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

Annual Report 2023

IndexReports from Research Groups
Kawakami Laboratory

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1

Asayama Laboratory

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8

Kubo Laboratory

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10

Setaka Laboratory

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12

Kajihara Laboratory

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14

Yanagishit Laboratory

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16

Takagi Laboratory

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18

Shishido Laboratory

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23

Analytical Chemistry Laboratory

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26

Shudo Laboratory

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29

Amano Laboratory

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30

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32

ColloquiumReports from Research Groups
Kawakami Laboratory■Members

1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO

Hiroyoshi KAWAKAMI
Professor / Dr. Eng.
Polymer Chemistry, Functional Polymers, Nanofiber
Engineering, Biomaterials, Epigenetics Engineering, Cell
Engineering
Rm. 9-638, +81-42-677-1111 Ext. 4972
kawakami-hiroyoshi@tmu.ac.jp

Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO 2). 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 conducted investigations using SAXS and othermethods on the gas permeation mechanism of composite
membranes with newly developed surface-modified silica
nanoparticles added, as well as the mechanism by which
toughness is not reduced. It was suggested that the structure ofparticle clusters is important for the manifestation of material
properties.

Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-Science, DAC, Fuel Cells, Organicinorganic Hybrid Material, Thin Film Process, Anisotropy
Control
Rm. 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 Chemistry, Exosomes,
Cell Engineering, Epigenetics Engineering
Rm. 9-349, +81-42-677-1111 Ext. 4886
sato-kiyoshi@tmu.ac.jp
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.jp
Hidetaka NORITOMIAssistant Prof. / Dr. Eng.
Biotechnology, Chemical Engineering, Colloid Chemistryroom: 9-148
TEL: +81-42-677-1111 Ext.4838
e-mail: noritomi @tmu.ac.jp
Masahiro YOSHIOKA
Research Associate Professor / Ph.D.
Molecular biology, Cancer Research, Cellular Biology
Rm. 9-649, +81-42-677-1111 Ext. 4974
masahiro-yoshioka@tmu.ac.jp

Figure 1. Schematic drawing of nanoparticle/PIM-1 composite
membrane.
2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA, Masafumi
YAMATO, Kiyoshi SATO, Yasuyo OGINO

Yasuyo OGINO
Research Associate / Dr. Sci.
Fuel Cells, Secondary Batteries, Layered Double Hydroxide,
Inorganic
Chemistry, Photochemistry,
Organometalic
Chemistry, Coordination ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
yogino@tmu.ac.jp
Keisuke Ashiba
Visiting Associate Professor / Dr. Eng.
Biomaterials, Cell Engineering, Regenerative
Engineering, Cell Culture Engineering
Rm. 9-349, +81-42-677-1111 Ext. 4886
ashiba@tmu.ac.jp

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, novel nanofiber composite membranes were
fabricated to improve proton conductivity. Blend nanofibers
consisting of polybenzimidazole and sulfonate poly(arylene
ether sulfone) (SPAES) were fabricated. After doping withphytic acid, the nanofibers were composed with Nafion to yield
nanofiber composite membranes. It was revealed that thecomposite membrane using SPAES with higher sulfonic acidcontents showed improved proton conductivity. Development ofnovel nanofiber composite membranes using novel sulfonatedpolymers as nanofibers and matrix polymer electrolytes werealso investigated. Radical quenchers to improve membranestabilities were also developed.
Another study on water electrolysis using anion exchange
membranes and anion exchange ionomers were also carried out.

MedicalDoctor’s course - 4
Master’s course - 19
Bachelor 4 - 11
Researcher - 3■Outlines of the Research1Reports from Research Groups

NF

Matrix(Nafion)

abnormalities. However, epigenomic alterations are reversible
and therefore can be reversed artificially, resulting in providing
a new therapeutic method.
To expand the therapeutic range of epigenetics-controlled
nanocarriers that can co-deliver three epigenetic drugs, theapoptosis- and cellular senescence-inducing effects were tested
in various type of cancer cells. Similar effects were confirmed
against multiple cancer cells, indicating the generality of thetherapeutic effects of the epigenetics-controlled nanocarriers.

NF composite
membrane

Figure 2. Fabrication of blend polymer nanofiber composite
membranes consisting of SPAESs with different sulfonic acidcontents for fuel cell applications.
3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA, Yasuyo OGINO

Figure 4. Gene expression control through chromatin
modifications.

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 developed polymer nanofiber composite
membranes for all solid state secondary batteries. The nanofiber
composite membranes consisted of poly(ethylene oxide) (PEO)based matrix electrolytes with different lithium salt
concentrations were fabricated. The nanofiber composite
membranes, especially with low lithium ion concentration,
showed high ion conductivity and lithium transference number
by composing with nanofibers.
Another study on rechargeable zin air batteries using anion
conductive nanofiber-based gel polymer electrolyte membranes
were also carried out.

5. Suppression of Cellular Senescence
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Masahiro
YOSHIOKA, Keisuke ASHIBA
Although cellular senescence functions as a tumor-suppressive
mechanism, the accumulation of senescent cells in various
tissues causes age-related diseases such as diabetes andAlzheimer's disease. Moreover, the cytokines and chemokines
secreted by senescent cells affect neighboring cells. Cellularsenescence is also a major factor in quality deterioration of thesource cells. Therefore, suppression of cellular senescence ofstem cells and immune cells during in vitro expansion is one of
the most important issues for the prevalence of regenerative
medicine and cell-based therapy.
In this year, we investigated that reactivation of mitophagy inearly- and late-passage mesenchymal stem cells and long-term
cultured T cells by mitophagy-induced liposomal nanocarriers(M-NC). The M-NC removed dysfunctional mitochondria fromthe senescent cells and restored the cell proliferation ability andcell function. Thus, M-NC will provide new strategies for the exvivo cell expansion for regenerative medicine and cell therapy.
Liposome

Mn Porphyrin (MnP)

DOTMA + DOPE (1:1)

N

p53 inhibitor(pifithrin-a)

N

Mn
N

N

N

N

O
H 3C

CH3

N

SOD activity:
kdis = 8.3± 5.0 (106 M-1s-1)

Particle size: 52± 13 (nm)
Zeta potential: 61± 2.5 (mV)

NH

CH3

S

Figure 5. Structure of mitophagy-induced liposomal nanocarrier.

Figure 3. Fabrication of nanofiber composite membranes
consisting of polymer matrix electrolytes with different lithium
salt concentrations for all-solid-state lithium ion batteries.

6. Fabrication of Engineering Exosomes
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Masahiro
YOSHIOKA

4. Epigenetics Engineering for Cancer Therapy
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Masahiro
YOSHIOKA

Exosomes are a type of extracellular vesicles with a diameterof 50 to 200 nm, and function as transport carriers forintercellular communications that selectively deliver miRNAs
and proteins to target cells. In recent years, its use in cancer
diagnosis has been investigated. Research of engineered
exosomes is also active due to the excellent biocompatibility andEpigenetics is a system to control the ON/OFF switch ofgene expression without altering the DNA base sequence, andmaintains the changes after cell division. Many diseases,
including cancer, are strongly associated with epigenetic

2

Reports from Research Groups
transport selectivity that can be used as DDS carriers bymodifying natural exosomes or by modifying mother cells to
produce exosomes with enhanced therapeutic efficacy.
In this year, we investigated the fabrication of engineered
exosomes that incorporate drugs or miRNA for the therapy oftarget cells into exosomes secreted from mesenchymal stem cells
and cancer cells. These engineered exosomes are expected toserve as new therapeutic methods and DDS carriers.

2.

3.

4.

Figure 6. An example for engineering exosome.
7. Processing of feeble magnetic materials under a magnetic
field
Masafumi YAMATO

5.

We are conducting research aimed at controlling the higherorder structure skillfully by utilizing the feeble magnetic
properties exhibited by many substances, with the goal of
improving material characteristics and manifesting novel
functionalities. This year, we investigated the magnetic
orientation of layered double hydroxide, specificallyhydrotalcites. It was revealed that the easy magnetization axis ofhydrotalcites varies depending on the constituent metal species.
Those containing transition metals exhibiting paramagnetism
transitioned to paramagnetic behavior, with the manifestation ofmagnetic dipole interactions becoming apparent. These findings
suggest that new methods of controlling higher-order structures
could be provided for the development of composite materials
including hydrotalcites.

6.

Conductive Mechanism and High Stability for NextGeneration Fuel Cells", ACS Applied Polymer Materials,
5,7,5177-5188(2023).
DOI:
https://pubs.acs.org/doi/10.1021/acsapm.3c00656
Keisuke Ashiba, Koki Mino, Yui Okido, Kiyoshi Sato,
Hiroyoshi Kawakami, “Senescence recovering by dual
drug-encapsulated liposomal nanoparticles for large-scale
human cell expansion”, Journal of Artificial Organs, 26,
246-250 (2023). DOI: 10.1007/s10047-022-01356-x
Kiyoshi Sato, Hiroyoshi Kawakami, “Mitochondrial
Dysfunction and Nanocarrier-Based Treatments in
Chronic Obstructive Pulmonary Disease (COPD)”,
Oxygen,3,
394-406(2023).
DOI:
10.3390/oxygen3040026
Momoka Chatani, Naomi Saito, Masahiro Yoshioka,
Yuichi Kinoshita, Hanae Nakamura, Yuki Hashimoto,
Akiko
Takenouchi,
Katsuhiko
Yoshizawa,“Pathophysiological effect of acerola in streptozicininduced cataract rat model”, Functional Food Research,
19, 90-99, (2023) (in Japanese).
Nagy L. Torad, Yuta Tsuji, Azhar Alowasheeir, Masako
Momotake, Kazuki Okazawa, Kazunari Yoshizawa,
Michio Matsumoto, Masafumi Yamato, Yusuke Yamauchi,
Miharu Eguchi, “Extraordinary Acceleration of an
Electrophilic Reaction Driven by the Polar Surface of 2D
Aluminosilicate Nanosheets”, Small, 2205857 (2023).
Yasuko Noritomi, Takashi Kuboki, Hidetaka Noritomi,“Enhancement of catalytic efficiency of enzymatic redox
reaction by composing a horseradish peroxidase-modified
electrode with ionic liquids”, Liquids, submitted.

■Books1.
Manabu Tanaka, Hiroyoshi Kawakami, "Electrospun
Sulfonated Polyimide Nanofibers for Polymer Electrolyte
Composite Membranes", in "Polyimides - Advances in
Blends and Nanocomposites", M.-D. Damaceanu, R. N.
Darie-Nita, Eds, Chapter 9, pp325-352, Elsevier (2023).
2.
Yuri Nara, Hiroyoshi Kawakami, Manabu Tanaka, “Water
Electrolysis using Anion Exchange Membranes”, in“Recent Trends of Methanation and Green Hydrogen”,
Yasushi Sekine, Ed, Chapter 7, Section 3, 208-215, CMC
Publishing (2023). (in Japanese)
3.
Manabu Tanaka, “Tips for Researching Abroad – Let’s goabroad for now !”, Sen’i Gakkaishi (Journal of The Societyof Fiber Science and Technology, Japan), 80, 1, P2-6
(2024).
4.
Hiroyoshi Kawakami, “Polymer Nanofiber Composite
Electrolyte Membrane” Journal of the Society of Polymer
Science, 72,11, p.p550-552 (2023).
5.
Hiroyoshi Kawakami, “CO2 separation using highly
permeable polymer membranes,” Separation Technology
Society Journal, 53,6, 352-359 (2023).
6.
Hiroyoshi Kawakami, “Polymer Materials Chemistry forEngineering [Newly Revised Edition]” Science Publishing,2024 edition.
7.
Masafumi Yamato, "Functional Control of Crystalline
Polymers Using Magnetic Orientation”, in “Enhancementof Performance through Polymer Crystallization andStretching”, CMC Publishing, (2024). (in Japanese)
8.
Masafumi Yamato, Hiroyoshi Kawakami, "Developmentof Ultra-High CO2 Permeable Separation Membranes

Figure 7. Crystal structure of hydrotalcite (left) and schematic
drawing of magnetic orientation (right).
Application of biochar to stress tolerance of enzymes
Hidetaka NORITOMI
To reduce greenhouse gas emissions, biochar was prepared fromforestry residues, which are carbon neutral, and was used as an
enzyme carrier. We found that biochar imparts high heat stress
tolerance and organic solvent stress tolerance to enzymes. This
result would be expected to the applications to bioprocesses suchas bioreactors, biosensors, and biofuel cells.
■Papers with Peer Review
1.
Kazuto Suzuki, Manabu Tanaka, Masahiro Kuramochi,
Shun Yamanouchi, Noriko Miyaguchi, Hiroyoshi
Kawakami, "Development of Blend Nanofiber Composite
Polymer Electrolyte Membranes with Dual Proton

3

Reports from Research Groups

9.

Using Nano-Spaces", in “Recent Trends in Methanation
and Green Hydrogen" CMC Publishing, (2023). (inJapanese)
Masafumi Yamato, Kazuma Komine, Kohki Takahashi,
Development of organic-inorganic composite materials
with high gas permeability II, 2022 Annual report of highfield laboratory for superconducting materials in institutefor materials research at Tohoku university，p.p. 161-162(2023) (in Japanese)

17.

18.

■Invited Lectures
1. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2022 Basic seminar of polymer science for young
engineers, Dec. 2023, Tokyo, Japan (in Japanese).
2. Masafumi Yamato and Hiroyoshi Kawakami, Advancing
nanoparticle-containing gas separation, International
Conference on Nano Research and Development, Dec.
2023 (Singapore)
3. Masafumi Yamato，Towards the realization of CO 2 Direct
Air Capture (DAC): the 371st Meeting of the Science andTechnology Outlook Conference，Jan. 2024, Tokyo, Japan(in Japanese)
4. Kiyoshi Sato, “Nanocarriers for designer exosomes”,
COSME Tech 2024 Tokyo (Tokyo), January 2024 (inJapanese).
5. Manabu Tanaka, Water Electrolysis using Anion Exchange
Membranes for Green Hydrogen Production, Johokiko
Seminar, June 2023, Online (in Japanese).
6. Manabu Tanaka, Anion Exchange Membrane Water
Electrolysis: From Fundamentals to State-the-art Research,
CMC research webinar, July 2023, Online (in Japanese).
7. Manabu Tanaka, Anion Conductive Polymers for Water
Electrolysis, JAIST seminar, August 2023, Ishikawa.
8. Manabu Tanaka, Fuel Cell Applications of Proton
Conductive Polymer Nanofiber Frameworks, Topical
Seminar, Hydrogenomics Alliance, Japan, October 2023,
Online (in Japanese).
9. Manabu Tanaka, Fundamentals and Key Technology ofAnion Exchange Membrane Water Electrolysis, Technical
Information Institute Seminar, November 2023, Online (inJapanese).
10. Manabu Tanaka, Anion Exchange Membrane Water
Electrolysis for Green Hydrogen Production, Johokiko
Seminar, December 2023, Tokyo (in Japanese).
11. Manabu Tanaka, Recent Advances on Anion Exchange
Membrane Water Electrolysis, 2nd UK-Japan Symposium
on Advanced Materials, January 2024, Online.
12. Manabu Tanaka, Organic Nanoionics in Polymers forEnergy Conversion System, Chemistry Department
Seminar, University of Cambridge, March 2024,
Cambridge, UK.
13. Kiyoshi Sato, “Production of functional exosomes using
designer cells created by nanocarrier treatment”, The 6th
Regenerative Medicine Industry-Academia Collaboration
Techno Action (Niigata), March 2024 (in Japanese).
14. Masafumi Yamato，”Study in Direct Air Capture”, EcoPro
2023 (Tokyo)，Dec. 2023.
15. Hiryoshi Kawakami, “Electrolyte membrane initiatives
with a view to 2030 and beyondt”, Fuel Cell ResearchGroup 158th Seminar (Tokyo), June 2023.
16. Hiroyoshi Kawakami, "Aiming for DAC with polymer

19.

20.

21.

22.

membranes - Development of ultra-high CO2 permeation
separation membranes-", RITE Industrialization Strategy
Council 23rd Seminar, (Online), July 2023.
Hiroyoshi Kawakami, "Creation of designer stem cells andtheir functions of modified exosomes produced", 5th
PharmaLab EXPO Tokyo, Tokyo, July 2023.
Hiroyoshi Kawakami, "Possibility of DAC using ultrahigh CO2 permeability separation membrane",
Information Technology Organization Seminar, Tokyo,
September 2023.
Hiroyoshi Kawakami, "Research and development of new
proton-conducting membranes for next-generation fuelcells", 14th New Electrocatalyst Symposium, Shizuoka,
October 2023.
Hiroyoshi Kawakami, "Polymer Revolution: New Global
Warming Countermeasures Opened Up by Mass
Transport", Science Techno Frontier Forum at Universityof Tokyo, Tokyo, March 2024.
Hiroyoshi Kawakami, "CO2 separation using highly
permeable polymer membranes", 29th Kansai Region
Separation Technology Lecture, (held online), March 2024.
Hiroyoshi Kawakami, " 2023 NEDO Fuel Cell/Hydrogen
Technology Development Roadmap Report Meeting",
NEDO, (held online), March 2024.

■Academic Meeting
1. Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami. Temperature dependence of gas permeation
properties in polymer of intrinsic microporosity (PIM-1)：
effect of physical aging. 72th SPSI Annual Meeting (GMESSE GUNMA), 100556, May 2023.
2. Kota Nagano, Masafumi Yamato, and Kawakami
Hiroyoshi, Pressure dependence of gas permeation
properties of surface-modified silica nanoparticle/PIM-1
composite membranes, 72th SPSI Annual Meeting (GMESSE GUNMA), 1Pa061, May 2023 (in Japanese)
3. Natsuki Inoue, Manabu Tanaka, Hiroyoshi Kawakami,
Chemical durability evaluation of nanofiber composite
membranes for polymer electrolyte fuel cells, The 72thSPSI Annual Meeting (G-Messe Gunma), 3Pb052, May
2023 (in Japanese)
4. Kazuki Takashio, Masafumi Yamato, Hiroyoshi Kawakami,
Effect of solvents on asymmetric fluorine-containing
polyimide membranes by dry-wet phase inversion process,The 72th SPSJ Annual Meeting (Gunma Convention
Center), 1Pb062, May 2023 (in Japanese)
5. Yusuke Fujita, Koki Mino, Keisuke Ashiba, Masahiro
Yoshioka, Kiyoshi Sato, Hiroyoshi Kawakami, Productionof Designer Stem Cells by Reactivation of Mitophagy, 72thSPSI Annual Meeting (Gunma), May 2023.
6. Ryodai Fujihashi, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Conductivity Evaluation of Nanofiber
Composite Electrolyte Membranes Consisted ofCarbonate-based Solid Polymer Electrolytes, The 72th
SPSJ Annual Meeting (Gunma Convention Center),
1Pa053, May 2023 (in Japanese)
7. Yasutaka Kuwahara, Toyotaka Nakae, Hiroyoshi
Kawakami, Fabrication of electrolyte composite
membranes using PVA nanofiber framework and its fuelcell property, The Annual Meeting of the society of fiber4

Reports from Research Groups

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

science and technology Japan (Tower Hall Funabori), 1C08,
June 2023 (in Japanese)
Natsuki Inoue, Kazuto Suzuki, Manabu Tanaka, Hiroyoshi
Kawakami, Fuel Cell Characterization of Nanofiber
Composite Electrolyte Membranes with High Proton
Conductivity and Durability, The Annual Meeting of thesociety of fiber science and technology Japan (Tower Hall
Funabori), 1C15, June 2023 (in Japanese)
Akari Tatsukawa, Toyotaka Nakae, Hiroyoshi Kawakami,
Effects of Post-treatment on Fuel Cell Properties ofPolymer Nanofiber Composite Membranes, The Annual
Meeting of the society of fiber science and technology
Japan (Tower Hall Funabori), 1C16, June 2023 (inJapanese)
Ryodai Fujihashi, Kenta Sando, Manabu Tanaka,
Hiroyoshi Kawakami, Lithium ion
conductive
characteristics of polymer nanofiber composite electrolyte
membranes fabricated from different polymer electrolytes,
The Annual Meeting of the society of fiber science andtechnology Japan (Tower Hall Funabori), 1C04, June 2023
(in Japanese)
Masahiro Yoshioka, Hiroyoshi Kawakami, Senescenceinduction in epigenetically modified cancer cells andalternation of extracellular vesicles, The 27th Annual
Meeting of the Japanese Association for Molecular Target
Therapy of Cancer (Saga City Cultural Center), P4-02,
June. 2023.
Hiyori Iitsuka, Shuntarou Kimura, Masayoshi Yoshioka,
Kiyoshi Sato, Hiroyoshi Kawakami, Characterization ofcancer senescent cells epigenetically modified byfunctional nanocarriers, The 52nd symposium on medical
polymers (Tokyo), July 2023 (in Japanese)
Kiyoshi Sato, Ayaka Mori, Koki Mino, Keisuke Ashiba,
Masahiro Yoshioka, Hiroyoshi Kawakami, “Exosomemimicking liposomal nanocarriers for rejuvenation ofsenescent stem cells”, 13th International Congress on
Membranes and Membrane Processes (ICOM 2023) July
2023 (Makuhari Messe)
14. Manabu
Tanaka,Hiroyoshi
Kawakami,
Development of All-Solid-State Lithium Ion Batteries
based on Polymer Nanofiber Composite Electrolyte
Membranes, 13th International Congress on Membranes
and Membrane Process (Makuhari Messe), O1.MF-10,
July 2023.
Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami. Effect of physical aging on the temperaturedependence of gas permeation properties of polymer of
intrinsic microporosity (PIM-1). 13th International
Congress on Membranes and Membrane Process(Makuhari Messe), P2-MH-06, July 2023.
Kota Nagano, Masafumi Yamato, and Kawakami
Hiroyoshi, Pressure dependence of gas permeation
properties of PIM-1 composite membranes loaded withsurface-modified silica nanoparticles, ICOM2023(MAKUHARI MESSE), P2-MX-08, July 2023
Natsuki Inoue, Manabu Tanaka, Hiroyoshi Kawakami,
Development of nanofiber composite electrolyte
membranes with high proton conductivity and durability
for fuel cell applications, 13th International Congress on
Membranes and Membrane Processes (Makuhari Messe),
P2-MF-12, July 2023 (in English)

18. Kazuki Takashio, Masafumi Yamato, Hiroyoshi Kawakami,
Effect of solvents on asymmetric polyimide membranes
containing surface-modified silica nanoparticles by drywet phase inversion process, 13th International Congress
on Membranes and Membrane Processes (Makuhari
Messe), P2-MX-09, July 2023.
19. Akari Tatsukawa, Toyotaka Nakae, Hiroyoshi Kawakami,
Effects of thermal treatment of polymer nanofiber
composite membranes on the proton-exchange properties,
The 13th International Congress on Membranes andMembrane Processes (Makuhari Messe), P2-MF-13, July2023.
20. Yusuke Fujita, Koki Mino, Keisuke Ashiba, Masahiro
Yoshioka, Kiyoshi Sato, Hiroyoshi Kawakami,
Development of mitophagy-inducing nanocarriers forrejuvenation of senescent mesenchymal stem cells,
ICOM2023 (Chiba), P1-BD-30, July 2023.
21. Kiyoshi Sato, Hiyori Iitsuka, Haruka Mitome, Masahiro
Yoshioka, Hiroyoshi Kawakami, “New strategy for cancer
therapy by cell conversion from cancer cells to senescentcells”, 72nd Symposium on Macromolecules, September
2023 (Kagawa Uviv,) (in Japanease)
22. Manabu Tanaka, Yubing Dong, Hiroyoshi Kawakami,
Fabrication of Cross-linked Network Polymer Electrolyte
Membranes and Their Application to Lithium Ion Batteries,
72nd Polymer Symposium in Japan, 1M15, September
2023 (Kagawa Univ.) (in Japanease).
23. Masahiro Yoshioka, Yusuke Fujita, Kiyoshi Sato,
Hiroyoshi Kawakami, Mitophagy-inducing nano-carrier
for the production of designer stem cells, The 72th Polymer
Symposium in Japan, (Kagawa Univ.), 2Pc89, Sept. 2023.
24. Yuri Nara, Shuhei Koyama, Kento Kasahara, Kensaku
Nagasawa, Yoshiyuki Kuroda, Shigenori Mitsushima,
Hiroyoshi Kawakami, Manabu Tanaka, Synthesis andwater electrolysis application of various anion conductive
polyfluorenes with different ion exchange capacities, 72nd
Polymer Symposium in Japan, 2M17, September 2023
(Kagawa Univ.) (in Japanease).
25. Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami. Gas Permeability Performance of Polymer ofIntrinsic Microporosity (PIM-1) at Temperatures Near
100 °C. 72nd Symposium on Macromolecules (Kagawa
University), September 2023.
26. Kota Iwasaki, Ryota Inahara, Natsuki Inoue, Akari
Tatsukawa, Manabu Tanaka, Hiroyoshi Kawakami,
Development of polymer nanofiber-based composite
electrolyte membranes and evaluation of the proton
conduction mechanism in the composite membranes, The
72th Polymer Symposium in Japan, (Kagawa Univ.), 2M12,
Sept. 2023. (in Japanese)
27. Kaito Udo, Mizuki Akatsuka, Masafumi Yamato,
Hiroyoshi Kawakami, Property of high gas permeable
polymer membranes at high temperature, The 54th SCSJ
Autmn meeting (Fukuoka Univ.), PA333, Sept. 2023.
28. Kota Nagano, Masafumi Yamato, and Kawakami
Hiroyoshi, CO2 permeation properties of surface-modified
nanoparticle/PIM-1 composite membrane at low feed
pressure, SCEJ 54th Autumn Meeting (Fukuoka Univ.),
K123, Sept. 2023
29. Kota Nagano, Masafumi Yamato, and Kawakami
Hiroyoshi, Pressure dependence of gas permeation of5

Reports from Research Groups

30.

31.

32.

33.

34.

35.

36.

37.

38.

surface-modified
nanoparticle/PIM-1
compositemembranes, SCEJ 54th Autumn Meeting (Fukuoka Univ.),
PA334, Sept. 2023
Yuri Nara, Moe Tomita, Kento Kasahara, Kensaku
Nagasawa, Yoshiyuki Kuroda, Shigenori Mitsushima,
Hiroyoshi Kawakami, Manabu Tanaka, Synthesis andWater Electrolysis Application of Poly(fluorene) Anion
Conductive Polymers, FEMS EUROMAT 2023 (Online
Virtual Meeting, Germany), #1663, September 2023.
Yasutaka Kuwahara, Miyui Ono, Yuri Nara, Hiroyoshi
Kawakami, Manabu Tanaka, Fabrication of Anion
Conductive Gel Polymer Electrolyte Membranes and Their
Application to Rechargeable Zinc Air Batteries, 45th
annual meeting of membrane science of Japan (ResearchInnovation Center Waseda University), P-31S, November
2023 (in Japanease).
Kaito Udo, Mizuki Akatsuka, Masafumi Yamato,
Hiroyoshi Kawakami, Temperature dependence ofpolymer composite membranes containing surface
modified nanoparticles with high CO2 permeability, 45th
annual meeting of membrane science in Japan &Membrane Symposium 2023, P-15A, Nov. 2023.
Natsuki Inoue, Manabu Tanaka, Hiroyoshi Kawakami,
Effects of polymer nanofibers on chemical stability ofnanofiber composite electrolyte membranes for fuel cells,
45th Annual Meeting of Membrane Science of Japan andMembrane Symposium 2023 in Japan, (Waseda Univ.), P32S, November 2023 (in Japanese)
Ellie Fujiwara, Hiyori Iitsuka, Haruka Mitome, Masahiro
Yoshioka, Kiyoshi Sato, Hiroyoshi Kawakami, Inductionof Cellular Senescence in Cancer Cells by Epigenetic
Control Carriers and Modification of Their Extracellular
Vesicles, 45th Annual Meeting of Membrane Science ofJapan and Membrane Symposium 2023 in Japan (Waseda
Univ.), P-66S, November 2023 (in Japanese)
Ryota Inahara, Natsuki Inoue, Kota Iwasaki, Akari
Tatsukawa, Manabu Tanaka, Masafumi Yamato, Hiroyoshi
Kawakami, Fabrication and fuel cell evaluation ofcomposite electrolyte membranes composed of acid-doped
nanofibers for higher proton conductivity over a wide
temperature and humidity range, The 64th Battery
Symposium in Japan (Osaka International Convention
Center), 2H14 , November 2023 (in Japanese)
Kenta Sando, Manabu Tanaka, Hiroyoshi Kawakami,Secondary battery evaluation of polymer nanofiber
composite electrolyte membranes with different lithium
salt concentrations, The 64th Battery Symposium in Japan(Osaka International Convention Center), 2A03,
November 2023 (in Japanese)
Dong Yubing, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Lithium Battery Application of Networkstructured Polymer Gel Electrolyte Membranes Containing
Solvate Ionic Liquid, The 64th Battery Symposium inJapan (Osaka International Convention Center), 2A02,
November 2023 (in Japanese)
Hiyori Iitsuka, Haruka Mitome, Masayoshi Yoshioka,
Kiyoshi Sato, Hiroyoshi Kawakami, Senescence-induction
in cancer cells by epigenetics-controlled carrier and antitumor exosome production, The 45th annual meeting ofJapanese society of biomaterials (Kobe), November 2023
(in Japanese)

39. Bunta Mizoguchi, Yusuke Fujita, Koki Mino, Masahiro
Yoshioka, Kiyoshi Sato, Hiroyoshi Kawakami, Enhanced
therapeutic efficacy of activated MSC by mitophagy
reactivation, The 45th Annual Meeting of Japanese Society
for Biomaterials(Kobe), November 2023
40. Yusuke Fujita, Masahiro Yoshioka, Kiyoshi Sato,
Hiroyoshi Kawakami, Production of designer stem cells byadministering functional nanocarriers, The 61st Annual
Meeting of the Japanese Society Artificial Organs (Tokyo),
November 2023.
41. Yosuke Saito, Shun Nakazawa, Kenta Sando, Manabu
Tanaka, Hiroyoshi Kawakami, Effects of Nanofiber
Composite to Solid Polymer Electrolyte Membranes for
Lithium-Ion Batteries, 31th Japan Polyimides & Aromatic
Polymers Conference (Tokyo Institute of Technology), P23,
November 2023
42. Hiroki Mizuta, Kota Iwasaki, Kazuto Suzuki, Motoki
Nishizawa, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Fuel Cell Evaluation of Composite
Electrolyte Membranes Based on Sulfonated Polyimide
Blend Nanofibers, 31th Japan Polyimides & Aromatic
Polymers Conference (Tokyo Institute of Technology), P24,
November 2023
43. Yuki Shinada, Masafumi Yamato, Magnetic alignment ofLayered Double Hydroxides P-18, The Magneto-Science
Society of Japan 17th annual convention (Fukui Universityof Technology), Nov. 2023 (in Japanease).
44. Hiyori Iitsuka, Haruka Mitome, Masahiro Yoshioka,
Kiyoshi Sato, Hiroyoshi Kawakami, “Antitumor effects ofextracellular vesicles secreted from senescence-induced
cancer cells”, The 46th Annual Meeting of the Molecular
Biology Society of Japan, December 2023 (Kobe Port
Island) (in Japanease).
45. Hanae Nakamura, Masahiro Yoshioka, Yuichi Kinoshita,
Momoka Chatani, Akiko Takenouchi, Katsuhiko
Yoshizawa, “Inhibitory effects of black soybean seed coat
extract (Chrono-Care®) supplementation on breast cancer
model in rats”, The 20th Annual Meeting of Society for
Functional Food Research (Yonago convention center), Y1, January, 2024 (in Japanese)
46. Kiyoshi Sato, Yusuke Fujita, Masahiro Yoshioka,
Hiroyoshi Kawakami, “Designer stem cells with enhanced
therapeutic efficacy by improving mitochondrial quality
control mechanisms”, The 23rd Congress of the JapaneseSociety for Regenerative Medicine, March 2024 (TOKI
MESSE Niigata Convention Center) (in Japanese).
47. Masafumi Yamato, Hiroyoshi Kawakami,Thermal
Properties of PIM-1 Membranes，The 13th International
Congresson
Membranes
andMembrane
Processes(ICOM2023) (Makuhari),July 2023
48. Masafumi Yamato, Hiroyoshi Kawakami, Ultra-gas
permeable mixed matrix membrane composed of polymer
of intrinsic microporosity (PIM-1) and surface-modified
silica nanoparticles, The 13th International Congress on
Membranes and Membrane Processes(ICOM2023)(Makuhari),July 2023
49. Masafumi Yamato, Hiroyoshi Kawakami, Development ofSurface-Modified
Nanoparticle/PIM-1
Composite
Membranes Targeting Membrane-based DAC, Sep. 2023
(Takamatsu) (in Japanese)
50. Masafumi Yamato, Hiroyoshi Kawakami, Structure and6

Reports from Research Groups
Physical Properties of Highly loaded membranes with
SilicaNanoparticles,
72nd
SymposiumonMacromolecules, Sep. 2023 (Takamatsu) (in Japanese)
51. Masafumi Yamato, Yuki Shinada, Magnetic Alignment ofLayered Double Hydroxide, 71 st JSAP Spring Meeting,Mar. 2024 (Tokyo) (in Japanese)■Patents
1.

2.

3.

Nanofiber adduct, electrolyte membrane, composite
electrolyte membrane, fuel cell, Hiroyoshi Kawakami,
Kiyoshi Sato, Patent application 2023-91800 (2022/6/2)
Complex for eliminating dysfunctional mitochondria andcomplex for suppressing cellular aging, Hiroyoshi
Kawakami, Kiyoshi Sato, Patent No. 7429035 (2024/1/30)
Gas Separation Membrane, Hiroyoshi Kawakami,
Masafumi Yamato, Takumu Morita, Mizuki Akatsuka，
PCT/JP2024/002225 (2024/1/25)■Awards
1.

2.

3.

4.

5.

6.

7.

8.

The 72th SPSI Annual Meeting, Poster Award, Natsuki
Inoue, “Chemical durability evaluation of nanofiber
composite membranes for polymer electrolyte fuel cells”.
he 52nd symposium on medical polymers, Student
Presentation Award, Hiyori Iitsuka, “Characterization ofcancer senescent cells epigenetically modified byfunctional nanocarriers”.
SCEJ 54th Autumn Meeting, Student Award, Kota Nagano,“Pressure dependence of gas permeation of surfacemodified nanoparticle/PIM-1 composite membranes”
45th annual meeting of membrane science in Japan &Membrane Symposium 2023, Student Award, Kaito Udo,
“Temperature dependence of polymer composite
membranes containing surface modified nanoparticles
with high CO2 permeability”.
45th Annual Meeting of Membrane Science of Japan andMembrane Symposium 2023 in Japan, Student Award,
Natsuki Inoue, “Effects of polymer nanofibers on chemical
stability of nanofiber composite electrolyte membranes forfuel cells”.
The 45th Annual Meeting of Japanese Society for
Biomaterials,
Highlight
Presentation,
Bunta
Mizoguchi, ”Enhanced therapeutic efficacy of activated
MSC by mitophagy reactivation”.
The Magneto-Science Society of Japan 17th annual
convention, Student Poster Award, Yuki Shinada,“Magnetic alignment of Layered Double Hydroxides”.
31th Japan Polyimides & Aromatic Polymers Conference,
Student Poster Award, Hiroki Mizuta, Fabrication and Fuel
Cell Evaluation of Composite Electrolyte Membranes
Based on Sulfonated Polyimide Blend Nanofibers”.

7Reports from Research Groups
Asayama Laboratory■Members

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

Shoichiro ASAYAMA
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

Doctor’s course -1
Master’s course -7
Bachelor 4 -4N

Protein■Outlines of the Research
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:+

Delivery toUnexplored
Space

O
H2N

N

N

1-x-y

Zn2+

n

3. Biomaterials with Funtional Surface
Shoichiro ASAYAMA

Mono-Ion Complex【MIC】
C(CH2)nN

In this year, we have prepared Zn²⁺-encapsulated Chol-Lactovesicles with targeting ability to hepatic parenchymal cells andprepared carriers for stable and specific delivery of Zn²⁺ tohepatic parenchymal cells. The resulting Zn²⁺-encapsulated
vesicles showed higher intracellular uptake of Zn²⁺ than Zn²⁺
alone. When we used the control cells without ASGP-R,
furthermore, the vesicles did not show the higher intracellular
uptake. Thus, it is proved that Chol-Lacto vesicles are usefulas Zn²⁺ delivery carriers.

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).

+

N

H
C CH2

y

Figure 2. Remote control of hypoglycemic hormone in blood.

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

+

H
C CH2

x

+
N
N
(CH2) CH3

N+

Survival insulin
to whole bodyZn 2+

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 (Figure
3).

PEG

H3C

Most Simple
Noncovalent
PEGylation
DiseaseCH3O

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

CH2CH2O

n

CH3
H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

In this year, we have focused on zwitterionic polymers as analternative material to PEG and used them as carriers instead of
surface modification to form PICs with pDNA, which has a near
neutral surface charge and excellent pharmacokinetics in the
body. As a result, we enhanced the effect of shRNA in vivo
and showed a specific RNA interference effect on Mstn. We
found that the zwitterionic polymer/pDNA PIC with high tissue
diffusivity in skeletal muscle and inhibition of target gene
expression in situ is effective for nucleic acid-based gene therapy.

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 maximum number of modifications per unit
surface area to PP surfaces at each coating concentration of
Chol-PEG was calculated from the QCM experiments. As aresult, more were estimated for PP surfaces coated with theshorter Chol-PEG500 compared to Chol-PEG2000, which has alonger PEG molecular weight. Compared to Chol-PEG2000,
the PP surface coated with Chol-PEG500 almost completely
inhibited the adsorption of BSA. Thus, the superiority of themodification density of PEG500 over PP surfaces in inhibiting
protein adsorption was revealed.

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

8

Reports from Research Groups■Papers with Peer Review
1. Ryoto Kon and Shoichiro Asayama, Synthesis ofguanidinium-dendrimer-type pDNA carriers for gene delivery
into floating blood cells, Polymers for Advanced Technologies,
34, 3289-3295 (2023).
2. Ren Misaizu and Shoichiro Asayama, Synthesis of N-oxidepoly(1-vinylimidazole) for pDNA delivery systems in vivo,
Chemistry Letters, accepted.
■Reviews
See the annual report in Japanese (2 articles).
■Academic Meeting
See the annual report in Japanese (15 articles).
■Patents
See the annual report in Japanese (1 patent).

9

Reports from Research Groups
Kubo Laboratory■Members

2. Turn-on type afterglow probe for Hg2+ sensing by a PVAmediated triplet sensitizer
Yuji Kubo
Abstract
Chemical stimulus afterglow systems have attracted muchattention because of their potential applications in time-gatedbioimaging and background-free chemosensors. However, thisdevelopment is at the frontier because introducing a chemicalstimulus acceptable site may facilitate a competitive deactivation
process by molecular vibration and oxygen, making it difficult
to stabilize the triplet state. Therefore, it remains challenging todevelop chemosensing in the afterglow. In this study,
benzophenone-containing boronate crosslinked poly(vinyl
alcohol) (PVA) (BPB@PVA) was prepared for the first time toinvestigate whether the resultant PVA served as a triplet
sensitizer. We found that 9H-thioxanthene-2-methoxy-9-thione
1 was doped into BPB@PVA film, and the resultant film
1/BPB@PVA (1:20:1000) displayed Hg2+-induced afterglow
response with a lifetime of 75.9 ms, accompanying withyellowish green emission after ceasing irradiation light at 254
nm. The desulfurization of 1 by Hg2+ in the PVA film produces
room-temperature phosphorescence (RTP)-active thioxanthene2-methoxy-9-one 2, the emission quantum yield being increased
by benzophenone-derived cross linkage (Figure 3).

Yuji Kubo
Professor /Dr. Eng.
Organic Chemistry, Supramolecular Chemistry, Functional Dye
Room: 9-448 TEL: +81-42-677-3134
e-mail: yujik@tmu.ac.jp
Masato Ito
Assistant Professor /Dr. Sci.
Structural Organic Chemistry, Main-group
Functional Dye
room:9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: mito@tmu.ac.jp

Chemistry,

Doctor’s course -2
Master’s course -7
Bachelor -6■Outlines of the Research
1. Organic room-temperature phosphorescence materials
Yuji Kubo
Abstract
Considering low-cost, abundant resources and low
environmental pollution compared to precious metal-containing
inorganic materials, organic room-temperature phosphorescence(RTP) materials with improvement of intersystem crossing (ISC)
channel and minimization of vibration-based and oxygenmediated quenching have attracted considerable attention. In thiscontext, boronate particles prepared by dehydration reaction ofbenzene-1,4-diboronic acid with pentaerythritol, which showed
RTP behavior with a green afterglow in water. The long-lived
lifetime has motivated us to develop afterglow materials forapplication in chemseonesors. As a successful example, thefabrication of lactam-ring-containing rhodamine-graftedboronate particles enabled us to detect change in afterglow byadding Al3+, as a result of Förster-type energy transfer from thephosphorescent BP to the Al3+-interacting rhodamine dye 1 on
the surface (Figure 1). Furthermore, quantitative structureproperty relationship (QSPR) analysis between thenanostructure and RTP behavior of boronate assemblies was
elucidated by chemometrics methodology (Figure 2).

Figure 3. Turn-on type afterglow material using benzophenonecontaining bronate crosslinked PVA.
.
3. Thermochromic afterglow from benzene-1,4-dibronic
acid-doped co-crystals
Yuji Kubo
Abstract
The accurate thermosensing requires a minimum impact ofautofluorescence and light scattering from the samples. In thisstudy, we discovered that commercially available benzene-1,4diboronic
acid(BDBA)
doped
co-crystals
withtrimethylolpropane (TMP) exhibit excellent thermochromic
dual phosphorescence properties over a wide temperature range
from ‒132 to 40°C, despite its simple structure that does not haveany donor-acceptor linkage. The dual phosphorescence wasconsisted of monomeric benzene-1,4-diboronate (BDBA ester)and aggregation-stabilized species (Figure 4).

Figure 1. Metal ion-responsive afterglow martials.

Figure 2. Chemometrics-assisted QSPR analysis.

10Reports from Research Groups■Papers with Peer Review
1. M. Kawashiro, T. Mori, M. Ito, N. Ando and S. Shigehiro,
Photodissociative modules that control dual-emission properties
in donor–π–acceptor organoborane fluorophores, Angew. Chem.
Int. Ed., 2023, 62, e20303725. DOI: 10.1002/anie.202303725
2. S. Takegawa, M. Ito and Y. Kubo, Turn-on type afterglow
probe for Hg2+ sensing by a PVA-mediated triplet sensitizer, New.
J. Chem., 2023, 47, 12554–12560. DOI: 10.1039/D3NJ01281F

Figure 4. Thermochromic afterglow using a co-crystal
approach.

4. Synthesis of dye-sensitized photocatalysts for hydrogen
Production
Yuji Kubo
Abstract
It is worthwhile to develop functional dyes that could contributeto the Sustainable Development Goals (SDGs). Given thatphotocatalysts for hydrogen production is remained to beresearched due to its low efficiency. Sensitization of dye which
has high light-harvesting capability is a promising approach for
improving efficiency. In this study, benzofuran-fused BODIPY
dye with cyanoacrylic acid as an anchoring group (1) was
synthesized for the first time. Dye 1 has an intense absorption
band at 605 nm (ε = 1.07×105 M−1 cm−1) in THF. In thepresentation, the photocatalytic activity of 1-loaded TiO2 isdiscussed.

3. R. Hasegawa, M. Ito, and Y. Kubo, Tuning the triplet
population of arylselanyl-BODIPY photosensitizers throughsubstituents engineering for triplet-triplet annihilation photon
upconversion with perylene, J. Porphyr, Phthalocyanines, 2023,
27, 757–764. DOI: 10.1142/S1088424623500037
4. K. Kawaguchi, N. Sugawara, M. Ito and Y. Kubo,
Thermochromic afterglow from benzene 1,4-diboronic aciddoped co-crystals, Chem. Eur. J., 2024, e202303924. DOI:
10.1002/chem.202303924

6. Evaluation of the effect of peripheral aryl groups on thephysical properties of electron-rich heteroacenes
Masato Ito
Abstract
Near-infrared luminescent materials are expected to be applied
to super-resolution biological imaging and information
technology. In this study, we focused on electron-richheteroacenes containing oxygen atoms in the acene skeleton andsynthesized derivatives with various substituents at appropriate
positions to achieve luminescence in the long-wavelength region.
We also clarified the effect of peripheral Aryl groups on not only
the photophysical properties but also diradical properties by
expanding central π-conjugated skeleton (Figure 5).

■BooksSee the annual report in Japanese 1 book (Y. Kubo wrote his
separate part.)■Academic Meeting＊Domestic
See the annual report in Japanese (17 articles)■Awards
See the annual report in Japanese.

Ar

Ar

Normalized intensity

Ar

1.0

0.5

0.0

500

600

700
Wavelength / nm

800

900

Figure 5. Molecular design of oxygen-containing heteroacenes
and their emission properties.

11

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
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

Figure 2. Fluorene-diyl bridged molecular gyrotops (article #3).
Phenylenediamine derivatives with oxidation properties,
specifically phenylene-bridged diazacycloalkanes of varying
chain lengths (C10, C12, and C14) were investigated. X-ray
crystallography revealed differences in the structures aroundnitrogen atoms depending on chain length, with C10 having aperpendicular benzene plane and C14 having a co-planar plane

Doctor’s course -1
Master’s course -8
Bachelor 5■Outlines of the Research
Development of Highly Designed Organic Molecules
Development 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 molecules withnew structures that incorporate silicon to develop molecules withnew functions. Specifically, we are studying the relationshipbetween molecular structure and molecular functionalities ofnovel organosilicon compounds.

2. Disilabicycloalkanes
In large bicycloalkanes, several in/out forms exist, wherein
substituents on the bridgehead atoms are oriented either outside
or inside the cage. The relative stability between the in,out andtwist-out,out forms, which can interconvert throughhomeomorphic conversion, was found to depend upon the cagesize. The in,out form demonstrated thermodynamic stability inthe smaller C10-chains derivative, whereas the twist-out,out
form prevailed in the larger derivatives of C14 and C18-chainsplausibly as a result of dispersion forces among the chains.
(Figure 3, article #1)

1. Artificial Molecular Rotors
A molecular machine has been defined as a discrete number ofmolecular components that perform mechanical-like movements
in response to specific stimuli. Macrocage molecules with abridged rotor have been synthesized as molecular gyroscopes
and molecular gyrotops given that the rotor can rotate even in
the crystalline state.

Figure 3. Disilabicycloalkanes (article #1).
Figure 4 displays the front cover of the journal issue that includes
the article #1.

Figure 1. molecular gyrotop.
The fluorescence of organic molecules has been extensively
studied for the development of functional materials. Clarifying
the relationship between molecular motion and fluorescencequantum yield (FQY) can aid in developing intensitycontrollable fluorophores. This study compared the FQYs of 9,9dimethylfluorene-diyl bridged disilabicyclo[n.n.n]alkanes insolution and solid state. Two macrocage derivatives, C18 (n =18) and C22 (n = 22), were synthesized, and their structures werecharacterized. The FQYs in solution were almost the same, but
the FQY in the solid state of large-cage C22 was smaller thanthat of small-cage C18. The lower FQY of C22 was attributed to
the librational motion, which occurs on a time scale close to thefluorescence time scale. The solid-state 2H NMR showed thatthe slight motion of the deuterated fluorophore, such as libration,
inside the cage causes more efficient relaxation. The results ofthis study are expected to contribute to the molecular design ofenvironmentally responsive fluorescent materials (Figure 2,
article #3).

Figure 4. A cover picture of the journal issue including thearticle #1.

12

Reports from Research Groups■Academic Meeting＊Domestic
See the annual report in Japanese (21 articles)

3. Stannane-based Mmolecular Bevel Gears
Ditriptycylmethanes are known as molecular bevel gears
because the two triptycyl groups act as wheels and display
correlated rotation in solution. However, introduction ofsubstituents on the methylene junction for chemical modificationof the bevel gears has been difficult due to steric hindrance ofthe triptycyls. In this study, stannane-based molecular bevel
gears with organic substituents on the tin linker were achievedby utilizing long Sn–C bonds. Ditriptycylstannanes with methyls
or phenyls on the tin atoms were synthesized. Their structures
were characterized by X-ray crystallography, and the angle oftriptycyl– Sn–triptycyl in the diphenyl derivative was observed
to be narrower than that of the dimethyl derivative due to sterichindrance of the phenyls. The gear rotation of these derivatives
was observed by NMR spectroscopy through observations of thephase isomers of the corresponding methyltriptycyl derivatives.
Gear slippage was observed in the high-temperature region, andthe activation energy of the diphenyl derivative was higher thanthat of the dimethyl derivative. The observed relationshipbetween gear rotation and substituents on the tin can aid in themolecular design of functional molecular bevel gears. (Figure 5,
article #2).

Figure 5. Stannane-based molecular bevel gears (article #2).
■Papers with Peer Review
1. Synthesis of Dimethyldisilabicycloalkanes: Cage-Size
Effects on the Relative Stabilities between In,Out andTwist-Out,Out Forms, Wataru Setaka*, Yuto Ikeda, Yusuke
Inagaki, Kazuaki Ohara, and Kentaro Yamaguchi, Org. Lett.
2023, 25, 7283–7286. (selected as a Front Cover)(DOI: 10.1021/acs.orglett.3c02382)
2. Synthesis and structure of stannane-based molecular bevel
gears having substituents on a tin linker, Satoshi Hosono,
Yusuke Inagaki and Wataru Setaka*, Org. Biomol. Chem.
2023, 21, 4781–4787.
(DOI: 10.1039/d3ob00666b)
3. Synthesis and fluorescence properties of 9,9dimethylfluorene-diyl bridged molecular gyrotops: Effects
of slight fluorophore motion on fluorescence efficiency insolid state, R. Yoshizawa, Y. Inagaki, H. Momma, E. Kwon,
K. Ohara, K. Yamaguchi, and W. Setaka, New. J. Chem.
2023, 47, 5946-5952.
(DOI:10.1039/D2NJ05873A)■Invited Lectures
1.

Wataru Setaka,
Dielectric Relaxation of Crystalline Molecular Gyrotops
with a Dipolar Rotor, 13th International Advances inApplied Physics & Materials Science Congress &Exhibition (APMAS2023), 2023.10.11-17. (Oludeniz,
Turkey)．(10/13 plenary talk, Invited).

13

Reports from Research Groups
Kajihara Laboratory■Members
Koichi KAJIHARA
Professor /Ph.D.
Inorganic Chemistry, Functional Material Chemistry,
Inorganic Materials/Physical Properties
Room:9-336 TEL: +81-42-677-2827
kkaji@tmu.ac.jp
Masanao ISHIJIMA
Assistant Professor /Ph.D.
Inorganic Chemistry, Metal nanoparticles
Room. 9-233 TEL:+81-42-677-2841
ishijima@tmu.ac.jp

Fig. 2 Cosolvent-free synthesis of hydrophilic thermosetresistant deep-ultraviolet-transparent poly(cyclohexylsilsesquioxane)-based glasses with low melting temperatures.
Masanao ISHIJIMACuPd alloy has two crystal phases, and crystal phase control ofnanoparticles was carried out by the annealing process.
controlled We developed a method for synthesizing CuPd
nanoparticles with different crystal phases by adjusting the
reduction rate using complexing agents in the alcohol reduction
method and investigated their properties as electrochemical
reduction catalysts for CO 2.

Doctor’s course - 2
Master’s course -9
Bachelor 4 -5■Outlines of the Research
1. Studies on inorganic materials and energy devices
Koichi KAJIHARA, Masanao ISHIJIMA
We are studying energy devices using inorganic solids. A newlithium-containing sodalite Li8B6Si6O24Cl2 was discovered. This
compound was the first alkali sodalite containing boron as themain framework cations, and the first sodalite that can form
glass-ceramics from uniform melts. The resulting glass-ceramics
were lithium ion conducting and stable in contact with lithium
metal. We also succeeded the synthesis oand single crystal X-ray
structure analysis of Na 4B4Al3O12Cl, which is the first sodium
boracite. The resulting structure data contribute to fundamental
solid-state sciences.

Fig. 3 Crystal phase control of CuPd nanoparticles■Papers with Peer Review
1. H. Arima, N. Tezuka, M. Ishijima, K. Kanamura, K. Kajihara,“Lithium-ion-conducting glass-ceramics of a boroncontaining alkali sodalite Li8B6Si6O24Cl2,” J. Ceram. Soc.
Jpn. 131, 291-297 (2023)
2. K. Kajihara, R. Suzuki, R. Seto, H. Itakura, M. Ishijima,“Poly(cyclohexylsilsesquioxane)-basedhydrophilic
thermoset-resistant deep-ultraviolet-transparent glasses withlow melting temperatures,” ACS Appl. Mater. Interfaces 15,
31880-31887 (2023).
3. Y. Shimbori, K. Nishikawa, K. Kajihara, K. Kanamura,“Application of 3DOM PI separator to Li metal battery withhighlyconcentrated
ionic
liquidelectrolyte,”
Electrochemistry 91, 127003 (2023).
4. N. Todoroki, M. Ishijima, J. L. Cuya Huaman, Y. Tanaka, J.
Balachandran, Composition sensitive selectivity and activityof electrochemical carbon dioxide reduction on Pd–Cu solidsolution alloy nanoparticles, Catal. Sci. Technol., 13, 5025
(2023).
5. M. Ishijima, N. Todoroki, J. L. Cuya Huaman, Y. Tanaka, J.
Balachandran, Kinetically Controlled Direct Synthesis of
B2- and A1-Structured Cu–Pd Nanoparticles, Inorg. Chem.,
62, 19270 (2023).
6. K. Kajihara, S. Nakagawa, R. Nakagawa, M. Suda, M.
Ishijima, H. Kuriyama, I. Serizawa, “Temperaturedependence of narrow-band uvb photoluminescence ofsilica–(Gd,Pr)PO4 transparent glass-ceramic phosphors,” J.

Fig. 1 Crystal structures of Li8B6Si6O24Cl2 (left) andNa4B4Al3O12Cl (right).
Silicon is a ubiquitous element and its utilization is inaccordance
with
SDGs.
We
found
that
poly(cyclohexylsilsesuquioxane) synthesized by cosolvent-freemethod developed in our lab is a glass with low melting
temperature.
In
contrasttothewell-known
poly(phenylsilsesquioxane)
glasses,poly(cyclohexylsilsesquioxan) glasses and their copolymers withalkylsilsesquioxanes were transparent to deep-UV light withwavelengths equal or less than 300 nm. In addition, they arehydrophilic and strongly bonded to glasses and metals becauseof the presence of residual SiOH groups. However, thepolycondensation between the SiOH groups was slow and theglasses maintained thermoplasticity upon heating to 200°C.

14

Reports from Research Groups
Phys: Condens. Matter 36, 085301 (2024).
7. S. Yoshino, H. Arima, M. Ishijima, K. Kajihara, “Crystal
structures of the alkali aluminoboracites A4B4Al3O12Cl (A =Li, Na),” Acta. Cryst. E 80, 169-173 (2024).
8. Y. Shimbori, S. Ooga, K. Kajihara, K. Kanamura, “Effect of
Polybenzimidazole Addition to Three-DimensionallyOrdered Macroporous Polyimide Separators on Mechanical
Properties
andElectrochemical
Performances”,
Electrochemistry, DOI: 10.5796/electrochemistry.23-00145.

■Reviews and Books
See the annual report in Japanese (3 articles)■Invited Lectures＊ International
1. Koichi Kajihara. Synthesis and characterization of lithiumion-conducting boracite and sodalite glass-ceramics. ICG
Annual Meeting 2023. 2023/11, China (Invited)＊ Domestic
See the annual report in Japanese (1 article)■Academic Meeting＊ International
2. Koichi Kajihara, Shingo Nakagawa, Masanao Ishijima.
Temperature dependence ofnarrow-band UVBphotoluminescence of silica–(Gd,Pr)PO4 transparent glassceramics. The 14th International Conference on SiO 2,
Dielectrics and Related Devices, 2023/6 , Italy
3. Yuma Shimbori, Koichi Kajihara, Kiyoshi Kanamura.
Improvement of Charge/Discharge Performance of Li Metal
Battery Using Ionic Liquid Electrolyte with 3DOM PI
Separator. 224th ECS Meeting. 2023/10, Sweden
4. Masanao Ishijima. Development of the Alcohol Reduction
Method for the Designed Synthesis of Bimetallic
Nanomaterials. Future Materials 2023. 2023/10, Online＊ Domestic
See the annual report in Japanese (9 articles)■Patents
See the annual report in Japanese (3 articles)■Awards
See the annual report in Japanese (3 articles)

15

Reports from Research Groups
Yanagshita Laboratory
control by using heteroatom-doped graphene derivatives as thecatalyst supports, and found that those with electron donating
properies are suitable to reduce the overpotential for ORR in
OH- conducting ionic liquids.

■Members
Takashi YANAGISHITA
Professor/ Dr. Eng.
Electrochemistry, Functional Metal Oxide Film
Room. 9-147 TEL:+81-42-6 77- 2842
yanagish@tmu.ac.jp

0.02

Current density / mA cm-2

Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry, Batteries andFuel Cells
Room:9-142, TEL: +81-42-677-2826
munakata@tmu.ac.jp

Doctor’s course -1
Master’s course -5
Bachelor 4 -4

Pt/C Eonset(Pt/C)

Eonset(Pt/RGO)

0
E

-0.02

onset(Pt/NG)-0.04

Pt/RGO
-0.06

Pt/NG

-0.08
-0.1
-0.12

O saturated at 120 °C
2

0

0.2

0.4
0.6
0.8
Potential / V vs. RHE

1

1.2

Fig. 1 Electrochemcial oxygen reduction reaction of platinum
catalysts suppoterd on Ketjen Black (Pt/C), reduced graphene
oxide (Pt/RGO) and nitrogen-doped graphene (Pt/NG) in OHconducting ionic liquid.

■Outlines of the Research
1. Fabrication of Nanofilters by Electrochemical Process
Takashi YANAGISHITA
We have investigated a membrane filter that can efficiently
separate fine particles by anodization of Al. Based on the
optimization of the geometry, a membrane filter was
successfully fabricated that significantly exceeds the solution
permeability of usual membranes.
2. Application of anodic porous alumina prepared by anodizationof Al
Takashi YANAGISHITA
A wettability gradient surface was formed by continuously
changing the surface pore size of porous alumina formed byanodic oxidation of Al. The obtained surface was found tofunction as a surface that spontaneously transports water
droplets. The formation of ultrafine nanofibers with uniform size
was also achieved by spinning polymer nanofibers using porousalumina as a mouthpiece.
3. Preparation of ordered nanohole arrays and their applications
Takashi Yanagishita, Hirokazu MUNAKATA
It was found that highly ordered nanohole arrays can be formedby anodic oxidation of various metals, including stainless steel.
The application of the obtained highly ordered nanohole arrays
to electrolytic capacitors was also investigated.
4. Research on fuel cells
Hirokazu MUNAKATA, Takashi YANAGISHITA
Elevating the operating temperature of fuel cells is crucial forenhancing the activity of fuel catalysts and mitigating their
poisoning with carbon monoxide. Toward achieving this goal,
we have synthesized and evaluated OH- conductive ionic liquids
with high thermal stability and ion conductivity as intermediate
temperature fuel cell electrolytes. The progress of oxygen
reduction reaction (ORR) was successfully confirmed in thoseionic liquids at temperatures above 100 °C under non-humid
conditions. However, the overpotential for ORR was high due tothe adsorption of ionic species on platinum catalytsts. To solve
this issue, the electronic state of platinum catalysts was tried to16

Reports from Research Groups■Papers with Peer Review

K. Kanamura, S.-S. Kim, Y.M. Lee, Adv. Energy Mater.,
13 2004328 (2023).
16. M.U. Salma, Y. Maruyama, M. Nagao, S. Watauchi, H.
Munakata, K. Kanamura, I. Tanaka, J. Ceram. Soc. Jpn.,
131, 72 (2023).
17. M.R. Khandaker, Y. Maruyama, M. Nagao, S. Watauchi,
H. Munakata, K. Kanamura, I. Tanaka, Cryst. Growth Des.,23, 5699 (2023).
18. Ji.S. Yun, O. Mukhan, W. Cho, J.-. Yu, H. Munakata, K.
Kanamura, S.-S. Kim, Adv. Sustainable Syst. 2300297,(2023).
19. O. Mukhan, J.-S Yun, H. Munakata, K. Kanamura, S.-S.
Kim, ACS Omega 2024, 9, 4004 (2024).

1. Preparation of alumina membrane filters with framework
structures by Al anodization
Y. Boushi and T. Yanagishita*, Langmuir, in press.
[Supplementary Cover Art]
2. Control of water droplet transport using anodic porousalumina with wettability gradientY. Boushi and T. Yanagishita*, Langmuir, in press.
[Supplementary Cover Art]
3. Anodic Porous Alumina Membranes with Chemical
Stability Improved by Atomic Layer Deposition Coating of
TiO2
H. Itoh and T. Yanagishita*, ECS J. Solid State Sci.
Technol., 13, 023002 (2024).
4. Preparation of ordered nanostructures by anodization of Ag
substrate with depression patterns
S. Teshima and T. Yanagishita*, J. Electrochem. Soc., 170,
123503 (2023).
5. Flat and roll-type translucent anodic porous alumina molds
anodized in oxalic acid for UV nanoimprint lithography
T. Yanagishita*, N. Kumagai, and H. Masuda, RSC Adv.,13, 33231 (2023).
6. Anisotropic Plasmonic Property of Al Nanowires Obtainedby AC Electrodeposition Using Anodic Porous Alumina
Template
T. Kondo*, T. Sano, T. Yanagishita, and H. Masuda, J.
Phys. Chem. C, 127, 21629 (2023). [Supplementary
Cover Art]
7. Fabrication of nanoparticle assemblies with a controlled
number of constituent nanoparticles by membraneemulsification using anodic porous alumina
T. Yanagishita*, K. Yuda, T. Kondo, and H. Masuda,
Mater. Adv., 4, 4369 (2023). [Inside Front Cover]
8. Effects of anodization conditions of stainless steel on theformation of ordered nanoporous structures with highaspect ratios
Y. Osada and T. Yanagishita*, Nanotechnology, 34,465601 (2023).
9. Investigation of conditions for preparation of ordered
nanohole arrays by anodization of iron substrates withdepression patterns
Y. Osada and T. Yanagishita*, J. Electrochem. Soc., 170,
063510 (2023).
10. Preparation of antireflection structures with heat resistanceby nanoimprinting using anodic porous alumina molds
T. Yanagishita*, R. Ooe, Y. Ishibashi, and T. Mitsuru, Jpn.
J. Appl. Phys., 62, 068002 (2023).
11. Preparation of Size-controlled LiCoPO4 Particles by
Membrane Emulsification Using Anodic Porous Alumina
and Their Application as Cathode Active Materials for Liion Secondary Batteries
T. Yanagishita*, R. Otomo, and H. Masuda, RSC Adv., 13,16549 (2023).
12. Fabrication of moth-eye structures with precisely controlled
shapes by nanoimprinting using anodic porous alumina
molds
T. Yanagishita*, M. Etani, and T. Kondo, J. Electrochem.
Soc., 170, 063501 (2023).
13. Preparation of polymer nanopillar arrays with controlled tip
shapes and their application to hydrophobic and oleophobic
surfaces
T. Yanagishita*, M. Kurita, Langmuir, 39, 8540 (2023).
[Supplementary Cover Art]
14. Fabrication of Ideally Ordered Anodic Porous Alumina on
Glass Substrates by Stamping Process Using Flexible
StampsK. Kato and T. Yanagishita*, ECS Adv.,2, 022501 (2023).
15. J. Song, S.-H. Lim, K.-G. Kim, N. Umirov, H. Lee, C.B.
Dzakpasu, J. Lim, J. Nam, J. Park, J.-N. Lee, H. Munakata,■Invited Lectures＊International
1. H. Munakata, R. Wakabayashi, K. Kanamura
Development of hydroxide ion conducting ionic liquids for
non-humidified intermediate temperature alkaline-type
fuel cells,International Conference on Nanomaterials and Energy
Storage Systems (INESS-2023), 2023 年 7 月, Akyaka,
Turkey2. T. Yanagishita and Y. Boushi
Fabrication of anodic porous alumina with wettability
gradient
ICSE 2023，2023 年 11 月，Korea.
＊Domestic
See the annual report in Japanese (4 articles)■Academic Meeting
See the annual report in Japanese (33 articles)■Patents
See the annual report in Japanese (3 articles)■Awards
See the annual report in Japanese (3 articles)

17

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

Especially when phthalocyanine was used as energy acceptor,
light harvesting type energy transfer was realized. In addition tothese, hydrogen evlution systems using sunlight as an energy
source has been developed.
Especially, photochemicalhydrogen and hydroperoxide formation were examined as anenergy related subject this year.

Chemistry,

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.

Tamao ISHIDA
Associate Professor /Dr. Eng.
Catalysis Chemistry,room:9-B51 TEL: +81-42-677-2845
e-mail: tamao@tmu.ac.jp
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 3
Doctor’s course 3
Master’s course 13
Bachelor 6■Outlines of the Research
Our group challenges to control photochemical reactions
such as electron and energy transfer, by controlling theorientation and alignment of dyes on the inorganic surfaces.
Recently, organic/inorganic hybrids composed of porphyrins andlayered materials have been the subject of intensive
investigations to explore their novel properties andfunctionalities. We found out that a precise matching of
distances between the negatively charged sites on the clay
mineral layers and that between the positively charged sites inthe dye molecule is one of the most important factors todetermine the structure of the clay–dye complex. We havetermed this the “Size-Matching Rule”. Our goal is finding out a
new methodology to control molecular assembly structure andrealizing functionalized photochemical reaction systems such as
an artificial light harvesting system.

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

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.

3. Research on protein behavior on inorganic nanosheets
Shinsuke TAKAGI, Tetsuya SHIMADA
Proteins take unique higher-order structures and exhibit
unique properties in an aquatic environment. For example,
enzymes have extremely high substrate selectivity based on theirhigher order structure. Horseradish peroxidase (HRP) is known
to selectively react with hydrogen peroxide. It was found thatwhen this HRP was adsorbed onto clay nanosheets, its structurechanged and the enzymatic activity changed. It becomes possible
to react with sterically bulky peroxides that cannot react in water.
It was also found that the heat resistance of HRP was greatly
improved on nanosheets.
4. Surface-induced emission (S-FIE) on the clay surface
Shinsuke TAKAGI, Tetsuya SHIMADA
Usually, dyes have their emission intensity determined by thecharacteristics based on their molecular structure. On the other
hand, in this study, we found that even dyes with extremely weakemission can often enhance emission by being adsorbed on

Fig. 1. Artificial light harvesting model on the nanosheet.

18

Reports from Research Groups
charged saponite surface and MQu+ stabilized the aldehyde sideenthalpically and destabilized it entropically. The major reason
for these results is considered to be the difference in adsorption
stabilization between MQu+-Aldehyde and MQu+-Diol onsaponite surfaces.

nanosheets in a non-associated state. Depending on the dye,emission enhancement of more than 100 times was observed,
and it is a useful technique for the development of optical
functional materials. This year, we found that emission
enhancement can be achieved not only with fluorescence but
also with phosphorescence.

7. Research on supported gold catalysts
Tamao ISHIDA
Au nanoparticles with a diameter of 5 nm or less are known
to show high catalytic activity for CO oxidation when supported
on reducible metal oxides such as Co3O4 and NiO. For CO
oxidation, the interface between Au and the supports is regarded
as the active site, and molecular oxygen is activated at theoxygen vacancies of the oxide supports near the interface.
Therefore, it is important to deposit Au particles as small as
possible on oxides having abundant oxygen vacancies in order
to exhibit high activity.
Layered double hydroxides (LDHs) are compounds in whichlayered divalent metal hydroxide is partly replaced by trivalent
metal ions, and LDH composed of various metals can beprepared. LDHs can be converted into mixed metal oxides(MMOs) by air calcination. It has been reported that when
nanometer-sized Ni-Ti LDHs are converted to MMOs, NiO andTiO2 domains in MMOs possess abundant Ni defects (Ni3+) andoxygen vacancies (Ti3+), respectively. Therefore, small Ni-Ti
MMO derived from LDH can be expected to be a suitablesupport for highly active Au catalysts.
In this study, we deposited ultrafine Ni-Ti LDH on SiO2 andimmobilized Au clusters of less than 2 nm in a diameter (Figure6a) by various preparation methods: LDH on SiO2 was converted
to MMO and then Au was deposited on MMO/SiO2 bydeposition-precipitation (DP) or DP with urea (MMO-DP,
MMO-DPU), and Au was deposited on LDH by DP or DPU
followed by transformation into MMO (LDH-DP, LDH-DPU).
The catalytic activity was evaluated by CO oxidation. LDHDPU exhibited the highest catalytic activity (Figure 6b). X-ray
photoelectron spectroscopy revealed that the amounts of Ni3+
and Ti3+ varied depending on the preparation method and that theamount of Ti3+ contributed to the catalytic activity. Given thatthe amount of Ti3+ is reflected the amount of oxygen vacancies
where O2 is activated, LDH-DPU having rich oxygen vacancies
exhibited the higest catalytic activity.
The LDH-DPU (Au/Ni-Ti MMO/SiO2), which exhibitedthe highest catalytic activity, showed a 50% CO conversion
temperature (T1/2) down to 10 °C. This value is the lowest
amoung Au on bulk Ni-Ti MMO (T1/2 24 °C) and conventional
Au catalysts such as Au/TiO2 and Au/NiO (Figure 6b). To
evaluate the O2 activation, temperature-programmed reaction of
CO (CO-TPR) was conducted. The catalyst was pretreated with
O2 and then heated under CO flow to monitor the amount of CO2
produced. LDH-DPU showed CO2 production from around−40 °C, while other catalysts showed the peak higher than room
temperature. The results suggest that O2 adsorbed on the oxygen
vacancies or the lattice oxygen of TiO2 domain more easily
reacted with CO to form CO2 at lower temperature than those ofother catalysts such as LDH-DP, MMO-DP, and MMO-DPU.
The catalytic activity of Au is known to strongly depend onon the type of supports, and the same trend is observed fororganic reactions. The transformation of CO2 to valuable
compounds is important in a view of carbon-neutral strategy andhas been intensively studied. In this study, N-formylation ofamines with CO2 and H2 was investigated over various kinds ofoxide-supported Au catalysts. It has been reported that Au/TiO2
is highly catalytically active for the N-formylation reaction,
while other basic, amphoteric, and acidic oxide-supported Au
catalysts are completely inactive.
However, it was found in this study that N-formylation
reaction proceeds by various Au catalysts (Table 1). Amongthem, Au on deformed orthorhombic Nb2O5 (Au/Nb2O5-DO)
exhibited higher activity (entry 8) than the previously reported
Au/TiO2 (entry 5). For CO2 hydrogention, methyl formate wasVideos can be viewed on thefollowing site.
https://www.apchem.ues.tmu.ac.jp/labs/takagi/S_FIEss.mp4
Fig. 3. Enhancement of emission by addition of nanosheets.

5. Research on preparation of semiconductor nanosheet-dye
complex
Shinsuke TAKAGI, Tetsuya SHIMADA
Since clay minerals are insulators, they themselves do nothave redoxactivity. Therefore, we designed and synthesized new
semiconductor nanosheets, and examined their complex
formation behavior with dyes. As a result, it was clarified that,like clay mineral nanosheets, it is possible to realize a highdensity, non-associated adsorption structure for dyes. As a result,
new knowledge was obtained for the construction of solar cells
and artificial photosynthetic systems.

Fig. 4. Visible-light hydrogen generation reaction using the anisotropyof semiconductor nanosheets.

6. “In-water” Dehydration Reaction of an Aromatic Diol on an
Inorganic Surface
Shinsuke TAKAGI, Tetsuya SHIMADA
The effect of a synthetic saponite surface on the “inwater”
dehydration reaction of diol was examined using 4-formyl-1methylquinolinium salt (MQu+) as a substrate. The equilibrium
between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was
affected by the surrounding environment. The equilibrium
behavior was observed by 1H nuclear magnetic resonance(NMR) and UV−vis absorption measurements. Although MQu+
was completely in the form of MQu+-Diol in water, theequilibrium almost shifted to the MQu+-Aldehyde side when
MQu+ was adsorbed on the saponite surface in water. In addition,
the MQu+- Aldehyde ratio depended on the negative charge
density of saponite.

Fig. 5. The equilibrium between aldehyde (MQu+-Aldehyde) and diol
(MQu+-Diol) in water without and with clay nanosheet.

The factors that determine MQu+-Aldehyde: MQu+-Diol ratio
were discussed from the thermodynamic analysis of the system.
These data indicate that the electrostatic interaction between the19Reports from Research Groups
obtained as the major product when amphoteric TiO2 and acidic
Nb2O5 were used as supports, while other oxide supported Au
catalysts gave methanol as the major product. From this result,the high activity for N-formylation was ascribed to the highmethyl formate selectivity. Furthermore, Au/Nb2O5-DO showed
higher activity than Au on amorphous Nb2O5-A (Au/Nb2O5-A)
and on orthorhombic Nb2O5-T (Au/Nb2O5-T). Given that
Au/Nb2O5-DO possesses higher acid and base sites than Nb2O5A and –T, the higher acid and base contents would affect thecatalytic activity.

(3.0 mL), 1 wt% Au catalyst (197 mg), CO2 (1.5 MPa), H2 (2.0 MPa), 5
h. The selectivity to methyl formate was calculated by the amount ofmethyl formate produced divided by the total amount of methyl formate
and methanol produced.

■Papers with Peer Review
1. Photo-Cyclization, Photo-Ring Opening and Thermo-Ring
Opening Reaction of Cationic Diarylethene Adsorbed on
the Clay Nanosheet Surface, K. Arakawa, T. Shimada, T.
Ishida, S. Takagi, Colloid. Surf. A Physicochem. Eng. Asp.
657, 130537-130543 (2023) .
DOI:10.1016/j.colsurfa.2022.130537
2. Enhanced Fluorescence Behavior of Safranine-O byComplexing with Inorganic Clay Nanosheets, M. R.
Melechalil, K. Arakawa, Y. Hirade, F. Kuttassery, T.
Shimada, T. Ishida, S. Takagi, J. Photoch. Photobio. 15,
100182-100188 (2023) . DOI:10.1016/j.jpap.2023.100182
3. Anionic Clay Surface Facilitates Electron Transfer between
an Excited Donor Encapsulated within a Cationic Capsuleand a Cationic Electron Acceptor, N. Morita, A. Raj, T.
Fujimura, T. Shimada, V. Ramamurthy, S. Takagi, J.
Photoch. Photobio. 17, 100204-100208 (2023) .
DOI:10.1016/j.jpap.2023.100204
4. Effect of Poly (N-Vinylpyrrolidone) Ligand on Catalytic
Activities of Au Nanoparticles Supported on Nb2O5 for CO
Oxidation and Furfural Oxidation, M. Lin, C. Mochizuki,
T. Ishida, Y. Zhang, M. Haruta, T. Murayama, Catal. Today
410, 143-149 (2023) . DOI:10.1016/j.cattod.2022.03.034
5. Selective Formation of Acetate Intermediate Prolongs
Robust Ethylene Removal at 0°C for 15 Days, M. Lin, H.
Wang, T. Takei, H. Miura, T. Shishido, Y. Li, J. Hu, Y.
Inomata, T. Ishida, M. Haruta, G. Xiu, T. Murayama, Nat.
Commun 14, 2885-2892 (2023) . DOI:10.1038/s41467-02338686-0.
6. Gold/Substituted Hydroxyapatites for Oxidative
Esterification: Control of Thin Apataite Layer on Gold
Based on Strong Metal-Support Interaction (SMSI) Resultsin High Activity, A. Taketoshi, Y. Gangarajula, R.
Sodenaga, A. Nakayama, M. Okumura, N. Sakaguchi, T.
Murayama, T. Shimada, S. Takagi, M. Haruta, B. Qiao, J.
Wang, T. Ishida, ACS Appl. Mater. Interrfaces 15, 3429034302 (2023) . DOI:10.1021/acsami.3c05974.
7. Metal-Support Interaction in Gold Zeolitic Octahedral
Metal Oxide and the Catalytic Activity for LowTemperature Alcohol Oxidation, Y. Wang, G. Zheng, Q.
Zhu, Q. Tong, B. Yu, T. Ishida, T. Murayama, Y. Li, W.
Ueda, Z. Zhang, Langmuir 39, 10162-10177 (2023) .
DOI:10.1021/acs.langmuir.3c01095.
8. In-situ Raman Unveiled Nb-O-Bond-Dependency
Selectivity for Methanol Electro-Oxidation at High Current
Density, X. Wang, C. Xiao, Y. Li, T. Murayama, T. Ishida,
M. Lin, G. Xiu, Appl. Catal. A: Gen. 664, 119341-119350(2023) . DOI:10.1016/j.apcata.2023.119341.
9. Au Clusters Supported on Defect-Rich Ni-Ti Oxides
Derived from Ultrafine Layered Double Hydroxides(LDHs) for CO Oxidation at Ambient Temperature, A.
Takahashi, A. Nakayama, T. Murayama, N. Sakaguchi, T.
Shimada, S. Takagi, T. Ishida, catalysts 13, 1155-1169(2023) . DOI:10.3390/catal13081155.
10. Supported Gold Nanoparticles Prepared from NHC-Au

Fig. 6. HAADF-STEM image of LDH-DPU (Au/Ni-Ti MMO/SiO2) (a)and conversion curves for CO oxidation (b). (b) ■: LDH-DP, ●: LDHDPU, ■: MMO-DP, ●: MMO-DPU, ◊: Au/TiO2, □: Au/NiO, ○: Au/SiO2.
Reaction conditions: 0.1 g of catalyst, 1 vol% CO in air (33.3 mL min−1),
and space velocity (SV) of 20,000 mL h−1 gcat−1.
Table 1. N-formylation of morpholine using CO2 and H2 over supported
Au catalysts.a

Au size

Temp.

Yield

HCO2Me

/nm

/°C

/%

Selec./%dEntry Catalystb

1

Au/ZnO

2.0±0.7

120

4

9

2

Au/CeO2

4.5±2.7

120

8

–

3

Au/ZrO2

3.3±1.8

120

11

11

4

Au/Al2O3

3.5±2.4

120

24

29

5

Au/TiO2

4.1±2.2

6
7

Au/Nb2O5-DO

2.8±0.7

8

a

c

120

59

66

100

55

–

120

69

–

100

80

96

9

Au/Nb2O5-T

2.8±0.7

100

48

–

10

Au/Nb2O5-A

2.6±0.6

100

24

–

Reaction conditions: morpholine (0.5 mmol), N,N-dimethylacetamide(DMAc) (3.0 mL), 1 wt% Au catalyst (197 mg, Au 2 mol%), CO2 (2.0MPa), H2 (1.5 MPa), 5 h. b Estimated by HAADF-STEM. c Yield was
calculated by gas chromatography using 1,2-dimethoxyethane as aninternal standard. d Reaction conditions for CO2 hydrogenation: DMAc

20

Reports from Research Groups
2. Enhanced Fluorescence Behavior of Safranine-O byComplexing with Inorganic Clay Nanosheets, M. R.
Melechalil, K. Arakawa, Y. Hirade, F. Kuttassery, T.
Shimada, T. Ishida, S. Takagi, The 31st International
Conference on Photochemistry, September, 2023, Sapporo,
Japan.
3. Monolayer Modification of Spherical Amorphous Silica by
Clay Nanosheets, N. Nishida, K. Arakawa, T. Shimada, S.
Takagi, The 12th Asian Photochemistry Conference (APC)
2023, November, 2023, Melbourne, Australia.
4. Remarkable Luminescence Enhancement of Alkaloid Dyes
in Aqueous Solution by Using Clay Nanosheets, H. Mori,
H. Tachibana, T. Shimada, T. Ishida, S. Takagi, The 12th
Asian Photochemistry Conference (APC) 2023, November,
2023, Melbourne, Australia.
5. Unique Photochemical Behavior of Dyes on The Inorganic
Flat Surface, H. Mori, K. Arakawa, T. Ishida, T. Shimada,E. Hasegawa, S. Takagi, The 12th Asian Photochemistry
Conference (APC) 2023, November, 2023, Melbourne,
Australia.
6. Development of Supported Gold Cluster Catalysts Utilizing
Layered Double Hydroxide (LDH) Nanoparticles, A.
Nakayama, A. Yoshida, T. Honma, N. Sakaguchi, A.
Taketoshi, T. Murayama, T. Shimada, S. Takagi, T. Ishida,
EuropaCat2023, August, 2023, Prague, Czech Republic.
7. Decoration of Au/SiO2 by Thin Metal Oxide Layer Derived
from Layered Double Hydroxides (LDHs), K. Okayama, A.
Nakayama, T. Murayama, N. Sakaguchi, T. Shimada, S.
Takagi, T. Ishida, EuropaCat2023, August, 2023, Prague,
Czech Republic.
8. Continuous transfer hydrogenolysis of THFA to 1,5pentanediol over stable Ni-La(OH)3: Towards selective
synthesis of biobased a,w-diols, M. Al-Yusufi, D. Michalik,
N. Steinfeldt, M. Sebek, H. Atia, R. Eckelt, C. Kubis, T.
Ishida, T. Murayama, A. AbdelMageed, A. Köckritz,
EuropaCat2023, August, 2023, Prague, Czech Republic.
9. Cluster-sized alloys on zeolite for robust ethylene removal
at 0 °C, M. Lin, H. Wang, T. Ishida, G. Xiu, T. Murayama,
EuropaCat2023, August, 2023, Prague, Czech Republic.
10. Oxidative Coupling Reaction of Dimethyl Phthalate overSupported Gold Catalysts, K. Arata, A. Nakayama, T.
Murayama, T. Shimada, S. Takagi, T. Ishida, 9th AsiaPacific Congress on Catalysis (APCAT-9), October, 2023,
Hangzhou, China.
11. Catalytic Properties of Supported Gold Catalysts Utilizing
Layered Double Hydroxide (LDH) Nanoparticles, A.
Nakayama, A. Yoshida, T. Honma, N. Sakaguchi, T.
Murayama, T. Shimada, S. Takagi, T. Ishida, 9th AsiaPacific Congress on Catalysis (APCAT-9), October, 2023,
Hangzhou, China.
12. Thin Metal Oxide Layer-Coated Au/SiO2 Using Layered
Doulble Hydroxide Nanosheets, K. Okayama, A.
Nakayama, N. Sakaguchi, T. Shimada, S. Takagi, T. Ishida,
9th Asia-Pacific Congress on Catalysis (APCAT-9),
October, 2023, Hangzhou, China.
13. Oxidative Homocoupling Reaction of Dimethyl Phthalate
over Metal Oxide Supported Au Catalysts, K. Arata, A.
Nakayama, T. Murayama, T. Shimada, S. Takagi, T. Ishida,
International Symposium on Catalysis and Fine Chemicals(C&FC2023), December, 2023, Tokyo, Japan.

Complex Precursors as Reusable Heterogeneous Catalysts,
Q.-A. Huang, M. Takaki, H. Murayama, A. Yoshizawa, E.
Yamamoto, L. X. Dien, T. Ishida, T. Honma, N. V. Tzouras,
T. Scattolin, S. P. Nolan, M. Tokunaga, Mol. Catal. 549,
113460-113468 (2023) . DOI:10.1016/j.mcta.2023.113460.
11. Au/Nb2O5-Catalyzed N-Formylation of Amines Utilizing
High Selectivity to Formate Intermediate in CO2
Hydrogenation, M. Hidaka, M. Lin, H. Yamakawa, A.
Nakayama, T. Murayama, T. Shimada, S. Takagi, T. Ishida,
Chem. Lett. 52, 874-877 (2023) . DOI:10.1246/cl.230365.
12. Low-Temperature Hydrogenation of CO2 to Methanol in
Water on ZnO-Supported CuAu Nanoalloys, J. Mosrati, T.
Ishida, H. Mac, M. Al-Yusufi, T. Honma, M. ParliniskaWojtan, Y. Kobayashi, A. Klyushin, T. Murayama, A. M.
Abdel-Mageed, Angew. Chem. Int. Ed. 62, e202311340e202311350 (2023) . DOI:10.1002/anie.202311340.
13. Decoration of Gold and Platinum Nanoparticle Catalysts by
1-nm-thick Metal Oxide Overlayer and its Effect on CO
Oxidation, K. Okayama, A. Nakayama, T. Murayama, N.
Sakaguchi, F. Hong, B. Qiao, J. Wang, T. Shimada, S.
Takagi, T. Ishida, ACS Appl. Mater. Interfaces 16, 45704580 (2024) . DOI:10.1021/acsami.3c14935.
14. Emission Enhancement of Anthracene Derivative Caused
by a Dramatic Molecular Orbital Change on the Nanosheet
Surface, K. Arakawa, T. Shimada, T. Ishida, S. Takagi, W.
Han, J. Phys. Chem. C 128, 1995-2002 (2024) .
DOI:10.1021/acs.jpcc.3c06631.
15. Structural Transformation of Azonia[5]helicene
Photoproduct via Reaction Field Function of Layered
Inorganic Material, K. Arakawa, T. Shimada, T. Ishida, K.
Sato, S. Takagi, Langmuir, in press.
DOI:10.1021/acs.langmuir.3c03589.
16. Monolayer Modification of Spherical Amorphous Silica by
Clay Nanosheets, N. Nishida, K. Arakawa, T. Shimada, S.
Takagi, Langmuir, in press.
DOI:10.1021/acs.langmuir.3c03494.

■Invited Lectures
1. Surface-Fixation Induced Emission (S-FIE) of Organic
Dyes on the Inorganic Flat Surface, S. Takagi, The 31st
International Conference on Photochemistry, July, 2023,
Sapporo, Japan.
2. Modification of Noble Metal Nanoparticle Surface by Thin
Metal Oxide Layer Improves Catalytic Activity andStability, T. Ishida, East China University of Science andTechnology, November, 2023, Shanghai, China.
3. Modification of Gold Nanoparticle Surface by Thin Metal
Oxides Aiming at Improvement of Catalytic Activity andStability, T. Ishida, Dalian Institute of Chemical Physics,
November, 2023, Dalian, China.
4. Enhanced
Activity of Au Nanoparticles Covered byHydroxyapatites, T. Ishida, International Symposium on
Catalysis and Fine Chemicals (C&FC2023), December2023,
Tokyo, Japan.
5. See the annual report in Japanese (1 more articles)■Academic Meeting＊International
1. Effect of Pt Co-Catalyst Loading Site on Photoreduction
Efficiency in Titania Nanosheet, Y. Hirade, K. Fukushima,
T. Shimada, S. Takagi, The 31st International Conference
on Photochemistry, September, 2023, Sapporo, Japan.

21

Reports from Research Groups＊Domestic
See the annual report in Japanese (16 articles)■Review Articles and Books
1. Supported Noble Metal Catalysts and Adsorbents with
Soft Lewis Acid Functions, H. Murayama, Q-A.
Huang, E. Yamamoto, M. Tokunaga, T. Ishida, M.
Okumura, T. Honma, T. Fujitani, A. Isogai, Chem.
Rec., 23, e202300148-e202300163(2023). (Review)
DOI:10.1002/tcr.202300148.

■Awards
1. Poster Award, The 31st International Conference on
Photochemistry ACS Applied Materials & Interfaces,
Effect of Pt co-catalyst loading site on photoreduction
efficiency in titania nanosheet
2. Excellent student presentation award, The solid and surface
photochemistry conference 2023, Jiahao LU (M1),
November, 2023.
3. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2023, Nanako NISHIDA (M2),
December, 2023.
4. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2023, Kunpei HARAKO (M2),
December, 2023.
5. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2023, Yoshinori TAHARA (M2),
December, 2023.

22

Reports from Research Groups
Shishido Laboratory■Members

plastics, which will lead to the proposal of a new resource
recycling system.

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
Associate 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

SET

chemistry,

Study on radical nature of gold nanoparticles
Radical reactions using single-electron transfer catalysts enableorganic transformations that are different from two-electron
redox processes. In this study, we found that gold nanoparticles
function as single-electron transfer catalysts to proceed radical
coupling reactions. The corresponding alkylsilanes could besynthesized in high yield by the reaction of disilanes and redoxactive esters.

PD -1
Doctor’s course -5
Master’s course -8
Bachelor 4 -5■Outlines of the Research

SET oxidation

Study on the reaction of mechane and NO for the production of
HCN and NH3e-

Methane (CH4) was converted to hydrogen cyanide (HCN) andammonia (NH3) at temperatures from 300 to 425 °C using a 5
wt% Pt/Al2O3 catalyst with nitric oxide (NO) as an oxidant.
HCN yield of ca.1% was maintained even after 100 h at 400 °C.
In situ X-ray absorption fine structure (XAFS) and Fouriertransform infrared (FTIR) spectra showed that Pt–CN species
emerged, and the extent of the adsorbed species roughly
correlated with the production of HCN. This study revealed that
the Pt–CN species can function not only as important reaction
intermediates, but also as inhibitors of the reaction. An
appropriate balance of Pt–CN species and hydrogen species overthe Pt surface is required to produce HCN continuously. Thisbalance of the relative amount of adsorbed species including PtCN varied remarkably depending on the support.

e-

SET reduction■Papers with Peer Review
1.

2.

3.

4.
Study on the catalytic conversion of stable C–O bonds
Utilization of biomass-derived compounds attarcts muchattention from the viewpoint of carbon recycling. Since biomass
compounds contain many C–O bonds, the development of an
efficient method for synthesizing useful compounds via directconvertion of C–O bonds. In this study, we have demonstrated
that silyl cross-coupling between hydrosilanes and alkyl esters
and alkyl ethers proceeded by using acidic oxide supported Au
catalysts to synthesize alkylsilanes under mild conditions. This
catalytic reaction enables rapid synthesis of organosiliconcompounds from biomass-derived compounds and waste

5.

6.

23

Acidic property and gas-phase glycerol-dehydration
activity of WO3/Al2O3 catalysts, Kanai, Ryuichi; Yagi,
Fuyuki; Omata, Kaori; Miura, Hiroki; Shishido, Tetsuya,
Mol. Catal., 2023, 113588.
Insights into Pt-CN Species on an Alumina-supported
Platinum Catalyst as Active Intermediates or Inhibitors for
Low-temperature Hydrogen Cyanide Synthesis from
Methane and Nitric Oxide, Takagaki, Atsushi; Bando,
Kyoko; Yamasaki, Tatsuya; Murakami, Junichi; Suganuma,
Nobuya; Ghampson, Isaac Tyrone; Kodaira, Tetsuya;
Ishihara, Tatsumi; Shishido, Tetsuya, Catal. Sci. Technol.,2023, 13, 5017–5024.
Harnessing Supported Gold Nanoparticle as a SingleElectron Transfer Catalyst for Decarboxylative CrossCoupling, Miura, Hiroki; Kaede, Ameyama; Shishido,
Tetsuya, Adv. Synth. Catal., 2023, 365, 62–69.
High-density formation of Ir/MoOx interface throughhybrid clustering for chemoselective nitrostyrenehydrogenation, Hayashi, Shun; Shishido, Tetsuya, ACS
Org. Inorg. Au, 2023, 3, 283–290.
Methane activation with nitric oxide at low temperatureson supported Pt catalysts: effects of the support, Suganuma,
Nobuya; Ghampson, Isaac Tyrone; Miura, Hiroki;
Murakami, Junichi; Bando, Kyoko; Kodaira, Tetsuya;
Yamasaki, Tatsuya; Takagaki, Atsushi; Ishihara, Tatsumi;
Shishido, Tetsuya, Catal. Sci. Technol., 2023, 13, 39273939.
Selective formation of acetate intermediate prolongs
robust ethylene removal at 0 °C for 15 days, Mingyue Lin,
Haifeng Wang, TakashiTakei ,Hiroki Miura, TetsuyaReports from Research Groups

7.

8.

9.

10.

11.

12.

13.

Shishido, Yuhang Li, Jinneng Hu, Yusuke Inomata, Tamao
Ishida, Masatake Haruta, Guangli Xiu, Toru Murayama,
Nature Commun., 2023, 14, 2885.
Highly Active and Durable Rh–Mo-Based Catalyst for the
NO–CO–C3H6–O2 Reaction Prepared by Using Hybrid
Clustering, Hayashi, Shun; Endo, Shinji; Miura, Hiroki;
Shishido, Tetsuya, ACS Materials Au, 2023, 3, 456–463.
Deoxygenative Silylation of C(sp3)–O Bonds with
Hydrosilane by Cooperative Catalysis of Gold
Nanoparticles and Solid Acids, Miura, Hiroki; Yasui, Yuki;
Masaki, Yosuke; Doi, Masafumi; Shishido, Tetsuya, ACS
Catal., 2023, 13, 6787–6794.
Experimental Evidence for Alloying Effects in Au-Ptcatalyzed Low-temperature CH4 Activation with NO,
Ghampson, I. Tyrone; Miura, Hiroki; Murakami, Junichi;
Bando, Kyoko; Kodaira, Tetsuya; Takagaki, Atsushi;
Ishihara, Tatsumi; Shishido, Tetsuya, ACS Catal., 2023, 13,6574–6589.
Diverse Alkyl–Silyl Cross-Coupling via Homolysis of
Unactivated C(sp3)–O Bonds with the Cooperation of Goldand Amphoteric Oxides Miura, H.; Doi, M.; Yasui, Y.;
Masaki, Y.; Nishio, H.; Shishido, T. J. Am. Chem. Soc.
2023, 145, 4613−4625
Inhibitory effect of trace impurities on methanol reforming
by Cu/ZnO/Al2O3 catalyst: Steam reforming andautothermal reforming of model bio-methanol Nomoto,K.; Miura, H.; Shishido, T. Appl. Catal. B Environ. 2023,
325, 122374.
Low-Temperature Selective Oxidation of Methane toMethanol over a Platinum Oxide, Takagaki, A.; Tsuji, Y.;
Yamasaki, T.; Kim, S.; Shishido, T.; Ishihara, T.;
Yoshizawa, K. Chem. Commun, 2023, 59, 286-289.
Catalytic aqueous CO2 reduction to formaldehyde at Ru
surface on hydroxyl-groups-rich LDH under mild
conditions, Deng, L., Wang, Z., Jiang, X., Xu, J., Zhou, Z.,
Li, X., You, Z., Ding, M., Shishido, T.; Liu, X.; Xu, M.,
Appl. Catal. B Environ. 2023, 322, 122134.

6.

7.

8.

9.

10.

11.

■Academic Meeting＊Domestic
See the annual report in Japanese (28 articles)■Invited Lectures
1.

2.

3.

4.

5.

H. Miura, 132nd Annual Meeting of Catalysis Society ofJapan, Hokkaido University, September 14, 2023
Supported Gold Nanoparticles as Single-Electron Transfer
Catalysts for Cross-Coupling Reactions
H. Miura，International Symposium on Catalysis and Fine
Chemicals 2023 (C&FC2023), 5, December, 2023, Tokyo,
Japan,
Silylation of Stable C–O bonds by Supported Gold
Catalysts and the Application for Depolymerization ofPolyesters
H. Miura，Asian Polyolefin Workshop 2023 (APO2023),
13, December, 2023, Nara, Japan,
CO₂ Hydrogenation by Metal Phosphides Control Factorsof Selectivity of CO₂ Hydrogenation
T. Shishido, The 23rd Hokkaido Division Conference of
the Japan Petroleum Institute December 21, 2023 MuroranInstitute of Technology
Biomass Conversion Based on Dehydration Reaction by
Solid Acid Catalysts
T. Shishido ， Lecture of Highly Selective Reaction
Subcommittee, The Japan Association for Chemical
Innovation, February 21, 2024
Heterogeneous Organic Synthesis Contributing to Carbon
Resource Recycling
H. Miura，104th Annual Meeting of the Chemical Societyof Japan (2024), March 21, 2024, Nihon University,
Funabashi Campus.
Effect of Hydrogen Spillover on the Property of Solid
Acids
T. Shishido, Academic Transformation Area (B) Surface
Hydrogen Engineering 6th Area Meeting, March 26-27,
2024, Shin-Yokohama International Hotel■Awards

Direct synthesis of lactic acid from glucose using
heterogeneous catalysts
D. Hata, K. Aihara, H. Miura, T. Shishido, The Japan
Petroleum Institute 71st Annual Meeting, May 30, 2023,
Tower Hall Funabori
Organic Synthesis on Solid Catalysts
H. Miura, The 34th Freshman Seminar of Catalysis
Society of Japan, June 3, 2023, Hongo Campus, The
University of Tokyo.
Development of Gold and Other Element Cooperative
Solid Catalysts for Highly Efficient Organic
Transformations
H. Miura, Academic Award Commemorative Lecture of
Frontier Materials Research Institute July 19, 2023 at
Tokyo Institute of Technology, Suzukakedai Campus
New Approaches of Heterogeneous Organic Synthesis by
Cooperation of Different Elements
H. Miura, 19th Workshop on Catalyst Chemistry, Shizuoka,
August 3, 2023, Shizuoka City Industry-Academia
Collaboration Center
Intermolecular Bond Formation Promoted by Cooperative
Catalysis of Gold and Other Elements

1.

2.

3.

4.

5.

24

Tokyo Institute of Technology, Institute of Innovative
Research, Frontier Materials Research Institute“Development of Gold and Other Element Cooperative
Solid Catalysts for Highly Efficient Organic
Transformations”
Hiroki Miura
Poster Award “Borylation of C(sp3)–O Bonds of Alkyl
Esters by Supported Au Catalysts”
M. Doi, H. Miura, T. Shishido, 69th Symposium on
Organometallic Chemistry
Poster Award “Reductive Cross-Coupling of C(sp3)–O
Electrophiles and Carbonyl Compounds by Supported Au
Catalysts”
Y. Yasui, H. Miura, T. Shishido, 69th Symposium on
Organometallic Chemistry
Outstanding poster prize “Cooperative Catalysis between
Au Nanoparticles and Metal Oxides for Rapid C–B Bond
Formation”
K. Imoto, H. Miura, A. Junkaew, M. Ehara, T. Shishido,International Symposium on Catalysis and Fine
Chemicals 2023 (C&FC 2023)
Outstanding poster prize “Reductive Cross-Coupling ofReports from Research Groups

6.

C(sp3)–O Electrophiles and Carbonyl Compounds by
Supported Au Catalysts”
Y. Yasui, H. Miura, T. Shishido, International Symposium
on Catalysis and Fine Chemicals 2023 (C&FC 2023)
The Japan Petroleum Institute, The Japan Petroleum
Institute Award for Distinguished Papers “Particle Size
Effect on Hydrogen Cyanide Synthesis with CH4 and NO
over an Alumina-supported Platinum Catalyst” Tatsuya
Yamazaki, Atsushi Takagaki, Tetsuya Shishido､Kyoko, K.
Bando, Tetsuya Kodaira, Jyunichi Murakami, Jun TaeSong, Eiki Niwa, Motonori Watanabe, Tatsumi Ihihara

25

Reports from Research Groups
Analytical Chemistry Laboratory■Members
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

2. Development of a Fluorescence Detection Genetic Testing
System Based on the LAMP Method
Hizuru NAKAJIMA, Shoji YAMAMOTO
While polymerase chain reaction (PCR) methods are widelyused in genetic testing, their reliance on large, expensive
equipment such as thermal cyclers, electrophoresis devices, andspectrophotometers/fluorometers
makes
onsitetestingchallenging. This study introduces a novel fluorescence-based
LAMP device utilizing an Indium Tin Oxide (ITO) transparent
glass heater. Our device is capable of simultaneous real-time
fluorescence measurement of up to eight samples. Furthermore,
we demonstrated the device's ability to quantitatively analyze
human genomic DNA within a concentration range of 2.11×10 2
to 2.11×104 ng/µL by measuring the real-time fluorescenceintensity of the sample.

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
Shoji YAMAMOTO
Project Prof. / Dr.Sci.
Ocean Chemistry, Analytical Chemistryroom: 9-343
TEL: +81-42-677-1111 Ext.4882
e-mail: shoji-yamamoto@tmu.ac.jp
Yoshinori INOUE
Tech. Assistantroom: 9-290
TEL: +81-42-677-1111 Ext.4872
e-mail: inoue-yoshinori @ jmj.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 -3
Master’s course -20
Bachelor 4 -7

■Outlines of the Research

3. Development of an Absorbance Detection Genetic Testing
System Based on the LAMP Method
Hizuru NAKAJIMA, Shoji YAMAMOTO
In addition to developing a genetic testing system based on
fluorescence detection, we also constructed a system using
absorbance detection. We successfully achieved real-time
simultaneous measurement of absorbance intensity for four
samples and determined positive/negative results. Furthermore,
we demonstrated the capability of this system to quantitatively
analyze human genomic DNA within an initial concentration
range of 2.11×102 to 2.11×104 ng/µL.

1. Development of an Electrochemical Analysis System Usinga Compact Disk-type Microfluidic Device
Hizuru NAKAJIMA, Shoji YAMAMOTO
Although simultaneous measurement of multiple components
and samples using microchips is highly beneficial, the need fornumerous pumps and valves often results in a bulky system. To
address this issue, we developed an electrochemical analysis
system that utilizes a compact disc (CD)-type microchip
equipped with an easily fabricated, cost-effective flow channel
chip. This system uses the force generated during rotation to
manipulate liquids, enabling automatic quantitative analysis ofpyrophosphate ions and fully automated loop-mediatedisothermal amplification (LAMP) method without relying on
expensive peripherals or operational expertise. The system
successfully determined positive/negative results.

26

Reports from Research Groups
at remote sites: cape Hedo in Okinawa, Suzu in Ishikawa.

4. Development of a Method for Measuring Exosomal
Membrane Proteins Using SPR Sensor
Hizuru NAKAJIMA, Shoji YAMAMOTO
Exosomes, extracellular vesicles approximately 100 nm indiameter, contain a diverse array of proteins, making thempromising tools for cancer diagnosis. In this study, we utilized asurface plasmon resonance (SPR) sensor to measure changes in
the SPR signal by adding various antibodies to exosomes fusedwith an artificial biomembrane on the gold surface of the sensor
chip. Our results successfully demonstrated real-timeobservation of exosome fusion to the artificial biomembrane andsubsequent antibody adsorption to exosomal membrane proteins.

10. Measurements of atmospheric pollutants at mountainsites
Shungo KATO
Carbon monoxide, ozone, and sulfur dioxide were observed at
the top of Mt. Fuji and the foot of Mt. Fuji (Tarobo observationsite). Clear diurnal cycle caused by air motion were observed.
Volcanic gas from Mt. Asama to Tarobo was observed.
11. Development of volcanic gas monitoring system using
small gas sensor
Shungo KATO
Realtime measurement of volcanic gas at the top of Mt. Fuji
during winter without commercial electric power was conductedwith low power gas sensor and LPWA ELTRES (SONY). Also,
measurement of volcanic gases using a portable system wasconducted at trails of Mt. Fuji and Owakudani, Hakone volcano.
12. Hydrogen measurement in ambient air
Shungo KATO
Gas chromatography/Reduction gas detector system wasconstructed for low level hydrogen measurements. Atmospherichydrogen concentration in suburban, urban, and remote sites
were observed.
13. Development of microchemical pen and its applications
Sifeng MAO
Micro-chemical pen (MCP), developed by our research group,
represents a novel versatile tool for nanowires fabrication. MCP
has been proven successful in generating silver nanowires,
however, the performance of nanowire fabricated by MCP in
sensing chemical/biological species never been investigated.
them difficult to use in nano-sensors. For a nanowire to be used
in a sensor, long nanowires would be more competitive. The
selective fabrication of highly ordered nanowires with highaspect ratios was of low reproducibility, which remains achallenge for laboratory research.

5. Development of a Multichannel ISFET Sensor for
Measuring pH Distribution of Pore Water in Marine
Sediments
Hizuru NAKAJIMA, Shoji YAMAMOTO
Recent increases in atmospheric CO2 concentrations areaccelerating ocean acidification (OA). This process impedes theformation of calcium carbonate skeletons in corals, shellfish, andother marine organisms, and may even dissolve coral reef sands,
thus threatening marine life. Therefore, it is vital to measure the
pH distribution in marine sediment pore water to assess theextent of OA and its impact on marine ecosystems. In this study,
a multi-channel EG-ISFET sensor with a tantalum oxide ionsensitive membrane was successfully used to observe the pH
distribution and diurnal variation in marine sediments off Bise,
Okinawa.

14. Insight into micro-chemical pen: microfluidic mechanism
for high-resolution surface processing
Sifeng MAO
We have confirmed the existence of an intermediate layer
when MCP is working, which provides MCP with extra
advantages in surface processing over the conventional openspace microfluidic systems. The variation of the size of IL
caused by adjusting relative parameters is further proved to be
an important factor for controlling the working area.

7. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
suburban site (Minamiosawa, Koto-ku, Kyoto). Emission
sources, contribution to ozone formation of each VOC were
estimated. From the comparison with NMHC analyzer,
concentration of oxygenated VOC has increased in recent year.
8. Hith time resolution measurement of VOCs by SIFT-MS
Shungo KATO
Measruemnts of ambient air by SIFT-MS was conducted aturban area (Kouto-ku). From the comparison with GC-FID, theperformance of SIFT-MS was examined.
9. Atmospheric trace species measurements at remote sites
Shungo KATO
Atmospheric carbon monoxide, ozone, various volatileorganic compounds, and hydrogen were continuously observed27

Reports from Research Groups
Acta Biomaterialia, 174, 177-190, 2024.
7. Anchen Fu, Sifeng Mao, Nahoko Kasai, Haiyan Zhu, Hulie
Zeng
Dynamic tissue model in vitro and its application forassessment of microplastics-induced toxicity to air-blood
barrier (ABB)
Biosensors and Bioelectronics, 246, 115858, 2024.
8. Sifeng Mao
Recent advances in nanowire sensor assembly using laminarflow in open space
TrAC Trends in Analytical Chemistry, 159, 116918, 2023.

15. Local pH control by using a laminar flow for liposome
fusion control
Sifeng MAO
In this work, a laminar flow method based on a chemical pen
has been proposed for local pH control. We successfully
fabricated the chemical pen with two injections and one
aspiration apertures, and it was demonstrated that the chemical
pen can conveniently control pH condition at a defined micromixing region by employing different pH buffer solution as
injection. Control of liposome fusion to supporting lipid bilayer
was achieved.

■Invited Lectures■Academic Meeting＊International
1. Shungo Kato
Long-term measurements of trace gases at the summit of Mt.
Fuji during summer
ACID RAIN 2020 ， 2023/4/19 Toki Messe ・ Niigata
Convention Center，S3A-3
2. Kazuhiro Morioka, Toshimasa Miyawaki, Kenta Suzuki, Nori
Fujita, Shoji Yamamoto, Hizuru Nakajima, Akihide Hemmi,
Hajime Kayanne
Microfluidic-Based ISFET Sensor Using Carbon Fiber Tapefor Monitoring of Seawater pH
PITTCON2024 ， 2024/2/26 San Diego Convention Center
USA， PS-E266
3. Sota Hirose, Ryo Ishii, Shoji Yamamoto, Kazuhiro Morioka,
Akihide Hemmi, Hizuru Nakajima
Development of a portable genetic testing device based on
fluorescence detection using the LAMP method
PITTCON2024 ， 2024/2/27 San Diego Convention Center
USA， PS-I111
4. Sifeng Mao
Microchemical Pen: Microfluidic approach for single cell
analysis
Beijing Conference and Exhibition on Instrumental Analysis
2023，2023/9/8 ，Beijing, China
5. Sifeng Mao
Real-time electrochemical detection of lactate response fromsingle cell
Advances in Pharmaceutical Analysis 2023/11/10-12,
Beijing, China＊Domestic
See the annual report in Japanese (24 articles)■Papers with Peer Review
1. Hiroya Murakami, Keisuke Iida, Yuki Oda, Tomonari
Umemura, Hizuru Nakajima, Yukihiro Esaka, Yoshinori Inoue,
Norio Teshima
Hydrophilic interaction chromatography-type sorbent
prepared by the modification of methacrylate-base resin with
polyethyleneimine for solid-phase extraction of polar
compounds
Analytical Sciences, 2023, 39_3 375-381
2. Kuizhi Qu, Kazuhiro Morioka, Konoka Nakamura, Shoji
Yamamoto, Akihide Hemmi, Atsushi Shoji, Hizuru Nakajima
Development of a C-reactive protein quantification method
based on flow rate measurement of an ink solution pushed out
by oxygen gas generated by catalase reaction
Microchimica Acta, 2023, 191 24-24
3. Ryo Ishii, Sota Hirose, Shoji Yamamoto, Kazuhiro Morioka,
Akihide Hemmi, Hizuru Nakajima
Development of Portable Multi-fluorescence Detection
System Using Indium Tin Oxide Heater for Loop-mediated
Isothermal Amplification
Sensors and Materials, 2024,
4. S. Itahashia, N.K. Kim, Y.P. Kim, M.J. Song, C.H. Kim, K.S.
Jang, K.Y. Lee, H.J. Shin, J.Y. Ahn, J.Y. Jung, Z. Wu, J.Y. Lee,
Y. Sadanaga, S. Kato, N. Tang, A. Matsuki
Distinctive features of inorganic PM1.0 components during
winter pollution events over the upwind and downwind
regions in Northeast Asia
Atmospheric Environment, 309, 119943, 2023
5. K. Shimda, Y. Geka, S. Kato, C. K. Chan, Y. P. Kim, C.-F. OuYang, N.-H. Lin, S. Hatakeyama
Possibility of condensation of nitric acid for cloud
condensation nucleus in the summer at Mt. Fuji
Atmospheric pollution Research, 15, 101940, 2024
6. Jianmin Yang, Yuxiang He, Zhendong Li, Xudong Yang,
Yueming Gao, Mingmao Chen, Yunquan Zheng, Sifeng Mao,
Xianai Shi
Intelligent wound dressing for simultaneous in situ detectionand elimination of pathogenic bacteria■Books■Awards
See the annual report in Japanese (1 articles)28

Reports from Research Groups
Shudo Laboratory■Members
Toshio Shudo
Professor /Dr. Eng.
Energy Engineering, Thermal Engineering,Engineerng, Hydrogen Energy
room: 9-455 TEL: +81-42-677-2715
e-mail: shudot@tmu.ac.jp

Automotive

Doctor’s course -2
Master’s course -4
Bachelor 4 -1

■Outlines of the Research
1. Research on Homogeneous Charge Compression Ignition
Combustion.
Internal combustion engines have advantages over polymer
electrolyte fuel cells in terms of power output and durability.
This study analyzed homogeneous charge compression ignition
combustion, which is expected to be a new combustion method
for increasing the efficiency of internal combustion engines,
using elementary reaction numerical simulations. Auto-ignition
control by fuel reforming using engine exhaust heat is alsostudied.
2. Research on closed-cycle hydrogen engine
The Argon circulation closed-cycle hydrogen engine is expected
to have high theoretical thermal efficiency due to the highspecific heat ratio of the working fluid. In this study, thefeasibility of a closed-cycle hydrogen engine with argon
circulation using homogeneous charge compression ignition,
which has not been reported in the past, is analyzed using
elementary reaction numerical simulations.
3. Performance improvement in polymer electrolyte fuel cell.
Polymer electrolyte fuel cells have an advantage over internal
combustion engines in terms of theoretical efficiency but adisadvantage in terms of power output. This research is toimprove the power output of PEFCs, mainly by improving thereactant supply channel to reduce diffusion polarization. An
electrochemical hydrogen compression system using the same
cell is also studied.
4. Performance improvement in direct methanol fuel cell.
Direct methanol fuel cells have the advantage of high fuel energy
density, but they are inferior to polymer electrolyte fuel cells interms of power output. This research investigates the effect ofporous metal flow field for enhancing the reactant supply andproduct removal at the electrodes.

■Papers with Peer Review
See the annual report in Japanese■Academic Meeting＊Domestic
See the annual report in Japanese29Reports from Research Groups
Amano Laboratory■Members

hydrogen evolution reactions. Based on the conceptual
framework of vapor-fed PEC hydrogen production and strategic
design of gas-phase PEC reaction interfaces, we developed
porous photoanodes such as TiO2, WO3, strontium titanate(SrTiO3), and bismuth vanadate (BiVO4). A significant
enhancement in the PEC efficiency was achieved through theapplication of a thin proton-conducting ionomer film on these
porous photoelectrodes for surface functionalization. The
rational design of proton exchange membrane-based PEC cells
will play a pivotal role in realizing renewable-energy-drivenhydrogen production from atmospheric humidity in the air.

Fumiaki Amano
Professor /Dr. Eng.
Energy Chemistry, Photoelectrochemistry, Photocatalysis
room: Frontier Research Building 201
TEL: +81-42-677-2852 (Ext. 5561)
e-mail: f.amano@tmu.ac.jp
Kosuke Beppu
Assistant Professor /Dr. Eng.
Inorganic Materials Chemistry, Heterogeneous Catalysis,
Electrocatalysis
room: Frontier Research Building 201
TEL: +81-42-677-2852 (Ext. 5561)
e-mail: beppu@tmu.ac.jp
Specially Appointed Associate Professor - 1
Postdoctoral Researcher - 1
Doctor’s course - 2
Master’s course - 4
Bachelor (4th year) - 3
Research student - 1■Outlines of the Research
1. Photoelectrochemical methane conversion
We developed a continuous gas-fed photoelectrochemical(PEC) system with a proton exchange membrane for CH4
activation at ambient temperature and pressure. We found thatboth water splitting and steam reforming of CH4 were induced
over oxide photoanodes. When the CH4 concentration was low,O2 and CO2 were formed on titanium oxide (TiO2) and tungsten
trioxide (WO3) photoanodes under ultraviolet light irradiation.
We also found that visible light enhanced CH4 activation andethane (C2H6) formation over the WO3 photoanode. When theCH4 concentration increased, O2 formation was suppressed, withincreasing production rates of CO2, C2H6, and CO. Under
optimized conditions, the selectivity of C2H6 reached 57% on acarbon basis over the WO3 photoanode under visible-lightirradiation. The production of C2H6 implies the formation of
methyl radicals during the CH4 gas-fed PEC process. We also
demonstrated the PEC coupling of ethane to n-butane and thevisible-light-induced oxidation of CH4 without external bias.

3. Anion exchange membrane PEC water splitting
The requirement for liquid electrolytes to maintain their ionic
conductivity hinders the practical implementation of PEC
systems. We fabricated membrane electrode assembly byincorporating porous α-Fe2O3 (hematite)-based photoanodes
with an anion-exchange membrane (AEM). We demonstrated
AEM–PEC water splitting in pure water without supporting
electrolytes over porous hematite photoanodes under visiblelight irradiation. This PEC system was operational even under
low conductivity and near-neutral conditions (∼1 mS/m and pH∼9). Action spectral analysis confirmed a visible-light response
extending up to 600 nm, surpassing that of previously reported
photoelectrodes with solid-electrolyte membranes.

4. Electrocatalysts for water electrolysis
Ruthenium oxide (RuO2) electrocatalysts possessing highactivity and stability are needed to sustain the oxygen evolution
reaction (OER) under harsh anodic conditions in acidic waterelectrolysis systems. We explored the activity and stability of
RuO2 particles coated on a Ti-fiber felt substrate. Amorphous
RuO2 particles of low crystallinity exhibited large
electrochemically active surface areas (ECSAs) and high OER
activity but were unstable during the OER in 0.1 M H2SO4.
However, the complete thermal decomposition of a RuCl3
precursor solution at temperatures above 250 °C yielded RuO2
particles with enhanced crystallinity and greater resistance todissolution under anodic conditions in H2SO4. An optimum
calcination temperature of 350 °C produced RuO2 nanoparticles
on a Ti-felt with balanced ECSAs and high crystallinity, while
simultaneously achieving high OER activity and enhanced

2. Proton exchange membrane PEC water splitting
We developed vapor-fed PEC systems specifically designed
for utilizing water vapor as a hydrogen resource. The PEC
system under water vapor feeding utilizes a proton exchange
membrane as a solid polymer electrolyte. Additionally, it utilizes
gas-diffusion photoelectrodes composed of a fibrous conductive
substrate with macroporous structures. Herein, the porous
photoelectrodes are composed of n-type oxides for oxygen
evolution reactions and used with a Pt electrocatalyst cathode for30

Reports from Research Groups■Invited Lectures

stability. The optimized nanocrystalline RuO2/Ti-felt(350)electrocatalyst was stable throughout 48 h of operation at 50 mA
cm−2 at pH 1.0 and delivered a stability number greater than 1 ×
105, which is comparable to the value provided by more costly
IrO2 electrocatalysts.

＊International
1. F. Amano, Proton exchange membrane photoelectrochemicalcell and gas-diffusion photoanodes for vapor-fed water
splitting, The Annual Nanotechnology Conference 2023,
August 27–30, 2023, Warsaw, Poland, Invited Talks＊Domestic
See the annual report in Japanese (2 lectures)■Academic Meeting＊International
1. F. Amano, S. Nakayama, and K. Beppu, Activation ofMethane Mediated by Water Molecules on the Surface of
Semiconductor Photocatalysts, The 19th Korea-Japan
Symposium on Catalysis, May 15–17, 2023, Seoul, Korea, Oralpresentation
2. D.O.B. Apriandanu, R.M. Surya, and F. Amano, Anion
Exchange Membrane Photoelectrochemical Water Splitting
Using Porous Hematite Photoanodes, The 19th Korea-Japan
Symposium on Catalysis, May 15–17, 2023, Seoul, Korea, Oralpresentation (Oral Presentation Award)
3. R.M. Surya, D.O.B. Apriandanu, K. Beppu, and Fumiaki
Amano, Surface Modification of Macroporous Cu2O
Photocathode for Hydrogen Evolution Reaction, The 19th
Korea-Japan Symposium on Catalysis, May 15–17, 2023,
Seoul, Korea, Poster presentation
4. F. Amano, S. Nakayama, and K. Beppu, Photocatalytic
Dehydrogenative Coupling of Methane Mediated by Water
Molecules on Semiconductor Photocatalysts, The Annual
Nanotechnology Conference 2023, August 27–30, 2023,
Warsaw, Poland, Poster presentation＊Domestic
See the annual report in Japanese (22 presentations)■Papers with Peer Review

1. F. Amano*, S. Nomura, C. Tateishi, S. Nakayama,
Clarification of Photoelectrochemical Oxygen Evolution Sites
in TiO2 Nanotube Array Electrodes by PbO2 Deposition
Method, Journal of The Electrochemical Society, 170, Article
026501, 2023
2. D.O.B. Apriandanu, S. Nakayama, K. Shibata, F. Amano*,"Ti-doped Fe2O3 Photoanodes on Three-Dimensional Titanium
Microfiber Felt Substrate for Photoelectrochemical Oxygen
Evolution Reaction", Electrochimica Acta, 456, Article
142434, 2023
3. J.J.M. Vequizo, K. Kato, F. Amano, and A. Yamakata*,"Unfolding the Impact of H2‑Reduction Treatment inEnhancing the Photocatalytic Activity of Rutile TiO2 Based on
Photocarriers Dynamics", The Journal of Physical ChemistryC, 127(22), pp 10411–10418, 2023
4. F. Amano*, A. Shintani, T. Sakakura, Y. Takatsuji, T.
Haruyama, "Photoelectrochemical C–H Activation of Methane
to Methyl Radical at Room Temperature", Catalysis Science &Technology, 13(16), pp 4640–4645, 2023
5. D.O.B. Apriandanu, R.M. Surya, K. Beppu, F. Amano*,"Anion Exchange Membrane Photoelectrochemical Water
Splitting Using Porous Hematite Photoanodes", ACS Applied
Energy Materials, 6(21), pp 10736–10741, 2023
6. K. Beppu, K. Obigane, F. Amano*, "Amorphous versus
Nanocrystalline RuO2 Electrocatalysts: Activity and Stability
for Oxygen Evolution Reaction in Sulfuric Acid", Catalysis
Science & Technology, 13, pp 6653–6661, 2023
7. F. Amano*, A. Ishikawa, H. Sato, C. Akamoto, S.P. Singh, S.
Yamazoe, T. Sugimoto, "Facilitating Methane Conversion andHydrogen Evolution on Platinized Gallium Oxide Photocatalyst
through Liquid-like Water Nanofilm Formation", Catalysis
Today, 426(15), Article 114375, 2024
8. F. Amano*, K. Tsushiro, "Proton Exchange Membrane
Photoelectrochemical Cell for Water Splitting under Vapor
Feeding", Energy Materials, 4, Article 400006, 2024, Mini
Review, Special Issue in Interface Engineering in(Photo)electrochemical Systems
9. T. Yamamoto*, S. Kawaguchi, T. Kosuge, A. Sugai, N.
Tsunoda, Y. Kumagai, K. Beppu, T. Ohmi, T. Nagase, K.
Higashi, K. Kato, K. Nitta, T. Uruga, S. Yamazoe, F. Oba, T.
Tanaka, M. Azuma, S. Hosokawa*, "Emergence ofDynamically-Disordered Phases During Fast Oxygen
Deintercalation Reaction of Layered Perovskite", Advanced
Science, 10(19), Article 2301876, 2023

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

31

Applied Chemistry Colloquium

400th

2023/09/08
Akihiko Kikuchi (Tokyo University of Science)” Thermo-Responsive Polymers for Biomaterials ”

401st

2023/09/22
Makoto Tokunaga (Department of Chemistry, Graduate School of Science,
Kyushu University)” Novel Topics in Sulfur Chemistry ー Adsorption and Decomposition
Desulfurization, Synthesis of sulfanes using hydrogen instead of hydrogensulfide ”

402nd

2024/01/23
Shigehiro Yamaguchi (Nagoya University)” Main-Group-Rich π-Electron Materials: Design and Application ”

403rd

2023/11/10
Hiroshi Yanagi (Graduate Faculty of Interdisciplinary Research, Faculty ofEngineering, Materials Science, University of Yamanashi)” Material design guidelines and practices for oxide-based semiconductormaterials ”

404th

2023/12/21
Ikuhiko NAKASE (Department of Biological Chemistry, Graduate School of
Science, Osaka Metropolitan University)” Development of drug delivery systems using extracellular vesicles andeffective use of functional peptides ”

405th

2024/01/22
Ali M. Abdel-Mageed (Surface Chemistry in Applied Catalysis, Leibniz
Institute for Catalysis, Germany)” Catalysis on Heterogeneous Single-Atom Catalysts Supported by
Metal-Organic Frameworks-Opportunities and Challenges ”

32Annual Report 2023
Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry for Environmental Sciences
April 1, 2024