of glycerol to trioses and subsequent
isomerization to lactic acid. In this catalytic reaction, thePt/Nb2O5 functioned as "hybrid catalysts" in which Pt
nanoparticles and Nb2O5 promoted the oxidation andisomerization, respectively.

■Papers with Peer Review
1.

2. Silylation of aryl chlorides by bimetallic catalysis of
palladium and gold on alloy nanoparticles
Supported palladium–gold alloy-catalyzed cross-coupling ofaryl chlorides and hydrosilanes enabled the selective formationof aryl–silicon bonds. Whereas a monometallic palladiumcatalyst 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 highselectivity. 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 thesurface of alloy nanoparticles independently functioned as active

2.

3.

4.

5.

29

“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】“Acid Property of Alumina-Based Mixed Oxides
Supported Tungsten Oxide” Saito, M.; Aihara, T.; Miura,
H.; Shishido, T. Catal. Today 2020, in press.
“Importance of the Pd and Surrounding Sites inHydrosilylation 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】“Investigation of the mechanism of the selectivehydrogenolysis of C-O bonds over a Pt/WO3/Al2O3
catalyst” Aihara, T.; Miura, H.; Shishido, T. Catal. Today
2020, in press.
“One-pot synthesis of lactic acid from glycerol over Pt/L-

Reports from Research Groups

6.

7.

8.

9.

10.

11.

Nb2O5 catalyst under base-free conditions” Shixiang, F.;
Takahashi, K.; Miura, H.; Shishido, T. Fuel Process.
Technol. 2020, 197, 106202“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.
“Effect of Perimeter Interface Length between 2D WO3Monolayer 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.
“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.
“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】“Catalysis of Cu Cluster for NO Reduction by CO:
Theoretical Insight into Reaction Mechanism andExperimental Evidence” Takagi, N.; Ishimura, K.; Miura,
H.; Shishido, T.; Fukuda, R.; Ehara, M.; Sakaki, S.ACS
Omega 2019, 4, 2596–2609.
“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.

3.

4.

5.

6.

7.

8.

■Invited Lectures
1.

2.

3.

4.

5.

124th CatSJ Meeting “Design of Brensted acid sites withhigh hydrophobicity and their catalysis toward hydrolysisof organic molecules” 2019/9/19 Nagasaki University
Design of High-Performance Alloy catalysts: Enhancing
Activity and Switching Selectivity by the Incorporation ofPalladium into Gold Nanoparticles,
T. Shishido, (Jan. 4th (Fri)), National Taiwan University,
Taipei, Taiwan.
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
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.
100th annual meeting of CSJ “Hydrogen production by
supported alloy nanoparticle catalysts” T. Shishido,
2020/3/22-26, Tokyo University of Science.

9.

10.

11.

12.

13.

■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
30

Symposium on Hybrid Catalysis for Enabling MolecularSynthesis on Demand, May 30-31, 2019, Tokyo, Japan
Development of perovskite type catalyst for oxidative
coupling of methane
A. Nishida, H. Miura, T. Shishido, The 8th Asia PacificCongress on Catalysis (APCAT-8) August 4-7, 2019,
Bangkok, Thailand
One pot conversion of glycerol to lactic acid oversupported platinum catalyst
K. Takahashi, S. Feng, H. Miura, T. Shishido, The 8th
Asia-Pacific Congress on Catalysis (APCAT-8) August 47, 2019, Bangkok, Thailand
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 47, 2019, Bangkok, Thailand
Interconversion between bicarbonate and formate oversupported 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[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
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
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
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
Supported Pd-based alloy catalysts for highly efficienthydrogen storage system based on carbon dioxide/formic
acid cycle
M. Waseda, E. Kawai, H. Miura, T. Shishido, The fourthInternational Symposium on Hydrogen Energy-based
Society August 22-23, 2019, Tokyo, Japan
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
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 andEco-materials, November 5-8, 2019, Yancheng, China＊Domestic
See the annual report in Japanese (40 articles)■Awards

Reports from Research Groups
1.

2.

3.

4.

5.

6.

7.

8.

9.

Poster Award "Alloying effect of Pd and Au on selectivehydrosilylation of allenes" Suguru Sasaki 121th CatSJ
Meeting (22-23 March 2018, The University of Tokyo).
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).
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.
Best Poster Award “Sillylation of sp2 C-H bonds inheteroaromatics by supported Au catalysts” Ryuji Hirata
17th catalysts chemistry workshop at Himeji, July 25,
2019, Hyogo
Excellent Poster Award ‘‘Sillylation of sp2 C-H bonds inheteroaromatics by supported Au catalysts” Ryuji Hirata
9th CSJ chemistry festa, Funabori. 23-25 October 2019,
Tower Hall Funabori
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
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,
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
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 andEco-materials, November 5-8, 2019, Yancheng, China

31

Reports from Research Groups
Shudo Laboratory■Members
Toshio Shudo
Professor /Dr. Eng.
Energy Engineering,room: 9-455 TEL: +81-42-677-2715
e-mail: shudot@tmu.ac.jp
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 performanceof polymer electrolyte fuel cell. This research investigates theeffect of porous metal flow field for even supply of reactants tothe whole area of electrodes.
2. Performance improvement in direct methanol fuel cell.
Toshio Shudo
Direct methanol fuel cell system has higher energy density andlower power density compared to polymer electrolyte fuel cellsystem. 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 ofEngineering, Kyoto University)”Development of functional luminescent materials based on nonluminescent 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

Development of Biomolecular Functions”

389th

2019/10/16

33

for

Enhancement

and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