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

Annual Report 2022

IndexReports from Research Groups
Kawakami Laboratory

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1

Asayama Laboratory

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7

Kubo Laboratory

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9

Setaka Laboratory

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12

Kanamura Laboratory

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14

Kajihara Laboratory

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16

Takagi Laboratory

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18

Analytical Chemistry Laboratory

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22

Shishido Laboratory

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26

Shudo Laboratory

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28

Amano Laboratory

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29

Colloquium

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31

Reports from Research Groups
Kawakami Laboratory
these particles. The composite membranes containing 50wt%
particles showed excellent toughness. In addition, the gas
permeability of the composite membrane was 5 to 10 times
higher than that of the matrix polymer, indicating that thecomposite membrane has better gas permeability than previous
composite membranes.

■Members
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
Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-ScienceRm. 9-137, +81-42-677-1111 Ext. 4837
yamato-masafumi@tmu.ac.jp
Kiyoshi SATO
Associate Professor / Dr. Eng.
Synthetic Organic Chemistry, Molecular Recognition,
Heterocyclic Chemistry, Physical Organic ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
sato-kiyoshi@tmu.ac.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

Figure 1. Schematic drawing of nanoparticle/PIM-1 composite
membrane.

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

2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA, Toyotaka NAKAE
Polymer electrolyte fuel cells have attracted much attention
as clean and sustainable energy systems. We have reported
composite polymer electrolyte membranes based on phytic acid(Phy)-doped polybenzimidazole nanofibers (PBINF) showed
outstanding fuel cell performances under low relative humidity
conditions.
In this year, we studied the stability of polymer electro
membranes for long-term durability of polymer electrolyte fuelcells. Most polymer electrolytes, including Nafion®, are known
to be degraded by reactive radicals generated by gas crossover
through the membranes (Fig.2). The Fenton tests were attempted
to analyze chemical degradation of the polymer electrolyte
membranes. As a result, the nanofiber composite membranes,
especially composite membranes based on blend nanofibers
consisted of sulfonated polymers and basic polymers, showed
higher chemical stabilities than the membrane without
nanofibers. In addition, the membrane fabrication processes
were also investigated for practical realization of fuel cells using
the nanofiber composite membranes.
Another study on water electrolysis using anion exchange
membranes were also carried out.

Toyotaka NAKAE
Research Associate Professor / Dr. Sci.
Organometalic Chemistry, Coordination Chemistry, Inorganic
ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
nakae-toyotaka@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
Doctor’s course - 4
Master’s course - 19
Bachelor 4 - 11
Researcher - 3■Outlines of the Research
1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO
Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO2). Recently, we
have reported that novel composite membranes composed of thefluorinated polyimide or polymers of intrinsic microporosity(PIM) and surface-modified silica nanoparticles exhibit high gas
permeability and selectivity.
This year, we developed new surface-modified silica
nanoparticles and evaluated composite membranes containing

Figure 2. Chemical degradation mechanism of polymer
electrolyte membranes.

1Reports from Research Groups
3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA

Epigenetics 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
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.

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 novel
polymer composite membranes consisted of poly(vinyl ethylene
carbonate) (PVEC)-based matrix polymer electrolytes, insteadof conventional poly(ethylene oxide) (POE)-based one, were
fabricated by combining the electrospun polymer nanofibers.
The novel nanofiber composite membranes showed significantly
high ion conductivity above 10-3 S/cm at room temperature,indicating the high potential of the nanofiber composite
membranes for high-performance secondary batteries.

Figure 5. Gene expression control through chromatin
modifications.
Figure 3. Schematic illustration of lithium ion conductive
polymer nanofiber composite membrane for all solid statelithium ion batteries.

6. Suppression of Cellular Senescence
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Masahiro
YOSHIOKA

4. Catalysts for Electrochemical CO2 Reduction
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Toyotaka NAKAE

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.

Electrochemical CO2 reduction is one of the promising
methods for CO2 conversion into fuels or valuable raw materials
for chemical products form recovered CO2 emitted by factories,
offices, commercial facilities, and households or exist in theatmosphere. However, an effective catalyst with both productselectivity and ability to suppress O2 reduction and H2 generation
has yet to be found.
In this year, we have prepared catalyst-modified electrodes
fabricated by drop-cast deposition of metal oxide nanoparticle
onto copper nanocrystals. The catalyst-modified electrodes
suppress the competitive reactions, i.e. O2 reduction and H2evolution, and improve the C2/C1 product selectivity provably
due to maintain the oxidative state of Cu surface. Further
improvement of the catalytic activity and the product selectivity
is under investigation.

Liposome

Mn Porphyrin (MnP)
Renewableenergy-based
electricity
Catalyst

DOTMA + DOPE (1:1)

Carbon monoxide
COFormic acidN

Methanep53 inhibitor(pifithrin-a)

N

Mn
N

N

N

N

O

Carbon dioxide
(CO2)

H 3C

CH3

N

Ethylene

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

Ethanol

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

NH

CH3

S

Figure 6. Structure of mitophagy-induced liposomal nanocarrier.

Figure 4. CO2 conversion by electrochemical CO2 reduction
catalyst.

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

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

Controls of higher-order structure of feeble magnetic
materials by using a magnetic field have been studied in order to2

Reports from Research Groups
improve some properties and to reveal new functions of thematerials.
This year, we investigated the magnetic orientation ofhydrotalcite, which is one of the layered double hydroxides. It
was found that the c-axis of hydrotalcite is oriented
perpendicular to the magnetic field. This result indicates that theanisotropy of hydrotalcite composite films can be controlled byusing a magnetic field.

7.

8.

9.
Figure 7. Crystal structure of hydrotalcite (left) and schematic
drawing of magnetic orientation (right).
Application of biochar to stress tolerance of enzymes
Hidetaka NORITOMI

10.

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.
Masafumi Yamato, Ayano Imai, Hiroyoshi Kawakami,“Thermal properties of polymer with intrinsic
microporosity membranes”, Polymer, 259, 125339 (2022).
DOI: 10.1016/j.polymer.2022.125339
2.
Yuta Yoshimoto, Yuiko Tomita, Kohei Sato, Shiori,
Higashi, Masafumi Yamato, Shu Takagi, Hiroyoshi
Kawakami, Ikuya Kinefuchi, “Gas Adsorption and
Diffusion Behaviors in Interfacial Systems Composed of a
Polymer of Intrinsic Microporosity and Amorphous Silica:
A Molecular Simulation Study”, Langmuir, 38, 7567-7570(2022)
3.
Yuri Nara, Manabu Tanaka, Kensaku Nagasawa,
Yoshiyuki Kuroda, Shigenori Mitsushima, Hiroyoshi
Kawakami, "Development of highly alkaline stable anion
conductive polymers with fluorene backbone for waterelectrolysis", Polymers for Advanced Technology, 33,
2863-2871 (2022) DOI: doi/full/10.1002/pat.5752
4.
Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, Solvated Ionic-Liquid Incorporated Soft
Flexible Cross-Linked Network Polymer Electrolytes for
Safer Lithium Ion Secondary Batteries, Macromolecular
Chemistry and Physics, 223, 2100317 (2022). DOI:
10.1002/macp.202100317
5.
Kazushi Enomoto, Kotaro Takeda, Naoto Iwata, Kiyohiro
Adachi, Tomoka Kikitsu, Yasuhiro Ishida, Daisuke
Hashizume, Manabu Tanaka, Hiroyoshi Kawakami, andYong-Jin Pu, "Colloidal CdS Quantum Dot Fibers
Prepared by Electrospinning of Their Wet Gel for
Quantum Nanowires", ACS Applied Nano Materials, 5,3756-3762 (2022) DOI: 10.1021/acsanm.1c04403
6.
Keisuke Ashiba, Koki Mino, Yui Okido, Kiyoshi Sato,

11.

12.

13.

Hiroyoshi Kawakami, “Senescence recovering by dual
drug-encapsulated liposomal nanoparticles for large-scale
human cell expansion”, Journal of Artificial Organs,
Advance online publication (2022). DOI: 10.1007/s10047022-01356-x
Kazuma Komine, Takashi Nakaoji, Masafumi Yamato,
Magnetic
OrientationofLiquidCrystalline
Montmorillonite in Ionic Liquids, Chemistry Letters, 51,
1008 (2022). DOI:
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 (2022)
Yasuko Noritomi, Takashi Kuboki, Hidetaka Noritomi,“Promotion of the Redox Reaction at Horseradish
Peroxidase Modified Electrode Combined with Ionic
Liquids under Irreversible Electrochemical Conditions”,
Results in Chemistry,4, 100666 (2022)
Hiroto Miyabe, Mizuha Ujita, Masaki Nishio, Toyotaka
Nakae, Tsukasa Usuki, Minako Ikeya, Chika Nishimoto,Suguru Ito, Mineyuki Hattori, Satoshi Takeya, Shigenobu
Hayashi, Daisuke Saito, Masako Kato, Hiroshi Nishihara,
Teppei Yamada, Yoshinori Yamanoi "A series of D‒A‒D
structured disilane-bridged triads: structure and stimuliresponsive luminescence studies" The Journal of Organic
Chemistry, 87, 8928–8938 (2022). DOI: 10.1021/acs.joc.
2c00641
Masahiro Yoshioka, Rio Matama, Mayu Miyoshi,
Momoka Chatani, Akiko Takenouchi, Yuichi Kinoshita,
Yoshiharu Okamoto, Katsuhiko Yoshizawa, “Evaluationof Chitosan Oligosaccharide Supplementation in Breast
Cancer using In Vitro and In Vivo model.”, Basic
Investigation of Breast Carcinoma, 29, 39-45 (2022) (inJapanese)
Akiko Takenouchi, Risa Enomoto, Yuka Horikawa,
Chihiro Koyama, Masahiro Yoshioka, Takafumi Iguchi,
Kazuhiko Yamashita, Yoshiharu Okamoto, Katsuhiko
Yoshizawa, “Effects of Sake-Lees-Derived Profine®
Supplementation In Rat Models of Acute Hepatic Injury”,
Functional Food Research, 17, 166-176 (2022) (inJapanese)
Momoka Chatani, Naomi Saito, Masahiro Yoshioka,
Yuichi Kinoshita, Hanae Nakamura, Yuki Hashimoto,
Akiko
Takenouchi,
Katsuhiko
Yoshizawa,“Pathophysiological Inhibitory Effect of Acerola in NMethyl-N-Nitrosourea-Induced Cataract Rat Model”, New
Food Industry, 65, 3, 143-151 (2023) (in Japanese)■Books1.
Kiyoshi Sato, Hiroyoshi Kawakami, “ Treatment of
Cellular Senescence with Functional Nanoparticles
Restoring Mitochondrial Quality Control System －Rejuvenation of Senescent Cells by Reactivation of
Mitophagy －”, The CELL, 55 (2), 111-114 (2023) (inJapanese)
2.
Kiyoshi Sato, Hiroyoshi Kawakami, “Engineering
Exosomes – A New Platform in Therapeutics”, Chemistry,
78 (3), 66-67 (2023) (in Japanese)3.
Masafumi Yamato, Kazuma Komine, Kohki Takahashi,

3

Reports from Research Groups

4.

Development of anisotropic gel with nano-expander
structure, 2022 Annual report of high field laboratory forsuperconducting materials in institute for materials
research at Tohoku university ，p.p. 152-153 (2022) (inJapanese)
Hidetaka Noritomi, Biochar: Characterization andApplications in Enzyme Technology, Durham, UnitedStates, Generis Publishing (2022)

Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami, Gas permeation property of PIM-1 membrane
at high temperature, 71th SPSI Annual Meeting (Online
Virtual Meeting), 2P3D017, May 2022 (in Japanese).
3. Kaito Udo, Masafumi Yamato, Hiroyoshi Kawakami,
Fabrication and gas permeation properties of gas
separation membranes based on nanofiber framework, 71th
SPSI Annual Meeting (Online Virtual Meeting), 2P1E013,
May 2022 (in Japanese).
4. Kenta Sando, Nohara Yokota, Manabu Tanaka, Hiroyoshi
Kawakami, Fabrication and evaluation of polymer
nanofiber composite electrolyte membranes with various
lithium salt concentrations, The 71st SPSJ Annual Meeting(Online), 2PA018, May 2022 (in Japanese)
5. Kohei Shibusawa, Koki Mino, Keisuke Ashiba, Kiyoshi
Sato and Hiroyoshi Kawakami, Restoration of
mitochondrial quality control mechanism in senescentstem cells by mitophagy-inducing nanocarriers., The 71th
SPSJ Annual Meeting (Online), 3P4B046 May 2022 (inJapanese)
6. Ryota Inahara, Kazuto Suzuki, Manabu Tanaka, Hiroyoshi
Kawakami, Fabrication and fuel cell evaluation ofcomposite electrolyte membranes composed of acid/basic
blend nanofibers for higher proton conductivity at hightemperature and under low humidity, The 29th Fuel Cell
Symposium (Tower Hall Funabori), No.11 May 2022 (inJapanese)
7. Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami, Temperature dependence of gas permeabilityof PIM-1 composite membrane with surface-modified
silica nanoparticles., 44th annual meeting of membranescience of Japan, June 2021, P-118S, (Online) (inJapanease).
8. Kaito Udo, Masafumi Yamato, Hiroyoshi Kawakami, Gas
permeation properties of composite membranes consistedof PIM-1 and nanofiber framework, 44th annual meetingof membrane science of Japan, June 2021, P-125, (Online)(in Japanease).
9. Ryota Inahara, Kazuto Suzuki, Manabu Tanaka, Hiroyoshi
Kawakami, Fabrication and evaluation of composite
electrolyte membranes composed of acid/basic blend
polymer nanofibers for fuel cell operation over wide
temperature range, The Annual Meeting of the Society ofFiber Science and Technology (Hybrid), IC07 June 2022
(in Japanese)
10. Kenta Sando, Nohara Yokota, Manabu Tanaka, Hiroyoshi
Kawakami, The effects of lithium salt concentration on
secondary battery properties of polymer nanofiber
composite electrolyte membranes, The Annual Meeting of
the society of fiber science and technology Japan (Tower
Hall Funabori, On-site & Online), 1C09, June 2022 (inJapanese)
11. Kota Iwasaki, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and evaluation of acid-functionalized andpolydopamine-modified nanofibers for fuel cellapplication, The Annual Meeting of the society of fiberscience and technology Japan, 1PA207, June 2022 (inJapanese)
12. Kota Iwasaki, Manabu Tanaka, Hiroyoshi Kawakami,
Introduction of acid functional groups to nanofiber surface
by in-situ polymerization and fabrication of nanofiber
2.

■Invited Lectures
1. Hiroyoshi Kawakami, Development of ultra-high CO2
permeable separation membranes for CCS- and DACoriented strategies, SPSJ, June 2022, Online (in Japanese).
2. Hiroyoshi Ionic conductive polymer nanofibers that improvebattery performance, SPSJ Webiner, July 20212, Online (inJapanese).
3. Hiroyoshi Kawakami, Development of polymer materials
realizes "decarbonization", 71th Polymer Symposium inJapan, September 2022 (Hokkaido Univ.), September
2022, (in Japanease).
4. Hiroyoshi Kawakami, Cell rejuvenation by nanocarrier,Cosme Tech 2022 Tokyo (Tokyo), January 2022 (inJapanese).
5. Hiroyoshi Kawakami, Development of electrolyte
membranes for fuel cells required after 2030s and 2040s,
Special lecture at Iwate University (Morioka), January 2023,(in Japanese).
6. Hiroyoshi Kawakami, Functional membranes that control
H2 and CO2 - H2O2 control leads to next-generation
infectious disease treatment -, Kobe University, Membrane
Technology (Hobe), March 2023 (in Japanese).
7. Kiyoshi Sato, “Potential of metalloporphyrin and copper
catalysts for electrochemical CO2 reduction", Technical
Information Institute seminar "CO2 catalysts", May 2022
(Online) (in Japanease)
8. Manabu Tanaka, Hiroyoshi Kawakami, Electrolyte
Membrane Applications of Electrospun Polymer Nanofibers
to Improve Fuel Cell and Battery Performances, The Annual
Meeting of the Society of Fiber Science and Technology(Tokyo), June 2022 (in Japanese)
9. Manabu Tanaka, Development of Battery Materials Basedon Organic Nanoionics, Summer Seminar for Young
Researchers, Society of Polymer Science Japan, Tohoku
Division (Online), July 2022 (in Japanese).
10. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2022 Basic seminar of polymer science for young
engineers, Dec. 2022, Tokyo, Japan (in Japanese).
11. Masafumi Yamato, Higher-order structure analysis ofmacromolecules,
Characterization
seminarfor
macromolecules 2022, Mar. 2023, Online (in Japanese)
12. Masafumi Yamato, Tokyo Metropolitan University x
Kansai University "~Considering the Future Global
Environment~" Online Environmental Symposium, Mar.
2023, Online (in Japanese)■Academic Meeting
1. Yasutaka Kuwahara, Kazuma Komine, Toyotaka Nakae,
Hiroyoshi Kawakami, Fabrication and properties ofcrosslinked-PVA
nanofiber-framework
compositemembrane for fuel cell, The 71th SPSJ Annual Meeting,(Online), 2P1C012, May 2022 (in Japanese)4

Reports from Research Groups

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

composite electrolyte membranes, The Annual Meeting of
the society of fiber science and technology Japan, 1C08,
June 2022 (in Japanese)
Shuntarou Kimura, Hiroyoshi Kawakami, Induction ofcellular senescence in cancer cells using epigenetics
control carriers, The 26th Annual Meeting of the Japanese
Association for Molecular Target Therapy of Cancer（ISHIKAWA ONGAKUDO）, P3-5 （June 2022)
Mizuki Akatsuka, Masafumi Yamato, Hiroyoshi
Kawakami, Temperature dependence of gas permeability
for mixed matrix membranes composed of PIM-1 andsurface-modified silica nanoparticles, The 13th conferenceof the Aseanian Membrane Society, (Online), P01, July2022.
Kazuma Komine, Takashi Nakaoji, Masafumi Yamato, andKawakami Hiroyoshi, Anisotropic properties of Liquid
Crystal comprising Clay and Ionic Liquid., IUMRSICYRAM2022, (Online), A-O3-013, August 2022.
Yuri Nara, Manabu Tanaka, Hiroyoshi Kawakami,
Synthesis and Water Electrolysis Evaluation of Anion
Conductive Polymers Bearing no heteroatoms in thepolymer main chains, 2022 ReHES Workshop(after thelecture meeting by Prof. Dario R. Dekel), (Tokyo
Metropolitan University), A20, September 2022.
Kiyoshi Sato, Koki Mino, Ayaka Mori, Keisuke Ashiba,
Masahiro Yoshioka, Hiroyoshi Kawakami, "Liposomal
nanoparticles for maintaining cell quality”, 71st Polymer
Symposium in Japan, September 2022 (Sapporo) (inJapanease).
Manabu Tanaka, Nohara Yokota, Kenta Sando, Ryodai
Fujihashi, Hiroyoshi Kawakami, Development of polymer
nanofiber-based composite electrolyte membranes andevaluation of the lithium ion conduction mechanism in thecomposite membranes, 71th Polymer Symposium in Japan,
September 2022 (Hokkaido Univ.) (in Japanease)
Masafumi Yamato, Shiori Higashi, Hiroyoshi Kawakami,
Structure and Gas Permeation Properties of Highly
Concentrated Silica Composite Membrane, 71st Polymer
Symposium in Japan, September 2022 (Sapporo) (inJapanese)
Yuta Yoshimoto, Yuiko Tomita1, Kohei Sato, Shiori
Higashi, Masafumi Yamato, Shu Takagi, Hiroyoshi
Kawakami, Ikuya Kinefuchi, Analysis of gas adsorption
and diffusion processes in interfacial systems composed ofa polymer of intrinsic microporosity and amorphous silica
using molecular simulation techniques, 71st Polymer
Symposium in Japan, September 2022 (Sapporo) (inJapanese)
Masafumi Yamato, Kaito Udo, Hiroyoshi Kawakami, Gas
Permeability of Composite Membranes using Polymer
Intrinsic Microporosity Matrix, 71st Polymer Symposium
in Japan, September 2022 (Sapporo) (in Japanese)
Masafumi Yamato, Mizuki Akatsuka, Shiori Higashi,
Hiroyoshi Kawakami, Structure and Physical Properties ofHighly Loaded Films with Silica Nanoparticles, 71st
Polymer Symposium in Japan, September 2022 (Sapporo)(in Japanese)
Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,
Particle-containing polymer membrane with highpermeability for Direct Air Capture, The 71th Polymer
Symposium in Japan, (Hokkaido Univ.), 3J01, Sept. 2022.

24. Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,High permeable PIM-1 complex membrane loaded withhigh concentration of particles, The 71th Polymer
Symposium in Japan, (Hokkaido Univ.), 3Pe065, Sept.
2022.
25. Akari Tatsukawa, Toyotaka Nakae, Hiroyoshi Kawakami,
Optimization of Fabrication Process for Polymer
Nanofiber Composite Membrane to Improve ProtonExchange Membrane Properties, The 71th Polymer
Symposium in Japan, (Hokkaido Univ.), 2Pa089, Sept.
2022.
26. Toyotaka Nakae, Kazuto Suzuki, Yasutaka Kuwahara,
Manabu Tanaka, Hiroyoshi Kawakami, Development of
Composite Polymer Electrolyte Membranes Containing
Nanofibers Working in Wide Temperature Range towards
Next Generation Fuel Cell, The 71th Polymer Symposium
in Japan, (Hokkaido Univ.), 2L13, Sept. 2022.
27. Manabu Tanaka, Nohara Yokota, Kenta Sando, Ryodai
Fujihashi, Hiroyoshi Kawakami, Lithium ion conductivity
evaluation and mechanism analyses of polymer nanofiber
composite electrolyte membranes, 63rd Battery
Conference (Fukuoka International Conference Center),November 2022 (in Japanease)
28. Yuri Nara, Manabu Tanaka, Kensaku Nagasawa, Yoshiyuki
Kuroda, Shigenori Mitsushima, Hiroyoshi Kawakami,
Synthesis and Water Electrolysis Evaluation of Anion
Conductive Polymers with Fluorene Backbone., The 31ｓｔ
Polymer Materials Forum, (Tower Hall Funabori), 1PB22,
November 2022 (in Japanese)
29. Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,
Gas permeation properties of ultra-high CO2 permeable
composite membranes loaded with highly concentrated
surface-modified nanoparticles, Membrane Symposium2022 in Japan, (Kobe Univ.), P-39S, Nov. 2022
30. Kota Nagano, Masafumi Yamato, and Kawakami
Hiroyoshi, Effect of pressure on gas permeability ofsurface-modified silica nanoparticle/PIM-1 composite
membranes, Membrane Symposium 2022, (Kobe
University Centennial Hall), P-14S, November 2022.
31. Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Magnetic orientation of Liquid Crystal
comprising Ionic Liquid and Sepiolite., 16th MagnetoScience Society of Japan , (Nihon Univ.), P-17, November
2022 (in Japanese)
32. Yusei Shinada, Masafumi Yamato, Hiroyoshi Kawakami,
Orientation control of layered double hydroxides using
magnetic field P-18, 2022 Annual Meeting of theMagneto-Science Society of Japan, (Online), Nov. 2022(inJapanese)
33. Yusei Shinada, Masafumi Yamato, Hiroyoshi Kawakami,
Anisotropy Control of PVA/Layered Double Hydroxide(LDH) Composites P15, 95th Musashino Area Polymer
Symposium, Nov. 2022(in Japanese)
34. Dong Yubing, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and Lithium Ion Conductivity Evaluation of
Cross-linked Network Polymer Electrolytes Containing
Solvated Ionic Liquid, The 12th Ionic Liquid Symposium,
Nov. 2022
35. Hidetaka Noritomi, Mariko Shimokawa, Jumpei
Nishigami, Satoru Kato, Kiyoshi Sato, Hiroyoshi
Kawakami, “Absorption of Enzymes on Hollow Carbon

5Reports from Research Groups

36.

37.

38.

39.

40.

Microparticles prepared from Lignin and Heat Stress
Tolerance of Adsorbed Enzymes”, SSPEJ Annual Meeting
2022, November 2022 (on line) (in Japanese)
Manabu Tanaka, Kazuto Suzuki, Hiroyoshi Kawakami,
Proton Conductive Nanofibers-based Polymer Electrolyte
Composite Membranes for Fuel Cells, MRS-J 2022
(Yokohama) December 2022
Momoka Chatani, Naomi Saito, Masahiro Yoshioka,
Yuichi Kinoshita, Hanae Nakamura, Yuki Hashimoto,
Akiko
Takenouchi,
Katsuhuko
Yoshizawa,“Pathophysiological Inhibitory Effect of Acerola on
Streptozotocin-Induced diabetic Cataract Rat Model”, the19th Annual Meeting of Society for Functional Foodresearch (WINC AICH, hybrid), Y-4, January, 2023 (inJapanese)
Akiko Takenouchi, Haruna Kibi, Yukino Mori, Momoka
Chatani, Hanae Nakamura, Yuki Hashimoto, Masahiro
Yoshioka, Yuichi Kinoshita, Katsuhuko Yoshizawa,“Inhibitory Effects of Acerola Supplementation In Rat
Model of Acute Hepatic Injury Derived from Green Tea
Extract”, the 19th Annual Meeting of Society for
Functional Food research (WINC AICH, hybrid), G-8,
January, 2023 (in Japanese)
Ayaka Mori, Koki MINO, Yui Okido, Keisuke Ashiba,
Masahiro Yoshioka, Kiyoshi Sato, Hiroyoshi Kawakami,"Liposomal nanoparticles for maintaining cell quality”,
71st Polymer Symposium in Japan, September 2022
(Sapporo) (in Japanease)
Dong Yubing, Manabu Tanaka, Hiroyoshi Kawakami,
Synthesis and Evaluation of Polymer Gel Electrolyte
Membranes Using Solvated Ionic Liquid and Their
Application to Lithium Ion Batteries, The 103rd CSJ
Annual Meeting, March 2023 (in Japanese)■Patents1.

2.

Gas separation membrane, Hiroyoshi Kawakami,
Masafumi Yamato, Shiori Higashi, Takumu Morita,
PCT/JP2022/030868（2022/8/15）
Gas separation membrane, Hiroyoshi Kawakami,
Masafumi Yamato, Takumu Morita, Mizuki Akatsuka，JP2023-021451（2023/2/15）■Awards1.

2.

3.

Membrane Symposium 2022 in Japan, Student Award,
Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,“Gas permeation properties of ultra-high CO2 permeable
composite membranes loaded with highly concentrated
surface-modified nanoparticles”.
The 71th Polymer Symposium in Japan, Publicity Award,
Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,“Particle-containing polymer membrane with highpermeability for Direct Air Capture”.
Student Special Award, Yuri Nara, Graduate School andFaculty of Urban Environmental Sciences, Tokyo
Metropolitan University

6

Asayama Laboratory■Members

function in respons to external stimuli. Recently, Zn2+ delivery
to liver is applied for remote control of hypoglycemic hormone(Figure 2).

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

Insulinsecretion

Survival insulin
to whole bodyZn 2+

InsulinPancreas

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

Liver

H
C CH2
N

ProteinAs water-soluble (liquid-phase) biomaterials, the carriers of
nucleic acid as a macromolecular drug have been designed for
unmet medical needs. Recently, the mono-ion complex (MIC)
to make plasmid DNA (pDNA), as a gene, highly condensed has
been formed for delivery to in vivo unexplored space (Figure 1).

++

Delivery toUnexplored
Space

O
H2N

N

N

N

1-x-y

Zn2+

n

3. Biomaterials with Funtional Surface
Shoichiro ASAYAMA

Mono-Ion Complex【MIC】
C(CH2)ny

In this year, we have focused on the in vivo skeletal muscle
pDNA delivery system by forming annealed pDNA/Zn2+/PVIm
PICs. The resulting pDNA/Zn2+/PVIm PICs increased in vitro
pDNA expression, as compared to unannealed pDNA/Zn 2+/
PVIm PICs.
Moreover, in vivo skeletal muscle pDNA
expression mediated by the resulting annealed PICs was also
greater than naked pDNA. Consequently, the annealed pDNA
is considered to lead to high expression both in vitro and in vivo
by retaining nonionic PVIm backbone and Zn 2+ ions.

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

N

Figure 2. Remote control of hypoglycemic hormone in blood.

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

+

x

H
C CH2

+
N
N
(CH2) CH3

N

■Outlines of the Research

H
C CH2

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

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

DiseaseCH2CH2OnCH3In this year, we have synthesized 2nd generationpolyamidoamine dendrimer modified with guanidinium groups,
PAMAM-G2-Gu, as a pDNA carrier for floating blood cells.
Especially, PAMAM-G2-Gu with a modification degree of 53
mol%, PAMAM-G2-Gu(53), showed almost no cytotoxicity.
The resulting PAMAM-G2-Gu(53)/pDNA polyion complex(PIC) showed the highest gene expression ability for humanleukemia cell line HL-60 among all PICs including liner carriers
and branched poly(ethyleneimine) as a golden standard.

H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

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

CH3

H3C

Insulin

7

8

9
10
11
Elution volume / mL

12

Figure 3. Development of novel bio-function by Chol-PEG.
In this year, to design more stable surface modification byincreasing the ratio of a cholesterol group per molecule of CholPEG. Short-chain PEG (Mn=500) close to molecular weight ofcholesterol anchor group was used (Chol-PEG500) for surface
modification. The Chol-PEG500-coated poly(propylene) (PP)surface showed about 98% inhibition after 3-day incubation,
negligible hemolysis, and inhibition of platelet adsorption. The
resulting Chol-PEG500-coated PP exhibited biocompatibility
comparable to long-chain PEG (Mn=2000).

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 and7

■Papers with Peer Review
1. Riku Kimura, Kei Nirasawa, Yoichi Negishi and Shoichiro
Asayama, Tunable gene expression in skeletal muscles by themolecular weight of PEG chain length of plasmid DNA monoion complexes, Chemistry Letters, 51, 840-843 (2022).
2. Yuki Kobayashi and Shoichiro Asayama, Design of the zinc
ion and plasmid DNA co-delivery system by poly(1vinylimidazole) derivatives for myoblast differentiation, ACS
Applied Bio Materials, 5, 5754-5761 (2022).
■Academic Meeting
See the annual report in Japanese (13 articles).
■Patents
See the annual report in Japanese (1 patent).

8

Reports from Research Groups
Kubo Laboratory■Members
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

2. Arylselanyl-BODIPYs as a sensitizer for triplet-triplet
annihilation upconversion
Yuji Kubo
Abstract
Triplet-triplet annihilation upconversion (TTA-UC) has attracted
increasing attention as promising method for energy conversion
from low-energy excitation to higher energy light. In this study,
the introduction of phenylselanide group at the 2- and 5- positionof boron-dipyrromethene (BODIPY) core led to production of
new triplet photosensitizer 1 (R = H), 2 (R = OMe), and 3 (R =F) The UC behavior of systems comprising the sensitizers andperylene as the acceptor in deaerated toluene was investigatedusing a 524 nm-wavelength laser to detect upconverted emission
at 449 nm; thus, the UC yield decreased in the order of 21%
for 3 > 16% for 2 > 12% for 1 (Figure 3).

Chemistry,

Doctor’s course -2
Master’s course -7
Bachelor -6

Triplet-triplet annihilation upconversion■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).

UC emission
449 nmExcitation
524 nm

TTET

R

H

ΦUC

OMe

12 %

τPhos 22.0 ms

F

16 %

21 %

21.4 ms

22.2 ms

Figure 3. Arylselanyl-substituted BODIPYs as triplet
sensitizers.
3. Near-infrared room-temperature phosphorescence inarylselanyl BODIPY-doped materials
Yuji Kubo
Abstract
Room-temperature phosphorescence (RTP) materials withemission bands in the NIR region are rare. Metal-freearylselanyl-BODIPY triplet photosensitizers were doped into abenzophenone (BP) matrix. When excited at 350 nm, RTP
emission was observed in the NIR region with λem values of 750–
816 nm, and the phosphorescence quantum yield was up to
0.48%. The detection of an extremely large Stokes shift
Host

BP

Normalized intensity

Figure 1. Metal ion-responsive afterglow martials.

4

Guest

R = H, OMe, F
Day-light

UV-light

3

NIR-RTPΦP = 0.48 %

2
1
0
40 0

60 0

80 0

Wavelength / nm

Figure 4. NIR-RTP properties of arylselanyl-substituted
BODIPYs in benzophenone matrix.

Figure 2. Chemometrics-assisted QSPR analysis.

9Reports from Research Groups
Masato Ito
Abstract
We report on the fluorescence properties of a new class ofemissive and stable π-radicals that contain a boron atom at a
position distant from the radical center. A fully planarized
derivative exhibited an intense red fluorescence with highfluorescence quantum yields even in polar solvents. To elucidate
the origin of this phenomenon, we synthesized another boronstabilized radical that contains a bulky aryl group on the boron
atom. A comparison of these derivatives, as well as withconventional donor–π–acceptor (D–π–A)-type emissive πradicals, unveiled several characteristic features in theirphotophysical properties. A theoretical analysis revealed that the
SOMO–LUMO electronic transition generates an emissive D1state. Unlike conventional D–π–A-type p-radicals, this state does
not undergo significant structural relaxation. The boronstabilized π-radicals demonstrated promising potential fororganic light-emitting diodes as an emitting materia (Figure 6)l.

(~400 nm) was responsible for the triplet-triplet energy transferfrom BP to the BODIPY guest. Furthermore, the RTP properties
were tuned by derivatization of the selenium-containing
BODIPY guests. NIR-RTP properties were also detected upon
excitation at 470 nm with a persistent lifetime of up to 17.5ms(Figure 4).
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.

Figure 6. a) Molecular structures of a boron-stabilized radicalwith an intense emission.

5. Chiral recognition using quaterphenyl-5′-carbaldehyde
Yuji Kubo
Abstract
Quaterphenyl-5′-carbaldehyde 1 with metal ion coordination
ability was synthesized for the first time and used for chiralanalyte-binding and chiroptical sensing. The formation of animine between 1 and amine analytes, such as alcohol amines,
diamines, and amino acids, enabled Zn(II)-assisted chiraltransfer from the analyte to the atropisomeric biphenyl unit,
thereby amplifying the circular dichroism (CD) signal, leading
to discernible Cotton effects in the range of 350–450 nm,
with g values on the order of magnitude of 10−3 in MeOH.
Linear relationships between the CD amplitude and enantiomer
excess (ee) of the analytes were observed, enabling use of 1 as achiroptical probe for amines. Interestingly, 1 showed afluorescence response to change in concentrations of Lphenylalaninol in the presence of Zn(II) upon excitation at 380
nm. It suggests that 1 could serve as a dual chemosensor for thedetermination of both the ee and concentration of analytes(Figure 5).

■Papers with Peer Review
1. S. Iwakiri, R. Hasegawa and Y. Kubo, Near-infrared roomtemperature phosphorescence in arylselanyl BODIPY-doped
materials, ChemPhotoChem, 2022, 6, e202200073. DOI:
10.1002/cptc.202200073
2. M. Ito, S. Shirai, Y. Xie, T. Kushida, N. Ando, H. Soutome, K.
J. Fujimoto, T. Yanai, K. Tabata, Y. Miyata, H. Kita and S.
Yamaguchi, Fluorescent organic π-radicals stabilized withboron: Featuring a SOMO–LUMO electronic trandition, Angew.
Chem. Int. Ed., 2022, 134, e202201965. DOI:
10.1002/anie.202201965
3. A. Koga, K. Kawaguchi, M. C. Maida and Y. Kubo, A
ratiometric afterglow response of aluminium ions in methanolwater, Chem. Asian J., 2022, 17, e202200402. DOI:
10.1002/asia.202200402R1
4. K. Omasa, M. Ito and Y. Kubo, Zn(II)-coordination-driven
chiroptical and emissive sensing for chiral amines using aquaterphenyl-5'-carbaldehyde, New. J. Chem., 2022, 46, 21845–
21851. DOI: 10.1039/D2NJ04781K
5. 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, 2022,
in press. DOI: 10.1142/S1088424623500037

Figure 5. Chiral recognition using quaterphenyl-5′carbaldehyde.

6. K. Kawaguchi, M. Ito and Y. Kubo, Chemometrics-assisted
mechanism study of the room-temperature phosphorescence on
nanoscopic boronate assemblies, Chem. Commun., 2023, inpress. DOI: 10.1039/D2CC07049A

6. Synthesis of boron-stabilized radical with an intenseemission.

10Reports from Research Groups■BooksSee the annual report in Japanese 1 book.

■Academic Meeting＊Domestic
See the annual report in Japanese (17 articles)■Awards
See the annual report in Japanese.

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 (paper #1).
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 planewith the alkyl frame. DFT calculations showed comparable
stabilization from conjugation and destabilization frommacroring strain. Structural differences caused changes in NMR
chemical shifts and oxidation potentials. C12's properties wereof interest due to its distributed structure. Overall, the findings
could aid in designing functional molecules withphenylenediamine moieties (Figure 3, paper #5).

Doctor’s course -1
Master’s course -9
Bachelor 7■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.
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. Phenylene-bridged diazacycloalkanes (paper #5).
Then, the development of artificial molecular rotors by novel
framed molecular rotors using 1,4-naphthylene bridged
diazamacrocycles were investigated. The dependence of rotation
on frame size was examined, with framed rotors CnNp (n = 12,
14, 16, 18) synthesized and their rotation in solution wasobserved. The rotor in C18Np showed rotation, as confirmed by
NMR signals, while the rotation of the naphthylene rotor in
C12Np, C14Np, and C16Np was nearly suppressed in solution.
The study suggests the possibility of developing functional
molecular rotors using this approach (Figure 4, paper #2).

Figure 1. molecular gyrotop.
Figure 4. Naphthalene-bridged diazacycloalkanes (paper #2).

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,
paper #1).

The chemistry of artificial molecular rotors has recently attracted
considerable attention in the field of molecular machines. This
study explores the potential of phenyltriptycene as a stepwise
molecular rotor by designing the relative energies of threerotamers using CH/π-interactions between a peri-hydrogen andphenyl. Two different phenyltriptycenes were compared for
CH/π-interactions, and the effects of substituents on the relative
energies were investigated through various analyses. The study's
findings suggest that this approach could aid in the design ofmolecular switches and/or rotors (Figure 5, paper #4).

Figure 5. Phenyltriptycene as a stepwise molecular rotor (paper
#4).

12

Reports from Research Groups
2. Facile Synthesis of Curved π-Electron Systems[n]Acediynes have unique properties owing to their highly
strained and extended π–electron system. The article discusses
the unique properties of [n]Acediynes. The synthesis of highorder silyl[n]acediynes via Eglington coupling between
silyldiethynylbenzene and silyltetraethynylbenzene were
investigated. The structures of silyl[1]acediyne andsilyl[2]acediyne were determined using X-ray crystallography,
and their spectroscopic properties were characterized with DFT
calculations. A redshift in their absorption and fluorescence
spectra occurred with an increase in the order number n of the[n]acediynes. The antiaromaticities of the dehydro[12]annulene
moieties at the center of the annulene ring in these silylacediynes
were also evaluated using NICS values. The calculated values
confirmed the weak antiaromatic character of the rings (Figure
6, paper #3).

Figure 6. Structure of silyl [2]acedyine (paper #3).

■Papers with Peer Review
1.

2.

3.

4.

5.

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., inpress. (DOI:10.1039/D2NJ05873A)
Synthesis and Rotational Dynamics of Diazamacrocycles
Having Bridged 1,4-Naphthylene as Framed Molecular
Rotors, T. Kurimoto, Y. Inagaki, K. Ohara, K. Yamaguchi,
and W. Setaka*, Org. Biomol. Chem. 2022, 20, 8465-8470.
(DOI: 10.1039/D2OB01613C)
Synthesis and Characterization of Silyl[n]acediynes(linearly-fused benzodehydro[12]annulenes): Utilizing
Bulkiness of Silyl Groups to Improve Selectivity, K.
Komatsubara, Y. Inagaki, and W. Setaka*, J. Org. Chem.
2022, 87, 12783-12790. (DOI:10.1021/acs.joc.2c01398)
Design of Rotational Potential in Phenyltriptycene
Molecular Rotor by Exploiting CH/π-Interaction between
Tripticil Hydrogen and Phenyl, H. Inami , Y. Inagaki, and
W. Setaka*, Org. Biomol. Chem. 2022, 20, 6328-6333.
(DOI:10.1039/D2OB01179D)
Structures and Oxidation Properties of Phenylene-Bridged
Diazacycloalkanes: Ring Size Effects on Structures andProperties, W. Setaka*, K. Kajiyama, and Y. Inagaki, J. Org.
Chem.
2022,
87,
10869-10875.
(DOI:10.1021/acs.joc.2c01174)■Invited Lectures
1.

Wataru Setaka,
Crystalline Molecular Gyrotops with a Fluorescent Rotor
ICEAN2022, 2022.10.17-21. (Newcastle, Australia) (oral,
Invited).

■Academic Meeting＊Domestic
See the annual report in Japanese (13 articles)

13

Reports from Research Groups
Kanamura Laboratory
electrode fabrication method is particularly important in order toimprove the cell performance.

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

EnergyChemistry,

Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-246 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp
Doctor’s course - 1
Master’s course - 6
Bachelor 4 - 0■Outlines of the Research

Fig. 2 Charge-discharge curves of a laminate-type rechargeable
magnesium-metal battry with -MnO2 cathode.

1. Research on next-generation rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
We carried out the research and development of nextgeneration rechargeable batteries with metals such as lithium andmagnesium as anode to realize higher energy density than that ofcurrently-used lithium-ion batteries.
The fabrication and evaluation of rechargeable lithium-metal
batteries were performed as laminate-type cells. The design ofpractical cells with an energy density of 500 Wh kg-1 wassuccessfully revealed (Fig. 1) by increasing the size and numberof electrode layers gradually to 1 Ah-class, in which it was also
clarified that a polyimide-polybenzimidazole mixed separator
with a three-dimensional ordered porous structure (3DOM) is
particularly effective on the improvement of cycleability.

2. Research on fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
To improve the energy conversion efficiency of fuel cells, theoperation at higher temperatures is basically needed, whichenables to use waste heat more effectively in addition to theactivity improvement and poisoning suppression of fuel cell
catalysts. We have focused on H+-conducting ionic liquids andtheir mixtures with phosphoric acid as new electrolytes usable ataround 200 °C, and been developing the intermediate
temperature fuel cells. However, the fuel cells using these H+conducting electrolytes basically require platinum-based noble

metals as catalysts. Therefore, we synthesized several OH-conducting ionic liquids and investigated them as newelectrolytes to realize intermediate temperature fuel cells with
non-platinum catalysts. In these OH--conducting new electrolyte
systems, oxygen reduction reaction proceeded not only on aplatinum electrode but also on a glassy carbon electrode unlikein H+-conducting electrolytes, suggesting a clear possibility of
the non-platinum operation of intermediate temperature fuelcells.
Fig. 3 Oxygen reduction reaction activity of (a) platinum and (b)glassy carbon electrodes in OH--conducting ionic liquid
electrolytes(BMImOH:
1-butyl-3-methylimidazoliumhydroxide,
BMImTFSI:
1-butyl-3-methylimidazoliumbis(trifluoromrthanesulfonyl)imide,
TBPOH:
tetrabutylphosphonnium hydroxide) at 120 °C.

Fig. 1 The development of laminate-type rechageable lithiummetal batteries with different capacities.
We also progressed the research on rechargeable magnesium
metal batteries. As one of promising cathode materials with both
high operating potential and capacity, -MnO2 was synthesized
and used in the development of laminate-type full-cells (Fig. 2).
From this full cell development, we revealed a practical cell
design with a prospective energy density of 300 Wh kg-1. This
result suggests that rechargeable batteries with an energy density
exceeding that of lithium-ion batteries can be realized using
magnesium as anode, which is an abundant resource. Various
fundamental technologies for practical cell development such ascarbon coating to suppress corrosion of Al current collector foil
and separator design for magnesium metal anode were also
developed, in which it was found that the optimization of■Papers with Peer Review
1.

14

Jik Soo Kim, Seonghyeon Lim, Rahul S. Ingole, Hirokazu
Munakata, Sung-Soo Kim, Kiyoshi Kanamura, Improving
the high-rate performance of LCO cathode by metal oxide
coating: Evaluation using single particle measurement,Reports from Research Groups
2.

3.

4.

5.

6.

7.

8.

Journal of Electroanalytical Chemistry, 933 (2023) 117190.
Koshin Takemoto, Jungo Wakasugi, Masaaki Kubota,
Kiyoshi Kanamura, Hidetoshi Abe, Dual additive of lithium
titanate and sulfurized pyrolyzed polyacrylonitrile in sulfur
cathode for high rate performance in lithium-sulfur battery,Physical Chemistry Chemical Physics, 25 (2023) 351-358.
Eric Jianfeng Cheng, Kei Nishikawa, Takeshi Abe, Kiyoshi
Kanamura, Polymer in ceramic fexible separators for Li ion
batteries, Ionics, 28 2022) 5089–5097.
M. Riju Khandaker, Yuki Maruyama, Masanori Nagao,
Satoshi Watauchi, Hirokazu Munakata, Kiyoshi Kanamura,and Isao Tanaka, TSFZ Growth and Anisotropic Ionic
Conductivity of Zr-Doped LiCoO2 Single Crystals, Crystal
Growth & Design, 22 (2022) 5624-5628.
Eric Jianfeng Cheng, Yosuke Kushida, Takeshi Abe,
Kiyoshi Kanamura, Degradation Mechanism of All-SolidState Li-Metal Batteries Studied by Electrochemical
Impedance Spectroscopy, ACS Appl. Mater. Interfaces 14(2022) 40881-40889.
Yueying Peng, Kei Nishikawa, Kiyoshi Kanamura, Effectsof Carbonate Solvents and Lithium Salts in HighConcentration Electrolytes on Lithium Anode, Journal of
The Electrochemical Society, 169 (2022) 060548.
Nurbol Tolganbek, Assel Serikkazyyeva, Sandugash
Kalybekkyzy, Madina Sarsembina, Kiyoshi Kanamura,
Zhumabay Bakenov and Almagul Mentbayeva, Interface
modification of NASICON-type Li-ion conducting ceramicelectrolytes: a critical evaluation, Mater. Adv., 3 (2022)
3055-3069.
Toshihiko Mandai, Ayaka Kutsuma, Masashi Konya,
Yukihiro Nakabayashi, Kiyoshi Kanamura, Room
Temperature Operation of Magnesium Rechargeable
Batteries with a Hydrothermally Treated ZnMnO3 DefectSpinel Cathode, Electrochemistry, 90 (2022) 027005.

■Academic Meeting＊Domestic
See the annual report in Japanese (28 articles)＊International
See the annual report in Japanese (8 articles)■Books and reviews
See the annual report in Japanese (5 articles)■Awards
See the annual report in Japanese (5 awards)

15

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
Takashi TAKEI
Associate Professor/Dr. Eng.
Solid Surface Chemistry, Colloid and Interface Science
Room. 9-142 TEL:+81-42-677-2822
takei-takashi@tmu.ac.jp

Fig. 2 Macroporous silica gels and silica glasses prepared bycosolvent-free sol–gel method.

Takashi YANAGISHITA
Associate Professor/ Dr. Eng.
Electrochemistry, Functional Metal Oxide Film
Room. 9-140 TEL:+81-42-6 77- 1111 (Ext. 4931)
yanagish@tmu.ac.jp

2. Verification of pore size distribution measurement methods
using porous solid by packed spheres
Takashi TAKEI
Pore size distribution is used for evaluating the basic physicalproperties of porous materials. The realistic pore model has been
prepared by the packed silica spheres. The pore size distribution
has been evaluated from the nitrogen adsorption method,
thermoporometry,andmercury-intrusion-porosimetry.
Comparative study of three methods have revealed the characterof these methods and the validity of the application to porous
solids having various pore shapes.

Masanao ISHIJIMA
Assistant Professor /Ph.D.
Inorganic Chemistry, Metal nanoparticles
Room. 9-248 TEL:+81-42-677-2841
ishijima@tmu.ac.jp

3. 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.

Doctor’s course - 1
Master’s course -14
Bachelor 4 -8

■Outlines of the Research
1. Studies on inorganic materials and energy devices
Koichi KAJIHARA, Masanao ISHIJIMA

4. 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.

We are studying energy devices using inorganic solids. A newlithium chloroboracite Li4B4Al3O12Cl discovered in our lab. isstable in contact with lithium. We demonstrated that thiscompound is usable as solid electrolytes of solid rechargeable
lithium metal batteries. In this year, single crystals of
Li4B4Al3O12Cl were obtained and the structure was solved bysingle-crystal X-ray diffractometry (Fig. 1). The resulting
structure data contribute to fundamental solid-state sciences.

Fig. 1 A single crystal (left) and refined crystal structure (right)of Li4B4Al3O12Cl.
Silica is a ubiquitous material and its utilization is inaccordance with SDGs. We are studying cosolvent-free sol-gel
method to form silca-based materials only from silicon alkoxides
and water without using cosolvents. The drying time of the
microporous gels was successfully diminishied to 30 h from 2
days, which had been the shortest record in our lab, and the yieldof silica glasses was demonstrated to be as good as ~99% (Fig.
2).

■Papers with Peer Review
1. K. Kajihara, M. Goto, Cosolvent-free synthesis ofmacroporous silica gels and monolithic silica glasses fromtetraalkoxysilane–water binary systems: comparison
between tetramethoxysilane and tetraethoxysilane, J. Sol-16

Reports from Research Groups
Gel Sci. Technol. 104, 497-502 (2022).
2. K. Kajihara, S. Nakagawa, R. Iwasaki, Energy transfer andquenching in sol–gel-derived silica glass green phosphors
doped with Tb3+ and Ce3+ ions: Distinct difference between
P- and Al-codoped glasses. Phys. Status Solidi A 219,
2100494 (2022)
3. T. Yanagishita, A. Koga, H. Masuda, Mater.Continuous
Spinning of Polymer Nanofibers with Uniform Diameters
Using Anodic Porous Alumina Spinneret with Holes ofDifferent Diameters. Adv., 4, 890 (2023). [Inside front
Cover]
4. T. Yanagishita, Y. Boushi. Preparation of anodic porousalumina with gradient hole size for directional droplet
transport. Langmuir, 39, 862 (2023). [Supplementary CoverArt]
5. T. Yanagishita, K. Murakoshi, H. Masuda,Effect of finestructures formed by nanoimprinting using anodic porousalumina mold on surface hydrophobicity, ECS J. Solid State
Sci. Technol., 11, 103004 (2022).
6. T. Kondo, M. Yoshida, T. Yanagishita, H. Masuda,
Electrodeposition and Electrodissolution of Li Metal in
Nanohole Arrays of Anodic Porous Alumina, J. Electrochem.
Soc., 169, 092507 (2022).
7. T. Yanagishita, Y. Maejima, and H. Masuda. Dependence ofSize Distribution of Nanoparticles on Hole Size Uniformity
in Membrane Emulsification,.Mater. Res. Express., 9,086404 (2022).
8. T. Yanagishita, T. Sou, H. Masuda.Micro-Nano HierarchicalPillar Array Structures Prepared on Curved Surfaces by
Nanoimprinting Using Flexible Molds from Anodic Porous
Alumina and Their Application to Superhydrophobic
Surfaces, RSC Adv., 12, 20340 (2022).
9. T.Yanagishita.T.Masuda,H.Masuda,PretexturingandAnodization of W for Fabricating Ordered Anodic Porous
WO3. J. Electrochem. Soc., 169, 072504 (2022).
10. T. Yanagishita, R. Kawato, H. Masuda,Highly ordered
anodic porous alumina prepared by anodization of Al in
extremely dilute H2SO4, J. Electrochem. Soc., 169, 073504(2022).
11. T. Yanagishita, Y. Osada, T. Masuda, H. Masuda Preparationof ordered nanohole arrays with high aspect ratios byanodization of prepatterned 304 stainless steel, J.
Electrochem. Soc., 169, 063502 (2022).
12. 11.
M. Ishijima, T. Takada, J. L. Cuya Huaman, T.
Mizutomi, O. Sakai, K. Shinoda, M. Uchikoshi, H. Mamiya,
K. Suzuki, H. Miyamura, J. Balachandran, Synthesis ofElectromagnetic Wave-Absorbing Co–Ni Alloys and Co–Ni
Core–Shell Structured Nanoparticles. Inorg. Chem., 61,
17144 (2022)

Nanoparticle. 11th International Conference on Fine Particles
Magnetism ICFPM2022, 2022/10 Yokohama, Japan Poster.
2. M. Ishijima, T. Matsumoto, J. L. Cuya Huaman, J.
Balachandran, Synthesis of Transition Metals and Alloys
Using Alcohol Reduction Technique, 11th International
Conference on Fine Particles Magnetism ICFPM2022,
2022/10, Yokohama, Japan, Poster.
＊Domestic
See the annual report in Japanese (28 articles)■Patents
See the annual report in Japanese ( 1 articles)■Awards
See the annual report in Japanese ( 3 articles)■Reviews and Books
1. K. Kajihara, K. Kanamori, A. Shimojima, “Current status of
sol–gel processing of glasses, ceramics, and organic–
inorganic hybrids: a brief review,” J. Ceram. Soc. Jpn. 130,575-583 (2022).
See the annual report in Japanese (3 articles)■Invited Lectures＊Domestic
See the annual report in Japanese (6 articles)■Academic Meeting＊International
1. M. Ishijima, J. L. Cuya Huaman, K. Shinoda, M. Uchikoshi,
H. Mamiya, J. Balachandran, Synthesis and Magnetic
Properties of Co-Ni Alloy and Core-shell Structured

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

Chemistry,

Tamao ISHIDA
Associate Professor /Dr. Eng.
Catalysis Chemistryroom:9-B51 TEL: +81-42-677-2845
e-mail: tamao@tmu.ac.jp

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

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

Tetsuya SHIMADA
Assistant Prof. / Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Visiting researcher 4
Doctor’s course 4
Master’s course 16
Bachelor 7■Outlines of the Research
Our group challenges to control photochemical reactions suchas electron and energy transfer, by controlling the orientation andalignment of dyes on the inorganic surfaces.
Recently,organic/inorganic hybrids composed of porphyrins and layeredmaterials have been the subject of intensive investigations to
explore their novel properties and functionalities. We foundout that a precise matching of distances between the negatively
charged sites on the clay mineral layers and that between thepositively charged sites in the dye molecule is one of the mostimportant factors to determine the structure of the clay–dye
complex. We have termed this the “Size-Matching Rule”. Our
goal is finding out a new methodology to control molecularassembly structure and realizing functionalized photochemical
reaction systems such as an artificial light harvesting system.
1. Research on Artificial Light Harvesting System
Shinsuke TAKAGI, Tetsuya SHIMADA
The quantitative excited energy transfer reaction between
cationic porphyrins on an anionic clay surface was successfully
achieved. The efficiency reached up to ca. 100% owing to the“Size- Matching Rule” that is our original technique. It was
revealed that the important factors for the efficient energy
transfer reaction are (i) suppression of the self-quenching
between adjacent dyes, and (ii) suppression of the segregatedadsorption structure of two kinds of dyes on the clay surface.
These findings indicate that the clay/porphyrin complexes arepromising and prospective candidates to be used for constructionof an efficient artificial light-harvesting system. Especially when
phthalocyanine was used as energy acceptor, light harvesting
type energy transfer was realized.
In addition to these,hydrogen evlution systems using sunlight as an energy source
has been developed. Especially, photochemical hydrogen andhydroperoxide formation were examined as an energy related
subject this year.

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

3. Research on protein behavior on inorganic nanosheets
Shinsuke TAKAGI, Tetsuya SHIMADA
Proteins take unique higher-order structures and exhibit uniqueproperties in an aquatic environment. For example, enzymes
have extremely high substrate selectivity based on their higher
order structure. Horseradish peroxidase (HRP) is known toselectively react with hydrogen peroxide. It was found that when
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

18

Reports from Research Groups
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
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.

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

7. Research on supported gold catalysts
Layered double hydroxides (LDHs) consist of hydroxide ofdivalent metal ions in which trivalent metal ions are partly
substituted, and manyl kinds of LDHs are synthesized. LDH has
several characteristic features: positively charged surface,intercalation of anions, converting to mixed metal oxides(MMOs) upon calcination, and exfoliating into monolayer
nanosheets (NS). On the other hand, gold (Au) exhibits highcatalytic activity for CO oxidation when supported as
nanoparticles (NPs) of 5 nm or less in diameter on reducible
metal oxides such as Co3O4 and NiO. However, it is difficult to
support Au as small nanoparticles on inert supports such as SiO2
and the resultant Au/SiO2 shows low activity. In this work, we
aimed at formation of active Au-oxide interface on Au NPs by
the decoration of Au with thin MMO layer and evaluated thecatalytic activity for CO oxidation. For this purpose, thepositively charged exfoliated M-Al LDH (M: Mg, Co, Ni, andZn) nanosheets (NS) were adsorbed on the negatively charged
Au/SiO2 to give Au/SiO2@M-Al LDH, and then it was calcined
to obtain Au/SiO2@M-Al MMO (Fig. 6).

Videos can be viewed on thefollowing site.
https://www.apchem.ues.tmu.aFig. 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. The factors that determine MQu+-Aldehyde:
MQu+-Diol ratio were discussed from the thermodynamic
analysis of the system. These data indicate that the electrostaticinteraction between the charged saponite surface and MQu+
stabilized the aldehyde side enthalpically and destabilized it
entropically. The major reason for these results is considered tobe the difference in adsorption stabilization between MQu+Aldehyde and MQu+-Diol on saponite surfaces.

Fig. 6. Schematic image of Au/SiO2@Co-Al MMO.

M-Al LDHs (M: Mg, Co, Ni, and Zn) were preparaed andexfoliated into monolayer NS according to the literatures. The
resultant LDH NS, Au/SiO2@M-Al LDH, and Au/SiO2@M-Al
MMO were characterized by XRD, TGA, AFM, elemental
analysis, ICP-AES, TEM, HAADF-STEM, and EDX. The sizeof Au NPs did not change before and after the formation of
MMO layer except when Mg-Al LDH was used. STEM
elemental mapping of Au/SiO2@Co-Al MMO revealed that Co
and Al were highly dispersed on the whole surface of Au/SiO2(Fig. 7). The formation of Co-Al MMO layer on the Au NP
surface was confirmed by STEM (Fig. 8).

19

Reports from Research Groups
S. M. Osman, L. G. Voskressensky, T. D. Lam, T. Ishida, T.
Murayama, Mol. Catal., 518, 112053-112057(2022).
9. Effect of poly(N-vinylpyrrolidon) 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).

■Reviews
See the annual report in Japanese (1 articles).

■Books
1. Surface-fixation Induced Emission, Y. Ishida ・ S. Takagi,
Wiley & Sons Ltd., "Handbook of Aggregation-Induced
Emission" (Y. Tang, B. Z. Tang, Ed.), (2022).

Fig. 7. STEM elemental mappings of Au/SiO2@Co-Al MMO (upper)
and of Co-Al/Au/SiO2 (bottom).

■Invited Lectures
1. The effect of flat inorganic surface on the photochemical
properties and reactions of molecules, S. Takagi, Saturday
Seminar Series (Hosted By Professor V Ramamurthy),
Online, March, 2022.
2. Decoration of Gold Nanoparticle Surface for Tuning theCatalytic Activity, T. Ishida, East China University of
Science and Technology, Shanghai (China), December,
2022.
3. See the annual report in Japanese (2 more articles)
Fig. 8. TEM image of Au/SiO2@Co-Al MMO.

■Academic Meeting＊International
1. Development of gold nanoparticle catalyst supported on NiTi mixed metal oxides using layered double hydroxides, A.
Takahashi, A. Nakayama, T. Murayama, N. Sakaguchi, T.
Shimada, S. Takagi, T. Ishida, GOLD2022, Quebec,
Canada, July, 2022.
2. Effect of strong metal-support interaction (SMSI) on
gold/substituted-hydroxyapatites for oxidative esterificationof aliphatic aldehydes, A. Taketoshi, Y. Gangarajula, R.
Sodenaga, A. Nakayama, N. Sakaguchi, T. Murayama, M.
Haruta, B. Qiao, J. Wang, T. Ishida, GOLD2022, Quebec,
Canada, July, 2022.
3. Enhanced catalytic activity utilizing strong metal-support
intreractions (SMSI) -Isomerization of alkenes overhydroxyapatite supported gold catalysts-, A. Nakayama, R.
Sodenaga, Y. Gangrajula, A. Taketoshi, T. Murayama, T.
Honma, N. Sakaguchi, T. Shimada, S. Takagi, M. Haruta, B.
Qiao, J. Wang, T. Ishida, GOLD2022, Quebec, Canada,
July, 2022.
4. Influence of Strong Metal-Support Interaction (SMSI) on
Catalytic Properties of Substituted-Hydroxyapatite
Supported Au Nanoparticles, A. Nakayama, R. Sodenaga, Y.
Gangrajula, A. Taketoshi, T. Murayama, T. Honma, N.
Sakaguchi, T. Shimada, S. Takagi, M. Haruta, B. Qiao, J.
Wang, T. Ishida, The 9th Tokyo Conference on Advanced
Catalytic Science and Technology (TOCAT9), Fukuoka,
July, 2022.
5. Depositoin of gold clusters on Ni-Ti mixed metal oxide/SiO2
having abundant oxygen vacancies and its catalytic
performance for CO oxidation,
A. Takahashi, A.
Nakayama, T. Murayama, N. Sakaguchi, T. Shimada, S.
Takagi, T. Ishida, The 9th Tokyo Conference on Advanced
Catalytic Science and Technology (TOCAT9), Online(Japan), July, 2022.
6. Surface Modification of Au/SiO2 Using Layered Double
Hydroxides (LDH) and Effect on CO Oxidation, K.
Okayama, A. Nakayama, T. Murayama, N. Sakaguchi, T.
Shimada, S. Takagi, T. Ishida, The 9th Tokyo Conference
on Advanced Catalytic Science and Technology (TOCAT9),
Online (Japan), July, 2022.
7. Decoration of Au/TiO2 surface by thin layer of metal-■Papers with Peer Review
1. Efficient non-volatile organogold complex for TiO2supported gold cluster catalysts: preparation and catalytic
activity for CO oxidation, L. X. Dien, T. Murayama, N. T.
Hung, Q. D. Truong, H. D. Chinh, M. Yoshimura, M. Haruta,
T. Ishida, J. Catal., 408, 236-244(2022).
2. Enhancement effect of strong metal-support interaction(SMSI) on the catalytic activity of substitutedhydroxyapatite supported Au clusters, A. Nakayama, R.
Sodenaga, Y. Gangarajula, A. Taketoshi, T. Murayama, N.
Sakaguchi, T. Shimada, S. Takagi, M. Haruta, B. Qiao, J.
Wang, J. Catal., 410, 194–205(2022).
3. Defective NiO as a Stabilizer for Au Single-Atom Catalysts,
C. Mochizuki, Y. Inomata, S. Yasumura, M. Lin, A.
Taketoshi, T. Honma, N. Sakaguchi, M. Haruta, K.-i.
Shimizu, T. Ishida, T. Murayama, ACS Catal., 12, 6149–
6158(2022).
4. Intramolecular cyclization of alkynoic acid catalyzed by Nasalt-modified Au nanoparticles supported on metal oxides,
Q.-A. Huang, T. Ikeda, K. Haruguchi, S. Kawai, E.
Yamamoto, H. Murayama, T. Ishida, T. Honma, M. Tokunga,
Appl. Catal. A: Gen., 643, 118765-118774(2022).
5. Precise evaluation of adsorption behavior of cationicporphyrin on monolayer of perovskite-type niobia
nanosheet by absorption spectroscopy, M. Oshima, K. Sano,
Y. Hirade, R. Nakazato, T. Ishida, T. Shimada, S. Takagi, J.
Phys. Chem. Solids, 161, 110423-110428(2022).
6. 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(2022).
7. Photochemical hydrogen evolution using Pt/titania
nanosheet catalysts prepared by chemical-reduction andphoto-deposition methods, H. Takimoto, Y. Hirade, T.
Shimada, T. Ishida, S. Takagi, Results Chem., 4, 100271100275(2022).
8. Facile synthesis of Co3O4@SiO2/Carbon Nanocomposite
Catalysts from Rice Husk for Low-Temperature CO
Oxidation, L. X. Dien, H. D. Chinh, N. K. Nga, R. Luque,20

Reports from Research Groups
organic framework and its catalytic activity, S. Kadowaki,
A. Nakayama, N. Sakaguchi, T. Murayama, S. Takagi, T.
Shimada, T. Ishida, The 9th Tokyo Conference on
Advanced Catalytic Science and Technology (TOCAT9),
Online (Japan), July, 2022.
8. Fluorescence enhancement of molecules on the clay surface
and its environmental responses, S. Takagi, AIPEA - XVIIInternational Clay Conference, Istanbul (Turkey), July,2022.
9. Adsorption and aggregation behavior of tetracationicporphyrins on clay and titania nanosheets, Y. Hirade, K.
Fukushima, T. Shimada, T. Ishida, S. Takagi, AIPEA XVII International Clay Conference, Istanbul (Turkey),
July, 2022.
10. “On surface synthesis” on saponite surface: A novel organic
reaction pathway of azonia[5]helicene by interaction withsaponite surface, K. Arakawa, T. Shimada, T. Ishida, S.
Takagi, AIPEA - XVII International Clay Conference,
Istanbul (Turkey), July, 2022.
11. Development of Suported Au Catalysts Toward the
Optimization of the Electronic State of Au, A. Nakayama,
The Röntgen-Angström Cluster (RÅC) International
Summer School 2022 (Focal theme: Advanced Materials
Design at X-ray and Neutron Facilities), Varberg (Sweden),August, 2022.
12. Effect of Covering Au Surface by Thin Layer ofHydroxyapatite on Alkene Isomerization, T. Ishida, A.
Nakayama, Y. Gangarajula, A. Taketoshi, T. Murayama, T.
Honma, N. Sakaguchi, T. Shimada, S. Takagi, M. Haruta, B.
Qiao, J. Wang,
Tateshina Conference on Organic
Chemistry, Nagano (Japan), November, 2022.
＊Domestic
See the annual report in Japanese (29 articles)■Awards
1. Excellent Presentation Award, The 47th meeting for young
scientists in photochemistry, Kyosuke ARAKAWA (D1),
June, 2022
2. The Clay Science Society of Japan Promotion FundAward, The Clay Science Society of Japan, Yugo
HIRADE (D2), July, 2022.
3. 2nd Best Poster Award, The Röntgen-Angström Cluster(RÅC) International Summer School 2022 (Focal theme:
Advanced Materials Design at X-ray and Neutron
Facilities) at Sweden, Akihiro NAKAYAMA, August,2022.
4. Travel Awards, GOLD 2022, , Akihiro NAKAYAMA,
August, 2022.
5. Excellent Poster Awards for Students, The 130th CATSJ
Meetings, Shintaro KADOWAKI (M2), September, 2022.
6. Excellent presentation award, The solid and surface
photochemistry conference 2022, Ryota SHIMADA (M2),
November, 2022.
7. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2022, Yugo HIRADE (D2),
December, 2022.

21

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 Portable ELISA System Using Pipette
Tips
Hizuru NAKAJIMA, Shoji YAMAMOTO
Enzyme-linked immunosorbent assay (ELISA) is an
immunological assay commonly used to measure antibodies,
antigens, proteins and glycoproteins in biological samples.
However, the conventional ELISA method relatively needs along analysis time and many expensive reagents. In addition,commercially available microplate readers are large-size andvery expensive. Therefore, it is not possible to measure
biological samples and environmental samples in the field by
ELISA. To overcome these drawbacks, we developed an ELISA
method using pipette tips (PT-ELISA) and the palm-sized
fluorescence detector for PT-ELISA. This PT-ELISA system was
successfully used in the determination of IgA in human saliva, amarker of stress.

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

3. Development of a Portable Genetic Testing System Basedon LAMP
Hizuru NAKAJIMA, Shoji YAMAMOTO
A genetic amplification method using polymerase chain
reaction (PCR) is commonly used in the genetic test. However,the PCR method is not suitable for the on-site genetic test since
the method needs large-sized and expensive assay devices suchas a thermal cycler, an electrophoresis equipment, and anabsorption/fluorescence detector. To overcome these drawbacks,
a portable genetic testing system based on LAMP was developed
using LEDs, photodiodes a transparent glass heater, and so on.
The genetic testing system was successfully used in the variety
identification of rice. We also succeeded in developing ISFETpH sensors for genetic testing.

Doctor’s course -4
Master’s course -13
Bachelor 4 -8

■Outlines of the Research
1. Development of Micro Total Analysis System Using a
Compact Disk-type Microfluidic Device
Hizuru NAKAJIMA, Shoji YAMAMOTO
We have developed a flow-based ELISA system using a
microfluidic device. However, many pumps and valves are
required for multiple immunoassays, which affects the total sizeof the analytical system. In this study, we developed a solution
sending method based on the centrifugal force generated byrotating a compact disk-type microfluidic device. A portable
fluorescence detection system, electrochemical detection system,and surface plasmon resonance sensor using the compact disktype microfluidic device were developed. Since these systems do
not need pumps and valves, these systems would be useful foron-site analysis, such as environmental monitoring, food safety
testing, and point-of-care testing.

22

Reports from Research Groups
4. Development of Quantitative Multi-ion Channel Activity
Evaluation Method Using Electrochemical Surface
Plasmon Resonance sensor
Hizuru NAKAJIMA, Shoji YAMAMOTO
Ion channels in biological membranes are one of the targets
for drug discovery, and it is important to analyze their function.
The activity of ion channels is generally evaluated byelectrochemical measurements, but the measurements require
skilled techniques. In this study, we developed a compact
multichannel electrochemical surface plasmon resonance sensor.
Using our sensor, we developed a simple and quantitative
method to evaluate the activity of ion channels.

6. Evaluation of Combined Temperature and CO2 Stress inCorals by Continuous Measurements of Calcification andPhotosynthesis
Hizuru NAKAJIMA, Shoji YAMAMOTO
Coral reef ecosystems are now facing the danger of global
warming and ocean acidification due to increased CO2 emissions.
Corals that support the ecosystem are cnidarians, but they are
curious organisms that obtain most of their energy to build theirown skeletons (=calcification) through photosynthesis byzooxanthellae that live symbiotically within their bodies.
Therefore, it is necessary to evaluate the combined stress ofwater temperature and CO2 by photosynthesis of zooxanthellae
and coral calcification. In this study, we successfully establisheda method to measure both the photosynthesis of zooxanthellae
and the calcification of corals on a minute scale by measuringcontinuous total alkalinity and dissolved oxygen in seawater.

7. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
uburban site (Minamiosawa, Koto-ku, Kyoto). Emission sources,
contribution to ozone formation of each VOC were estimated.
Test measruemnts of ambient air by SIFT-MS was conducted.

5.

Development of Multichannel ISFET Sensor for
Measuring pH Distribution of Interstitial Water inMarine Sediment
Hizuru NAKAJIMA, Shoji YAMAMOTO
Recently, marine acidification is progressing with increasing
the concentration of CO2 in the atmosphere. Ocean acidification
not only decreases the skeletal formation of calcium carbonate
in corals, shellfish, and other marine organisms, but can also
cause the dissolution of coral reef sands, raising concerns about
the impact on marine organisms. Therefore, the measurement of
the pH distribution of pore water in marine sediment is importantfor evaluating the effect of ocean acidification on the ecosystem.
In general, the pH value of interstitial water in marine sedimentis measured by divers using the pH meter with a glass electrode.
However, the measurement work is very hard, the glass electrodeis fragile, and the pH distribution of interstitial water could not
be measured at the same time. To overcome these drawbacks, anovel multichannel ISFET sensor using Ta2O5 as an ion-sensitive
membrane was developed for measuring the pH distribution ofpore water in marine sediment.

8. Atmospheric trace species measurements at remote sites
Shungo KATO
Atmospheric carbon monoxide, ozone, various volatile organic
compounds, and hydrogen were continuously observed atremote sites: cape Hedo in Okinawa, Suzu in Ishikawa.
9. Measurements of atmospheric pollutants at mountain sites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide 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.
10. Development of volcanic gas monitoring system using
small gas sensor
Shungo KATO
Realtime measurement of volvanic gas at the top of Mt. Fuji
during winter without commercial electric power was donductedwith low power gase sensor and LPWA ELTRES (SONY). Also,
measuremnent of volcanic gases using a portable system wasconducted at trails of Mt. Fuji and Owakudani, Hakone volcano.

Extended Gate electrodeIon sensitive membrane
Commercial FET

Gate
N
N-channel

SourceN
P-Silicon

イオン感応膜 (Ta2O5)

Drain

エポキシ樹脂マルチチャンネル
ISFETセンサー

10 mm

海⽔

300 mm

間隙⽔100 mm堆積物

ISFET 回路基板

Id

沖縄県 恩納村

バッテリー

WQC [⽔質計](ガラスpH電極)

ISFETセンサー

ISFET回路基板

11. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen concentration in suburban, urban, and remote sites
were observed. Measeruemts on tunnels to observe car exhaust
were conducted.

データロガー

WQC

23

Reports from Research Groups
15. Development of 4-nozzle chemical pen for single celldifferentiation
Sifeng MAO
In this study, we developed a system using a 4-nozzle
chemical pen for single cell differentiation using NGF. possible
to confine the solution in the limited area in a medium. In thisstudy, PC12 cells in the solution area were stimulated by NGF
using a 4-nozzle chemical pen, and the changes in the cells wereobserved to examine the single cell differentiation. As a result of
stimulating PC12 cells with NGF for 3 hours using this system,
it was confirmed that the localization of mitochondria andlysosomes migrated to the neurites.

12. 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. Moreover, the mechanism andthe fabrication of gold nanowires are still in progress.
13. 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.

16. Local pH control by using a laminar flow
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.

■Papers with Peer Review
1. Yuki Nishitani, Nahoko Kasai, Hizuru Nakajima, Shungo
Kato, Sifeng Mao, Katsumi Uchiyama
Regioselective fabrication of gold nanowires using openspace laminar flow for attomolar protein detection
Chemical Communications, 2022, 58(27) 4308-4311
2. Shuhui Si, Tsuguhiro Kaneko, Lingrui Xu, Huan Luo, Hizuru
Nakajima, Nahoko Kasai, Katsumi Uchiyama, Danhong Wu,
Hulie Zeng
Microsphere amplified fluorescence and its application insensing
Biosensors and Bioelectronics, 2022, 218 114791-114791
3. Haifeng Lin, Nahoko Kasai, Ning Xu, Hizuru Nakajima,
Shungo Kato, Hulie Zeng, Jin-Ming Lin, Sifeng Mao,
Katsumi Uchiyama
Localized hydrodynamic flow confinement assisted
nanowire sensor for ultrasensitive protein detection.
Biosensors and Bioelectronics, 2022, 218, 114788.
4. Masakazu Kagawa, Kazuhiro Morioka, Moeko Osashima,
Akihide Hemmi, Shoji Yamamoto, Atsushi Shoji, Katsumi
Uchiyama, Hizuru Nakajima
Development of small-sized fluorescence detector for pipettetip-based biosensor for on-site diagnosis
Talanta, 2023, 124311-124311
5. Sifeng Mao
Recent advances in nanowire sensor assembly using laminarflow in open space.
TRAC Trends in Analytical Chemistry, 2023, 116918.

14. Regioselective fabrication of gold nanowire using openspace laminar flow for attomolar protein detection
Sifeng MAO
Gold nanowires are expected to be applied to biosensing due
to their advantages, such as high stability and biocompatibility.
However, it is still inconvenient to fabricate a single gold
nanowire at a precise position, and without a special demanding
environment. In this study, we present an open-space laminarflow approach for fabricating a single gold nanowire at a precise
position under normal conditions. The fabricated gold nanowire
demonstrated excellent biosensing of IgA with an extremely low
limit of detection (1 aM).

24

Reports from Research Groups
6. Nanase Kohno, Jun Zhoua, Jiaru Li, Marina Takemur,
Natsuki Ono, Yu Bai, Yasuhiro Sadanaga, Yoshihiro
Nakashima, Kei Sato, Shungo Kato, Kentaro Murano,
Yosuke Sakamoto and Yoshizumi Kajii
Impact of OH missing reactivity and aerosol uptake of HO2
radicals on tropospheric O3 production during the AQUASKyoto summer campaign in 2018, Atmospheric
Environment, 281, 119130, 2022
7. N.K. Kim, Y.P. Kim, Y.S. Ghim, M.J. Song, C.H. Kim, K.S.
Jang, K.Y. Lee, H.J. Shin, J.S. Jung, Z. Wu, A. Matsuki, N.
Tang, Y. Sadanaga, S. Kato, A. Natsagdorj, S. Tseren-Ochir,
B. Baldorj, C.K. Song, J.Y. Lee
Spatial distribution of PM2.5 chemical components during
winter at five sites in Northeast Asia: High temporal
resolution measurement study
Atmospheric Environment, 290, 119359, 2022

■Invited Lectures■Academic Meeting＊International＊Domestic
See the annual report in Japanese (23 articles)■Books■Awards
See the annual report in Japanese (1 articles)25

Reports from Research Groups
Shishido Laboratory■Members

give diverse organosilicon compounds. In addition, this novel
reaction technology for C(sp3)–O bond transformation could beapplied to the upcycling of polyesters. Mechanistic studies
corroborated the notion that the generation of alkyl radicals is
involved in C(sp3)–Si coupling and the cooperation of gold andan acid–base pair on amphoteric oxide is responsible for thehomolysis of stable C(sp3)–O bonds. The high reusability and air
tolerance of the heterogeneous gold catalysts as well as a simple,
scalable, and green reaction system enabled the practicalsynthesis of diverse organosilicon compounds.

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

chemistry,

PD -1
Doctor’s course -4
Master’s course -10
Bachelor 4 -6

Base site■Outlines of the Researchδ+Acid site

Inhibitory effect of trace impurities in biomass-derived methanol
on methanol reforming by Cu-based catalysts
Continuous production of lactic acid from glycerol overbifunctional catalysts using a liquid-phase flow reactor

Steam reforming (SR) and autothermal reforming (ATR) of
methanol are important reactions to produce chemicals andsupply hydrogen to fuel cells. Methanol is mainly produced fromfossil fuels. Therefore, utilization of biomass-derived methanol(bio-methanol) is desired from the perspective of carbon
neutrality. However, the effect of impurities such as lower
alcohols and aromatics in bio-methanol on methanol reforming
was unclear. In this study, the effect of impurities on methanol
reforming was investigated in reforming of “model bio-methanol”
contained trace ethanol as model impurities. In SR, the catalytic
activity of copper-zinc oxide-aluminum oxide (CZA) was
remarkably decreased due to ethanol adsorption on the active site.
In ATR, carbonaceous species was deposited on CZA and leaded
to decrease the activity. These results suggest that Cu-based
catalyst are affected by the inhibitory effect of lower alcohols
due to the inability of Cu to cleave C-C bonds in lower alcohols.

The highly efficient conversion of glycerol into value-added
chemicals with high selectivity is an attractive issue inbiorefineries. In this study, the performances of metal-acidbifunctional catalysts for converting glycerol to lactic acid were
investigated under an oxygen atmosphere without additives,
such as strong bases using a continuous liquid-phase flow reactor.
We found that Pt/L-Nb2O5 (L-Nb2O5: layered Nb2O5) is the mostpromising catalyst for the continuous production of lactic acidfrom glycerol due to the optimal oxidation ability and the highLewis and Brønsted acidities of Pt/L-Nb2O5. Furthermore, Pt/LNb2O5 exhibited a stable catalytic performance for 80 h withouta strong base.
Base free
GlycerolPt

Lactic acid

Sel. > 70 % for 80 h
L-Nb2O5■Papers with Peer Review
1.

Alkyl–silyl cross-coupling with the cooperation of gold
nanoparticles and amphoteric zirconium oxides
2.
The universal transformation of C(sp3)–O bonds will be a key
technology for achieving carbon neutrality. In this study, wedemostrated that gold nanoparticles supported on amphoteric
metal oxides, efficiently promoted C(sp3)–Si bond formation to26

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.

Reports from Research Groups
3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

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.
Transient Temperature Response of Supported Rh
Nanoparticles in Photothermal Dry Reforming of
MethaneAn Operando Dispersive Xray Absorption
Spectroscopy Study, Takami, D.; Yamamoto, A.; Kato, K.;
Shishido, T.; Yoshida, H., J. Phys. Chem. C, 2022, 126,
15736-15743.
【Featured as a Supplementary Cover】
Development of ruthenium catalysts for environmentallyfriendly organic transformation via C–H bond activation(Review Paper) Miura, H.; Shishido, T. J. Jpn. Petrol. Inst.
2023, 66, 8–14. 【Featured as a Journal Cover】
Continuous liquid-phase upgrading of glycerol to lactic
acid over bifunctional catalysts under base-free conditions
Kano, E.; Aihara, T.; Ghampson, I. T.; Miura, H.; Shishido,
T. ACS Sustainable Chem. Eng. 2022, 10, 12072–12081.
【Featured as a Supplementary Cover】
Effect of Support and Pd Cluster Size on Catalytic
Methane Partial Oxidation to Dimethyl Ether Using an
NO/O2 Shuttle, Ghampson, I. T.; Yun, G-N.; Kaneko, A.;
Vargheese, V.; Bando, K.; Shishido, T.; Oyama, S. T., ACS
Catal. 2022, 12, 11190-11205.
Production of hydrogen by the autothermal reforming of
methanol over Cu/ZnO/Al2O3-based catalysts: Improved
durability and self-activation upon Pd-doping, Nomoto,K.; Kubo, Y.; Miura, H.; Shishido, T.
J. Jpn. Petrol. Inst. 2022, 65, 161–170.
Particle Size Effect on Hydrogen Cyanide Synthesis with
CH4 and NO over an Alumina-supported Platinum
Catalyst, Yamasaki, T.; Takagaki, A.; Shishido, T.; Bando,
K.; Kodaira, T.; Murakami, J.; Song, J. T.; Niwa, E.;
Watanabe, M.; Ishihara, T., J. Jpn. Petrol. Inst. 2022, 65,
184-191.
【Featured as a Journal Cover】
Direct Air Capture of CO2 Using Liquid Amine–Solid
Carbamic Acid Phase-Separation System Kikkawa, S.;
Amamoto, K.; Fujiki, Y.; Hirayama, J.; Kato, G.; Miura,
H.; Shishido, T.; Yamazoe, S. ACS Environ. Au 2022, 2,
354–362.
Understanding the distinct effects of Ag nanoparticles andhighly dispersed Ag species on N2 selectivity in NH3-SCO
reaction Wang, H.; Murayama, T.; Lin, M.; Sakaguchi, N.;
Haruta, M.; Miura, H.; Shishido, T. ACS. Catal. 2022, 12,6108–6118.
Gold-Catalyzed Thioetherification of Allyl Benzyl andPropargyl Phosphates Miura, H.; Toyomasu, T.; Nishio,
H.; Shishido, T. Catal. Sci. Technol. 2022, 12, 1109–1116.

3.

4.

5.

6.

7.

■Academic Meeting＊Domestic
See the annual report in Japanese (25 articles)■Awards
1.

2.

3.

4.

■Invited Lectures1.

2.

Selective catalytic reduction of NO over Rh supported onhydroxyapatite
S. Doi, H. Miura, T. Shishido, 12th International
Conference on Environmental Catalysis (ICEC2022) July
30-Aug. 2, 2022 Osaka, Japan
Organic Transformations by Concerted Catalysis of Pd andAu on Alloy Nanoparticles
H. Miura, JPI-KSIEC joint symposium “Advances inMaterial and Processing for Energy-Environmental
Applications”, November 3, 2022. Daejeon, Korea.
Catalytic Synthesis of Α-Amino Acids: Selective
Conversion of Glyceric Acid to Alanine over Bifuncitional
Ru/TiO2 Catalysts
S. Saito, H. Miura, T. Shishido, 48th Science andTechnology for Advancing Toward SDGs (48th STT）Nov.
29-Dec. 1, 2022, Bangkok, Thailand
Basis of XAFS
T. Shishido，103th annual meeting of CSJ March 22—25,
2023 Tokyo university of science
Cooperative catalysis between gold and other elements
enabling efficient organic transformation over solid
surface
H. Miura，103th annual meeting of CSJ March 22—25,
2023 Tokyo university of science

Novel heterogeneous organic synthesis by cooperation ofgold and other elements
H. Miura，13th Meeting of catalysis scienece June 10,2022 Satelite plaza Kanazawa university
Ag Size/Structure-Dependent Effect on Low-Temperature
Selective Catalytic Oxidation of NH3 over Ag/MnO2
H. Wang, M. Lin, T. Murayama, M. Haruta, H. Miura, T.
Shishido, Taipei International Conference on Catalysis(TICC2022) July 20-22, 2022 Taipei, Taiwan

5.

27

The japan petroleum institute, The Japan Petroleum
Institute Award for Distinguished Papers“Lactic acid production from glucose over Y2O3-based
catalysts under base-free conditions”
Daichi Hata, Takeshi Aihara, Hiroki Miura, Tetsuya
Shishido
The japan petroleum institute, The Japan Petroleum
Institute Award for Encouragement of Research andDevelopment “The Japan Petroleum Institute Award for
Encouragement of Research and Development”
Hiroki Miura
Royal Society of Chemistry Poster Award “Lowtemperature hydrogenation of CO2 to methanol oversupported gold catalysts”
Takumi Nakagawa, Hiroki Miura, Tetsuya Shishido, The
9th Tokyo Conference on Advanced Catalytic Science andTechnology (TOCAT9, Fukuoka, Virtual) July 24-29, 2022,
Fukuoka, Japan
Presentation Award “Inhibitory effect of trace impurities
on the catalytic activity in methanol reforming”
Katsutoshi Nomoto, Hiroki Miura, Tetsuya Shishido, 12th
International Conference on Environmental Catalysis(ICEC2022, Osaka, Virtual) July 30-August 2, 2022,
Osaka, Japan
Chemical society of japan, 37th Special presentation by
young researchers“Cooperative catalysis between gold and other elements
enabling efficient organic transformation over solid
surface” Hiroki Miura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 -3
Bachelor 4 -4■Outlines of the Research
1. Performance improvement in polymer electrolyte fuel cell.
Because polymer electrolyte fuel cell has higher energy
efficiency and lower power density compared to internal
combustion engine, it is important to improve the performanceof polymer electrolyte fuel cell. This research investigates theeffect of porous metal flow field for even supply of reactants tothe whole area of electrodes. Performance of electrochemicalhydrogen compression system using the cell is also analyzed.
2. Performance improvement in direct methanol fuel cell.
Direct methanol fuel cell system has higher energy density andlower power density compared to polymer electrolyte fuel cellsystem. This research investigates the effect of porous metal
flow field for enhancing the reactant supply and product removal
at the electrodes.
3. Ignition control in homogeneous charge compression ignition
combustion.
Internal combustion engine has higher power density and lower
energy efficiency compared to fuel cell system. This research
investigates a new combustion system by the compression
ignition of homogeneous fuel-air mixture for achieving higher
thermal efficiency in internal combustion engines. Combustion
characteristics of alternative fuels such as hydrogen andammonia in this engine system are also analyzed.

■Papers with Peer Review
See the annual report in Japanese■Academic Meeting＊Domestic
See the annual report in Japanese■Awards
See the annual report in Japanese28

Reports from Research Groups
Amano Laboratory
evolution under visible-light irradiation. We found that the 2hydroxy group enhances the electron injection and suppresses
the back electron transfer from TiO2 particles to the dye.

■Members
Fumiaki Amano
Professor /Dr. Eng.
Photoelectrochemistry, Energy Chemistry, 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, Catalytic Chemistry, Electrocatalysis
room: Frontier Research Building 201
TEL: +81-42-677-2852 (Ext. 5561)
e-mail: beppu@tmu.ac.jp
Doctor’s course - 1
Master’s course - 4
Bachelor (4th year) - 1

4. Highly active rutile TiO2 photocatalyst
Anatase TiO2 photocatalyst can only work under UV light.
Rutile TiO2 can absorb visible light at wavelengths less than 410
nm; however, its photocatalytic activity is not high. We activatedrutile TiO2 using hydrogen reduction treatment at 700 °C. The
photocatalytic activity of the H2-treated TiO2 was significantly
higher than anatase TiO2 under violet light irradiation at 405 nm
for the oxidative decomposition of acetic acid owing to the H2O2
formation.

■Outlines of the Research
1. Photocatalytic methane conversion
We have observed that photocatalytic dehydrogenative
coupling of methane (2CH4 → C2H6 + H2) proceeds using
Ga2O3-based photocatalysts under UV light irradiation in thepresence of water vapor. Electron spin resonance study using
DMPO as a spin-trapping agent revealed that the hydroxyl
radical (•OH) concentration was high in Au/Ga2O3, which
exhibited a high C2H6 production rate. The reaction mechanism
accelerated by water vapor was assumed in which CH4 wasactivated by •OH.

■Papers with Peer Review
1. F. Amano*, A. Yamamoto, J. Kumagai, Highly Active Rutile
TiO2 for Photocatalysis under Violet Light Irradiation at 405
nm, Catalysts, 12(10), Article 1079, 2022.
2. F. Amano*, Y. Akaki, A. Yamakata, Effects of HydroxyGroups in Anthraquinone Dyes on Photocatalytic Activity of
Visible-light-sensitized Pt-TiO2 for Hydrogen Evolution,
Catalysis Surveys from Asia, 27, pp 75–83, 2022.
3. F. Amano*, S. Koga, Electrochemical ImpedanceSpectroscopy of WO3 Photoanodes on Different Conductive
Substrates: The Interfacial Charge Transport between
Semiconductor Particles and Ti Surface, Journal of
Electroanalytical Chemistry, 921, Article 116685, 2022.
4) D.O.B. Apriandanu, S. Nomura, S. Nakayama, C. Tateishi,
F. Amano*, Effect of Two-Step Annealing on
Photoelectrochemical Properties of Hydrothermally Prepared
Ti-Doped Fe2O3 Films, Catalysis Today, in press, 2022.
5. F. Amano*, S. Nakayama, Improvement of Water Splitting
Activity of Silver-Excess AgTaO3 Photocatalysts via Nitric
Acid Washing Treatment, Journal of Environmental Chemical
Engineering, 10(4), Article 108089, 2022.
6. F. Amano*, M. Ishimaru, Hydroxyl Radical Formation on
Metal-Loaded Ga2O3 Photocatalysts for Dehydrogenative
Coupling of Methane to Ethane with Water, Energy Fuels,
36(10), pp 5393-5402, 2022.
7. F. Amano*, Y. Furusho, S. Yamazoe, M. Yamamoto,
Structure-Stability Relationship of Amorphous IrO2-Ta2O5
Electrocatalysts on a Ti Felt for Oxygen Evolution in Sulfuric
Acid, The Journal of Physical Chemistry C, 126(4), pp 18171827, 2022.
8. M. V. Makarova*, F. Amano*, S. Nomura, C. Tateishi, T.

2. Electrocatalyst for water electrolysis
A mixed layer of IrO2 and Ta2O5 deposited on a Ti fiber felt isan effective electrocatalyst for oxygen evolution reaction. We
have studied the local structure of the amorphous IrO2–Ta2O5
electrocatalysts through X-ray absorption spectroscopy. The
local [IrO6] octahedron structure in the amorphous IrO2
nanoparticles was essential not only to achieve high activity but
also high stability. During the preparation process, polyethylene
glycol assisted in a complete ligand exchange from the [IrCl6]
octahedron to the [IrO6] octahedron.

3. Dye-sensitized photocatalysts for hydrogen generation
Alizarin (1,2-DHAQ) is a stable red dye. We explored theeffect of the hydroxy substituents of anthraquinone molecules on
the photocatalytic H2 evolution over a dye-sensitized Pt-TiO2
system. The 2-hydroxy group was necessary to induce H229

Reports from Research Groups
Fukuma, Y. Takahashi*, Y. E. Korchev*, Direct
Electrochemical Visualization of the Orthogonal Charge
Separation in Anatase Nanotube Photoanodes for Water
Splitting, ACS Catalysis, 12(2), pp 1201-1208, 2022.
9. S. Ishizuka*, J. Nishinaga, K. Beppu, T. Maeda, F. Aoyagi,
T. Wada, A. Yamada, J. Chantana, T. Nishimura, T. Minemoto,
M. M. Islam, T. Sakurai, N. Terada, Physical and Chemical
Aspects at the Interface and in the Bulk of CuInSe2-based Thinfilm Photovoltaics，Physical Chemistry Chemical Physics，24,
pp 1262-1285, 2022.
10. R. Yoneda, K. Beppu, T. Maeda, T. Wada*，
Crystallographic and Optical Properties of Wide Bandgap
Photovoltaic Semiconductor System, Cu(Al,In)Se2, Japanese
Journal of Applied Physics, 61，SC1080, 2022.
11. S. Hosokawa, Y. Oshino, K. Beppu, T. Tanabe, T.
Motohashi, H. Asakura, K. Teramura, T. Tanaka*, Dynamic
Behavior of Pd/Ca2AlMnO5+δ for Purifying Automotive
Exhaust Gases under Fluctuating Oxygen Concentration，Catalysis Today，in press, 2022.

■Reviews＊Domestic
See the annual report in Japanese (1 article)■Invited Lectures＊International
1. Fumiaki Amano, Photocatalytic Dehydrogenative Coupling of
Methane in the Presence of Water Vapor, Post Symposium of
TOCAT9, 60th Aurora seminar, The 9th International
Symposium of Institute for Catalysis, August 1, 2022, Hokkaido
University, Institute for Catalysis＊Domestic
See the annual report in Japanese (3 lectures)■Academic Meeting＊International
1. Fumiaki Amano, Vapor-fed photoelectrochemical water
splitting by gas diffusion photoelectrodes, The 9th Tokyo
Conference on Advanced Catalytic Science and Technology(TOCAT9), July 25, 2022, Fukuoka International Congress
Center, Oral presentation
2. Satoshi Nakayama, Fumiaki Amano, Improvement of
Photocatalytic Activity of Ag-excess AgTaO3 via HNO3
Treatment, TOCAT9, July 25, 2022, Fukuoka International
Congress Center, Short presentation, Poster presentation
3. Fumiaki Amano, Gas-Phase Photoelectrochemical Reactions
using WO3 Photoanode Decorated with Tungsto(VI) Phosphoric
Acid, The 73rd Annual Meeting of the International Society ofElectrochemistry (ISE), September 13, 2022, Online, Oralpresentation
4. Dewangga Oky Bagus Apriandanu, Shinpei Nomura, Satoshi
Nakayama, Kento Shibata, Fumiaki Amano, Fe2O3 Photoanodes
on Different Conductive Substrates for Photoelectrochemical
Oxygen Evolution Reaction, The 73rd Annual Meeting of theISE, September 13, 2022, Online, Oral presentationc＊Domestic
See the annual report in Japanese (11 presentations)30

Applied Chemistry Colloquium

397rd2022/8/10
Hiroyuki Isobe (Department of Applied Chemistry, The University of Tokyo)” A versatile synthetic method for nanocarbon molecules: The first step”

398th

2022/10/5
Kazuya Yamaguchi (Department of Applied Chemistry, School ofEngineering, The University of Tokyo)” Development of Environmentally Friendly Dehydrogenative Oxidation
Reactions Using Multi-Functional Heterogeneous Catalysts”

399th

2022/11/25
Junya Ohyama (Faculty of Advanced Science and Technology, Kumamoto
University)” Study on structure effect on supported metal catalysts by atomic-scale
analysis and machine learning”

31Annual Report 2022
Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry for Environmental Sciences
April 1, 2023