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

Annual Report 2020

IndexReports from Research Groups
Kawakami Laboratory

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1

Asayama Laboratory

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6

Kubo Laboratory

▪▪▪▪▪

8

Setaka Laboratory

▪▪▪▪▪

10

Kanamura Laboratory

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12

Kajihara Laboratory

▪▪▪▪▪

14

Takagi Laboratory

▪▪▪▪▪

16

Uchiyama Laboratory

▪▪▪▪▪

19

Shishido Laboratory

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23

Shudo Laboratory

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25

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26

ColloquiumReports from Research Groups
Kawakami Laboratory
Figure 1. Schematic drawing of nanofiber/nanoparticle/PIM-1
composite membrane.Enhancement of gas permeability by
expansion of nano-space.

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

2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA
Polymer electrolyte fuel cells have attracted much attention
as clean and sustainable energy systems. We have reported
composite polymer electrolyte membranes based on phytic acid(Phy)-doped polybenzimidazole nanofibers (PBINF) showed
outstanding fuel cell performances under low relative humidity
conditions.
In this year, we fabricated novel polymer composite
membranes containing proton conductive acid-base blend
polymer nanofibers. The nanofibers bearing efficient proton
conductive pathways using the sulfonated and phosphonatedacid groups enhanced proton conductivity, especially at low
relative humidity. Proton conductivity and gas barrier properties
at high temperatures above 100oC was were evaluated for future
fuel cell operation.
New study on water electrolysis using anion exchange
membranes was also carried out.

Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-Science, Polymer Gas separation
MembraneRm. 9-137, +81-42-677-1111 Ext. 4837
yamato-masafumi@tmu.ac.jp
Kiyoshi SATO
Associate Professor / Dr. Eng.
Synthetic Organic Chemistry, Molecular Recognition,
Heterocyclic Chemistry, Physical Organic Chemistry,
Biomaterials
Rm. 9-349, +81-42-677-1111 Ext. 4886
sato-kiyoshi@tmu.ac.jp
Manabu TANAKA
Associate Professor / Dr. Eng.
Polymer Chemistry, Polymer Energy Materials, Fuel Cells,
Secondary Batteries, Nanofibers, Polymer Membranes
Rm. 9-639, +81-42-677-1111 Ext. 4586
tanaka-manabu@tmu.ac.jp
Doctor’s course - 3
Master’s course - 19
Bachelor 4 - 9

Figure 2. Novel proton conductive blend nanofiber composite
membrane.

■Outlines of the Research

3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA

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

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 focused on the development of polymer
nanofiber composite membranes for all solid state secondary
batteries. The novel polymer composite membranes containing
polar crystalline poly(vinylidene fluoride-co-trifluoro ethylene)
nanofibers showed higher ion conductivity and better secondary
battery performances, even at low temperatures.
New study on lithium-air battery using hydrophobic
nanofibers were also carried out.

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.
Decreasing the gas permeability due to physical aging of PIM1 is a major issue for practical use. We have succeeded insuppressing the deterioration of physical properties bycombining the nanofiber framework with PIM-1. Furthermore,
the particle dispersibility in the composite membrane composedof the nanofiber framework and PIM-1 was improved and themechanical properties of the composite membrane were also
improved successfully.

1

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

Superoxide dismutase (SOD) or catalase (CAT) are wellknown to efficiently eliminate superoxide radicals or hydrogen
peroxide as the most important antioxidants. We demonstrated
that a water-soluble cationic Mn-porphyrin with SOD activity or
catalase activity exhibited anticancer activity as well as
antioxidative activity.
In this year, we have studied intracellular ONOO--erasing
ability of the cationic manganese N-confused porphyrin(MnNCP), a novel coreductant-free catalyst for ONOOdisproportionation. The pyridinium-appended tetracationic
MnNCP showed a higher ONOO- eliminating activity towards
LPS-stimulated macrophage cells than that of corresponding
cationic manganese porphyrin.

4. Design of Multi-electron Redox Catalysts
Hiroyoshi KAWAKAMI, Kiyoshi SATO
Native metallo-enzymes facilitate various types of chemical
reactions under mild conditions in water. Thus, an artificial metal
complex as a bioinspired metallo-enzyme has application
potential for wide field of chemistry such as energy chemistry
and medicinal chemistry.
In this year, we have prepared modified electrodes withmetalloporphyrins bearing phenolic OH substituents spatiallyclosed to the metal centers. The catalyst-modified electrodes
show a proton-coupled multi-electron CO2 reduction andselective conversion of CO2 to CO revealed by rotating ring-discelectrode (RRDE) measurements.

HO

OH
HO

OH

N

N

M
N

N

HO

OH
HO

OH

Figure 4. Proton-coupled multi-electron redox catalyst forelectrocatalytic CO2 reduction.

Figure 6. Cationic manganese N-confused porphyrin (MnNCP)
with peroxynitrite eliminating activity.

5. Study of Epigenetics Engineering
Hiroyoshi KAWAKAMI, Kiyoshi SATO

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

The development and maintenance of an organism isorchestrated by a set of chemical reactions that switch parts ofthe genome off and on at strategic times and locations.
Epigenetics is the study of these reactions and the factors that
influence them.
In this year, we have prepared novel epigenetics control(EpC) carriers for suppression of epithelial-to-mesenchymaltransition (EMT) of carcinoma cells. The EpC carriers
successfully control the expression of EMT-related markers andsuppression of EMT in cancer cells by combined effect of
encapsulated epigenetic drugs. We also investigated the action
mechanism of mitophagy-inducing liposome nanocarrier for
elimination of damaged mitochondria in senescent cells. Thesebiomaterials will provide new treatment strategies for acquired
diseases caused by epigenomic alterations and for regenerative
therapy.

Controls of higher-order structure of feeble magnetic
materials by using a magnetic field have been studied in order toimprove some properties and to reveal new functions of thematerials.
In this year, we succeeded in evaluating the magnetic
properties and adsorption properties of nanosheets we used byusing a magnetic birefringence measurement and quantitative
NMR method. We also investigated a method for solidifying theliquid crystal phase formed by nanosheets into a nanocomposite
gel.

Figure 7. Schematic drawing of adsorption of organic molecules
to clay (left) and 2D-SAXS pattern of NC gel with liquid crystal
structure (right).

Figure 5. Epigenetic gene expression control by chromatin
conformations.

■Papers with Peer Review
1. Takeru Wakiya, Manabu Tanaka, Hiroyoshi Kawakami,“Fabrication and electrolyte characterizations of

6. Study of Free Radical Control by Artificial Enzyme
Hiroyoshi KAWAKAMI, Kiyoshi SATO,

2

Reports from Research Groups

2.

3.

4.

5.

6.

nanofiber framework”, Research Group on Inorganic
Polymers in The society of Polymer Science, Nov. 2020,
Online (in Japanese).
5. Hiroyoshi Kawakami, “Breaking the trade-off of polymer
electrolyte membrane properties”, Research Group on
Materials for hydrogen and PEFC in The society of Polymer
Science, Jan. 202, Online (in Japanese).
6. Hiroyoshi Kawakami, “Rejuvenation of cellular senescenceby nanocarrier”, Cosme Tech 2021 Tokyo (Tokyo), Jan. 202,
(in Japanese).

nanofiber
framework-based
polymercompositemembranes with continuous proton conductive pathways”,
Membranes, 11, 90, 1-11 (2021).
Yuki Kudo, Hiroto Mikami, Manabu Tanaka, Tadayuki Isaji,
Kazutoshi Odaka, Masafumi Yamato, Hiroyoshi Kawakami,"Mixed matrix membranes comprising a polymer of
intrinsic microporosity loaded with surface-modified nonporous pearl-necklace nanoparticles", Journal of
Membrane Science, 597, 117627 (2020).
Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami,"Fabrication and characterizations of soft and flexible
Poly(dimethylsiloxane)-incorporated network polymer
electrolyte membranes", Polymer 186,122045 (2020).
Hiroto Mikami, Shiori Higashi, Takuya Muramoto, Manabu
Tanaka, Masafumi Yamato, Hiroyoshi Kawakami “Gaspermeable mixed matrix membranes composed of apolymer of intrinsic microporosity (PIM-1) and surfacemodified pearl-necklace silica nanoparticles: Effect of
expansion of nano-space on gas permeability”, Journal of
Photopolymer Science and Technology, 33, 313-320(2020).
Takushi Shimane, Tsukasa Watanabe, Nohara Yokota,
Futoshi Matsumoto, Manabu Tanaka, Hiroyoshi Kawakami“Secondary battery performance of solid polymer
electrolyte membranes based on lithium ion conductive
polyimide nanofibers”, Journal of Photopolymer Scienceand Technology, 33, 321-325 (2020).
Masafumi Yamato, Tsunehisa Kimura, “Magnetic
processing of diamagnetic materials”, Polymers, 12, 1491
(2020).

■Academic Meeting
1. Masafumi Yamato, Takuya Muramoto, Manabu Tanaka,
Hiroyoshi Kawakami, Gas permeation characteristic of
mixed matrix membranes based on the polymer of intrinsic
microporosity PIM-1 and surface-modified pearl-necklace
silica nanoparticles, The 69th SPSJ Annual Meeting, May
2020 (in Japanese).
2. Masafumi Yamato, Kazumasa Komine, Takahiro Miyazaki,
Takashi Nakaoji, Hiroyoshi Kawakami, Effect of clay typeand size on mechanical properties of nanocomposite gel. The
69th SPSJ Annual Meeting, May 2020 (in Japanese).
3. Manabu
TANAKA,
Hiroki
HARADA,
MotokiNISHIZAWA, Moeri SHIMIZU, Hiroyoshi KAWAKAMI,
Fabrication and evaluation of novel composite electrolyte
membranes based on proton conductive polymer nanofiber
frameworks for next-generation fuel cells, The 69th SPSJ
Annual Meeting, 2Pa059, May 2020 (in Japanese).
4. Manabu TANAKA, Yu MATSUDA, Mitsuki OCHIAI, Aika
SASAKI, Nohara YOKOTA, Hiroyoshi KAWAKAMI,
Lithium ion conductive characteristics and all-solid-statebattery applications of polymer nanofiber composite
electrolyte membranes, The 69th SPSJ Annual Meeting,
2Pb060, May 2020 (in Japanese).
5. Aika Sasaki, Tanaka Manabu, Hiroyoshi Kawakami. All
solid state secondary battery application of polymer
electrolyte membrane composited with PVDF copolymer
nanofiber. The 42th membrane society of Japan, May 2020
(in Japanese).
6. Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami,
Preparation of polymer membrane containing particles by
dry – wet phase inversion method and the gas permeation
properties., 42st annual meeting of membrane science ofJapan, May 2020, Tokyo, Japan (in Japanese).
7. Takashi Nakaoji, Masafumi Yamato, and Hiroyoshi
Kawakami, Effect of clay size on the cross-linked structureof nanocomposite hydrogels, 42th The Membrane Society ofJapan, P-44S (May, 2020), (in Japanese).
8. Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Evaluation of lithium conductivity of nanofiber composite
electrolyte membranes with high salt concentration, 42th
The Membrane Society of Japan, P-408, June, 2020 (inJapanese).
9. Nohara Yokota, Takushi Shimane, Tsukasa Watanabe,
Manabu Tanaka, Hiroyoshi Kawakami, Secondary Battery
Performance of Solid Polymer Electrolyte Membranes
Based on Lithium Ion Conductive Polyimide Nanofibers,
The 37th International Conference of Photopolymer Scienceand Technology, 2020.
10. Aika Sasaki, Manabu Tanaka, Hiroyoshi Kawakami.
Improved ion conductivity and secondary battery■Books1.
Masafumi Yamato ， Hiroyoshi Kawakami, ” Frontier
Functional Polymer Metal Complex (Chapter 5, Section 3,
Separation Membrane Based on Polymer Complex )”,Sankyo Shuppan (Tokyo, Japan), 490-508 (2020). (inJapanese)2.
Manabu Tanaka, Hiroyoshi Kawakami, “Chemistry for
Hydrogen Energy Society”, Chemical education, 68, 384387 (2020).
3.
Hiroyoshi Kawakami, “Trends in university entrance
examination research”, National Center for University
Entrance Examinations (Tokyo, Japan), 179-191 (2020).
(in Japanese)
4.
Hiroyoshi Kawakami, “Electrospray/Electrospinning
Methods and Its Applications: Material Synthesis,
Molding, and Processing”, CMC Publisher (Tokyo, Japan),210-217 (2021). (in Japanese)■Invited Lectures
1. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2020 Basic seminar of polymer science for young
engineers, Dec. 2020, Online (in Japanese).
2. Masafumi Yamato, Higher-order structure analysis ofmacromolecules,
Characterization
seminarfor
macromolecules 2020, Dec. 2020, Online (in Japanese)
3. Manabu Tanaka, Aromatic Polymer Nanofibers and Their
Fuel Cell Applications, The 28th Japan Polyimides &Aromatic Polymers Conference (Kiryu), Dec. 2020 (inJapanese).
4. Hiroyoshi Kawakami, “Battery characteristics of solid
electrolyte membrane composed of ionic conductive3

Reports from Research Groups
performance of composite electrolyte membranes containing
PVDF-TrFE nanofibers. The society of fiber science andtechnology Japan, A1, Jun 2020 (in Japanese).
11. Aika Sasaki, Tanaka Manabu, Hiroyoshi Kawakami.
Improved ion conductivity and secondary battery
performance of composite electrolyte membranes containing
PVDF-TrFE nanofibers. The 42th membrane society ofJapan, P2 May 2020 (in Japanese).
12. Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami,
Preparation and gas permeation of asymmetric membranes
containing surface-modified nanoparticles., The Annual
Meeting of the Society of Fiber Science and Technology(Tower Hall Funabori), 2P219, June 2020(in Japanese).
13. Shiori Higashi, Takuya Muramoto, Manabu Tanaka,
Masafumi Yamato, Hiroyoshi Kawakami,
Temperaturedependence of gas permeability of PIM-1 composite
membrane containing surface-modified silica nanoparticles,
The Annual Meeting of the Society of Fiber Science andTechnology (Tower Hall Funabori), 3E13, June 2020(inJapanese).
14. Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Evaluation of ionic conductivity of high-Li salt concentrated
nanofiber composite electrolyte, The Annual Meeting of theSociety of Fiber Science and Technology, 3E04, June 2020
(in Japanese).
15. Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Lithium-ion conductive characteristics of nylon11 nanofiber
composite electrolyte membranes, The Annual Meeting of
the Society of Fiber Science and Technology, 1P216, June
2020 (in Japanese).
16. Takashi Nakaoji, Masafumi Yamato, and Hiroyoshi
Kawakami, Effect of clay size on the mechanical propertiesof nanocomposite hydrogels, The Annual Meeting of theSociety of Fiber Science and Technology (Not held), 2P266(June 2020), (in Japanese).
17. Keisuke Ashiba, Honomi Miyashita, Kiyoshi Sato,
Hiroyoshi Kawakami, Effet of functional liposome
nanocarrier for suppressing cell senescence, The 41st Annual
Meeting of the Japanese Society of Inflammation andRegeneration (Tokyo), P8-4 (July 2020).
18. Masafumi Yamato, Manabu Tanaka, Hiroyoshi Kawakami,
Development of high gas permeable separation membrane
containing surface modified nanoparticles, SPSJ 69th
Autumn Meeting，Sep. 2020, Online (in Japanese).
19. Manabu TANAKA, Motoki NISHIZAWA, Yu MATSUDA,
Mitsuki OCHIAI, Hiroyoshi KAWAKAMI, Fuel Cellapplications of ion conductive polymer nanofibers for thegrowing use of hydrogen energy, SPSJ 69th Autumn
Meeting，2M05, Sep. 2020, Online (in Japanese).
20. Masafumi Yamato, Manabu Tanaka, Hiroyoshi Kawakami，Gas permeation properties of polymer composite
membranes containing surface-modified nanoparticles: Gas
permeation mechanism, SCEJ 51st Autumn Meeting，Sep.
2020, Online (in Japanese).
21. Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami,
Asymmetric Membrane Containing Nanoparticles for Gas
Separation: Control of Particle Aggregation in Surface Skin
Layer Prepared by Dry - wet Phase Conversion Method.,
The SCEJ 51st Autumn Meeting (Online), PA344,
September 2020(in Japanese).
22. Hiroshi Kubota, Yoshio Kawashita, Makoto Wada,

Hiroyoshi Kawakami, Research on N2-enriched lean
combustion engine system using ultrahigh permeable gas
separation membrane that enables improved fuel efficiency,
The SCEJ 51st Autumn Meeting (Online), PA344,
September 2020(in Japanese).
23. Soma Miura, Yushi Minami, Risa Mitsuhashi, Riku Kubota,
Kiyoshi Sato, Hiroyoshi Kawakami, Intracellularantioxidant evaluation of Mn N-confused porphyrin, 70th
Conference of Japan Society of Coordination Chemistry(Online Conference), 3PF-01 (September 2020).
24. Takashi Nakaoji, Takahiro Miyazaki, Masafumi Yamato, andHiroyoshi Kawakami, Effect of clay size on the mechanicalproperties of nanocomposite hydrogels and magnetic
birefringence, 81th JSAP Autumn Meeting (Online), 8aZ10-7 (Sep. 2020), (in Japanese).
25. Ayano Imai, Yamato Masafumi, Hiroyoshi Kawakami,
Fabrication of composite membrane including surfacemodified nanoparticles and nanofiber framework,
Membrane Symposium 2020 (Online), November 2020 (inJapanese).
26. Mitsuki Ohiai, Manabu Tanaka, HIroyoshi Kawakami,
Suppression of dendrite growth and evaluation of battery
characteristics in lithium ion secondary batteries using
polymer nanofiber composite electrolyte membrane,
Membrane Symposium 2020, Online, (November, 2020).
27. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi
Kawakami, Fabrication and evaluation of proton
conductivity of composite electrolyte membrane bynanofiber containing polyvinylphosphonic acid, The
Membrane Symposium 2020, (Online), E-207 (November2020).
28. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami.
Lithium ion conductive characteristics of composite
electrolyte membranes consisted of polymer nanofibers withpolar group Membrane symposium 2020.
29. Honomi Miyashita, Keisuke Ashiba, Kiyoshi Sato,
Hiroyoshi Kawakami, Suppression of Cellular Senescenceby nanocarrier, The 58th Annual Meeting of the Japan
Society for Artificial Organs, Kochi (November 2020).
30. Kazuma Komine, Masafumi Yamato, Hiroyoshi Kawakami,
and Noriyuki Hirota, Mechanical properties of clay-polymer
network gel prepared in magnetic fields., 3rd G'L'owing
Polymer Symposium in KANTO (GPS-K 2020), (Online),
B01, November 2020.
31. Takeru Yamazaki, Kohei Arima, Riku Kubota, Kiyoshi Sato,
Hiroyoshi Kawakami, a novel application of polymer-lipid
nanoparticles to inhibition of cancer epithelial-tomesenchymal transition, 3rd G'L'owing Polymer
Symposium in KANTO (On-line), C22，(November 2020).
32. Aika Sasaki, Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi
Kawakami. Ion conductivity and secondary battery
characterizations of lithium salt-containing polymer
nanofiber composite electrolyte membranes. The 61 thBattery Symposium in Japan, 3F14, November 2020 (inJapanese).
33. Kazuma Komine, Masafumi Yamato, Hiroyoshi Kawakami
and Noriyuki Hirota, JSAP Magneto-Science Society 9th
meeting (Online),P-8A , December 2020.
34. Takashi Nakaoji, Masafumi Yamato, Hiroyoshi Kawakami,
Structure control of lyotropic nanosheet liquid crystal by
mixing different inorganic nanosheets and its application to4

Reports from Research Groups
nanocomposite gel, 9th Meeting of Magneto-Science
Society of Japan 2020 (Online), P3-A (December 2020), (inJapanese).
35. Haruhi Fujii, Masafumi Yamato, Hiroyoshi Kawakami, Theorientation control of inorganic nanoparticles in organicinorganic composite membrane, 9th Meeting of JSAP
Magneto-Science Society (December 2020).
36. Yui Okido, Takeru Yamazaki, Honomi Miyashita, Haruka
Nishimura, Keisuke Ashiba, Koki Mino, Kiyoshi Sato,
Hiroyoshi Kawakami, Suppression of Cellular Senescenceby Inducing Mitophagy in Senescent Cells, The 43 th Annual
Meeting of the Molecular Biology Society of Japan (Online),
December 2020.
37. Keisuke Ashiba, Yui Okido, Haruka Nishimura, Koki Mino,
Takeru Yamazaki, Honomi Miyashita, kiyoshi Sato,
Hiroyoshi Kawakami, Effect of liposome nanocarrier for
suppressing cell senescence targeting age-related disease,
The 20th Congress of the Japanese Society for Regenerative
Medicine (Kobe Convention Center), a90042 (March 2021).
38. Keisuke Ashiba, Takeru Yamazaki, Honomi Miyashita,kiyoshi Sato, Hiroyoshi Kawakami, Effect of liposome
nanocarrier inducing mitophagy for cellular senescence ofstem cell, The 20th Congress of the Japanese Society for
Regenerative Medicine (Kobe Convention Center), a90043(March 2021).
39. Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Lithium conductivity of nylon 11 nanofiber-based solid
polymer electrolytes with high salt concentration, The 88th
ECSJ Spring Meeting, March 2020 (in Japanese).
40. Kazuma Komine, Masafumi Yamato, Hiroyoshi Kawakami
and Noriyuki Hirota, Fabrication of clay/polymer network
gel with anisotropic structure., The 68th JSAP Spring
Meeting, (Online Virtual Meeting), 16a-Z19-6, March 2021.

■Patents
1. JP2020-76024,A “Secondary battery electrolyte”, Hiroyoshi
Kawakami, Manabu Tanaka, Manjit Sinh Grewal (published2020. 5. 21)
2. JP2020-82002,A “Multi-electron redox catalyst”, Hiroyoshi
Kawakami, Riku Kubota, Tomokazu Aoyama (published2020. 6. 4)■Awards
1. MSSJ Excellent Research Award 2020, Masafumi Yamato,
Research on control of polymeric material using magnetic
processing

5

Asayama Laboratory■Members

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

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

Insulinsecretion

InsulinPancreas

Liver

H
C CH2

Master’s course -8
Bachelor 4 -3

N

Protein■Outlines of the Research

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

+

Delivery toUnexplored
Space

O
H2N

Mono-Ion Complex【MIC】
C(CH2)n

N

N

N

1-x-y

Zn2+

n

In this year, to give an ability of not only complex formation
with both pDNA and Zn2+ but also active targeting for liver cells,
we have synthesized aminopropyl PVIm (PVIm-Pr-NH2),
followed by the modification with lactose residues as livertargeting ligand (PVIm-Pr-Lac). Then, we have prepared
Zn2+/pDNA/PVIm-Pr-Lac complex and evaluated the properties
of Zn2+/pDNA/PVIm-Pr-Lac as liver-cell-specific Zn2+/pDNA
co-delivery carrier. The resulting Zn2+/pDNA/PVIm-Pr-Lac
complex showed the low cytotoxicity and efficient Zn 2+/pDNA
co-delivery for liver-cell-targeting, leading to the suppression of
the internalization of insulin recepotors on the surface of liver
cells.

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

+

N

H
C CH2

y

Figure 2. Remote control of hypoglycemic hormone in blood.

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

+

H
C CH2

x

+
N
N
(CH2) CH3

N+

Survival insulin
to whole body

Zn 2+

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

PEG

H3C

Most Simple
Noncovalent
PEGylation

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

CH3O

CH2CH2O

n

CH3
H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

In this year, a mono-cationic guanidinopropyl end-modified
PEG (Gu-PEG) is used to form MIC with pDNA by thermal
treatment to anneal double helix structure for enhancement of
the MIC formation. After thermal treatment, Gu-PEG/pDNA
MIC formed the compact spherical structure with diameter ofaproximately 20 nm.
The resulting hMIC enhanced thestability under physiological conditions for in vivo application.
Hence, thermal treatment is expected to be promising potential
in development of MIC for gene therapy.

CH3

H3C

Insulin

7

8

9
10
11
Elution volume / mL

12

Figure 3. Development of novel bio-function by Chol-PEG.
In this year, carboxymethyl poly(1-vinylimidazole)polyampholytes with cholesterol or octyl groups as pendantgroups (partial hydrophobic CM-PVIm) have been synthesized
for biocompatible biomaterials.
A poly(propylene) (PP)surface was immersed into the resulting partial hydrophobic
CM-PVIm aqueous solution, resulting in suppression of protein

2. Bioactive Substance (Zn2+, protein) Delivery System
Shoichiro ASAYAMA
To give DDS carrier the ability for definitive treatment, wehave designed pH-sensitive polyvinylimidazole (PVIm)
derivateives as intelligent materials to change their structure andfunction in respons to external stimuli. Recently, Zn2+ delivery
6

adsorption. These results suggest that PP surface was coatedwith the CM-PVIm using a cholesterol or octyl anchor.

■Papers with Peer Review
1. Yuya Sone, Masayuki Nogawa, Shoichiro Asayama,
Designing a bioinert surface y simple coating with cholesterol
end-modified poly(ethylene glycol), Langmuir, 36, 1204512052 (2020).
2. Amika Mori, Yuki Kobayashi, Kei Nirasawa, Yoichi Negishi,
Shoichiro Asayama, Structure-activity relationship of mono-ion
complexes for plasmid DNA delivery by muscular injection,
Pharmaceutics, 13,78-88 (2021).
3. Yuki Kobayashi, Kei Nirasawa, Yoichi Negishi, Shoichiro
Asayama,, Noncorrelative relation between in vitro and in vivo
for plasmid DNA transfection by succinylated polyethyleneimine muscular injection, Journal of Biomaterials Science,
Polymer Edition, 32, 405-416 (2021).
■Academic Meeting
See the annual report in Japanese (7 articles)

7

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
Ryuhei Nishiyabu (retirement)
Assistant Professor / Dr. Eng.
Supramolecular Chemistry, Organic Chemistry,
Chemistry
Room: 9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: ryuhei@tmu.ac.jp

Material
Figure 2. Arylselanyl-substituted BOPHYs as triplet
sensitizers.
3. Synthesis of near-infrared absorbing dyes for applicationin opto-electronics
Yuji Kubo
Due to our ongoing program to develop near-infraredabsorbing dyes for application in opto-electronics, isoindolebased asymmetric N2O2-BODIPYs were synthesized.
Replacement of benzene with the corresponding
thiophene counterpart led to a redshift in the absorption
band. Notably, it was found that the absorption
properties were dependent on not only the position of
the thiophene unit but also number of the unit in the
structure. The structure-photophysical property
relationship was investigated by electrochemicalmeasurements, theoretical calculation, and X-ray
crystallographic analysis.

Master’s course; 14
Bachelor; 4Outlines of the Research
1. Synthesis of dye-sensitized photocatalysts for hydrogen
Production
Yuji Kubo
Abstract
It is worthwhile to develop functional dyes that
could contribute to the Sustainable Development Goals(SDGs). Given that photocatalysts for hydrogenproduction is remained to be researched due to its low
efficiency. Sensitization of dye which has high lightharvesting capability is a promising approach for
improving efficiency. In this study, benzofuran-fused
BODIPY dye with cyanoacrylic acid as an anchoringgroup (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 the presentation, the photocatalytic
activity of 1-loaded TiO2 is discussed.

Figure 3. Unsymmetric BODIPY dyes.
4. Organic room-temperature phosphoresncece materials
Yuji Kubo
Abstract
Our ongoing program to develop boronic acid-based
supramolecules with phosphorescence properties makes it
possible to propose afterglow-based functional systems. In thisstudy, given that polyvinyl alcohol (PVA) has a good oxygen
barrier property with a strong hydrogen bonding network, a
thiophene boronate ester-cross-linked PVA (1-PVA) was
fabricated for the first time, which emitted an efficient cyan
afterglow (em = 475 nm, ex = 254 nm), the quantum yield being
determined to be 6.3%. Furthermore, the emission color was
successfully tuned via triplet-to-singlet Förster-type resonanceenergy transfer by doping sulforhodamine B that shows thecomplementary color emission. The resulted films showed
multi-color afterglow, including white light.

Figure 1. Dye-sensitized photocatalytic hydrogen production.
2. Arylselanyl-BOPHYs 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 2and 7- position of bis(difluoroboron)1,2-bis((1H-pyrrol-2yl)methylene)hydrazine (BOPHY) core led to production of
new triplet photosensitizer 1. Setting up TTA-UC system of 1
and a triplet acceptor 9,10-diphenylanthracene allowed a UC
emission with large anti-Stokes shift of 94 nm and UC quantum
yield (ФUC) of 3.9% in toluene when excited with 524 nm laser(50 mW).

8

Reports from Research Groups■Books, etc.
See the annual report in Japanese.

■Invited Lectures
1. Emissive boronate supramolecules; preparation andfunctionalization, Yuji Kubo, Keynote Speaker, International
Conference on Chemistry and Science Education (ICChSE2020), cancelled.
Figure 4. Multi-color afterglow emission based on triplet-tosinglet FRET.

■Academic Meeting＊Domestic
See the annual report in Japanese (8 articles)

5. Synthesis of an environment-sensitive probe
Yuji Kubo
abstract
Tricyanopyrroline (TCP)-based intermolecular charge transfer(ICT) dye 1 was synthesized by incorporating phenothiazine
and diphenylamine groups, and it was shown to absorb nearinfrared light at 734 nm with a molar extinction coefficient(εmax) of 1.67×104 M–1 cm–1 in toluene, resulting in a broad
absorption band ranging from 600 to 900 nm. By combining
the properties of the amide (-NHCO-) group of the TCP
acceptor with its ICT character, the photophysical properties of
1 were found to be environment-sensitive.

■Patents
1. See the annual report in Japanese■Awards
1. See the annual report in Japanese

Figure 5. A TCP-containing ICT dye and solvent dependencyof the chromogenic property.

■Papers with Peer Review
1. R. Hasegwa, S. Iwakiri, and Y. Kubo, Synthesis and triplet
sensitization of bis(arylselanyl)BOPHYs; potential applicationin triplet-triplet annihilation upconversion, New J. Chem., 2021,
accepted, DOI: 10.1039/D1NJ00721A
2. M. Kanakubo, Y. Yamamoto, Y. Kubo, Room-temperaturephosphorescence of thiophene boronate ester-cross linked
polyvinyl alcohol; a triplet-to-singlet FRET-induced multi-color
afterglow luminescence with Sulforhodamine B, Bull. Chem.
Soc. Jpn., accepted, DOI:10.1246/bcsj.20210004
3. Y. Kubo, T. Nozawa, K. Maeda, and Y. Hashimoto,
Asymmetrical benzo[a]-fused N2O2-boron-chelated BODIPYs
as red to near-infrared absorbing chromophores: Synthesis,characteristics and device applications for opto-electronics,
Mater. Adv., 2021, 2, 1059-1071. DOI: 10.1039/D0MA00910E
4. T. Arai and Y. Kubo,
Chemical stimulus-responsive tricyanopyrroline-based ICT
chromophore as a potential environment-sensitive probe, Dyes
Pigm.,, 2021, 108927. DOI: 10.1016/j.dyepig. 2020.108927
5. Y. Sasaki, S. Kojima, V. Hamedpour, R. Kubota, S. Takizawa,
I. Yoshikawa, H. Houjou, Y. Kubo and T. Minami, Accuratechiral pattern recognition for amines, albeit a single chemosensor.
Chem. Sci., 2020, 11, . 3790-3796 DOI: 10.1039/D0SC00194E

9

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. Structure and dielectric spectra (powder sample) of
1,2-difluorophenylene bridged molecular gyrotops (paper #1).
We have recently reported the synthesis and crystal structure ofa phenylene-bridged macrocage as a gyroscope-like molecule (1,Figure 3) in the crystalline state. The dynamics of the phenylene
moiety was probed by solid-state 13C CP/MAS proton dipolardephasing NMR spectroscopy. Herein, solid-state 2H NMR
studies were performed to study the dynamics of the gyroscopelike molecule with a deuterated rotor in the crystalline state. A
spectrum with a narrow line shape was obtained at 300 K. The
facile exchange among three stationary states, which wasobserved by X-ray crystallography, was clearly confirmed.
(Figure 3, paper #2).

Doctor’s course -0
Master’s course -7
Bachelor 6
Development of Highly Designed Organic Molecules
Wataru SETAKA, and Yusuke INAGAKIDevelopment of organic molecules of which strucrure andfunctions are highly designed would improve our daily life withrespect to energy saving and environmental consequence. Ourinterest lies in the design and synthesis of organic 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. Crystalline Molecular Gyrotop
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. Solid-state 2H NMR spectra of gyroscope-likemolecule 1 (paper #2).
A novel molecular gyrotop with a furan-2,5-diyl was synthesized.
The furan-diyl rotor showed rotation inside the cage in a solution.
However, no furan-rotor dynamics was observed in a crystalline
state, while a corresponding thiophene-diyl derivative showedrotation in the same condition. The lack of dynamics in the furan
derivative resulted from the deformed structure of the cagecaused by the small intersecting angle between two SiC(aromaric) bonds.

Figure 1. molecular gyrotop.
In this year, following papers were published.
1,2-Difluoro-3,6-phenylene-bridged macrocages were designed
and synthesized as crystalline molecular gyrotops with a dipolar
rotor. The thermal ring dynamics of the dipolar rotor in the
crystal were investigated by solid-state NMR and dielectric
spectroscopy. The gyrotop that was surrounded by three C14alkyl chains exhibited an exchange between two stationary
positions in the crystalline state. In contrast, the gyrotop cage
consisting of C18 chains exhibited no dynamics in the crystalline
state. Although the corresponding phenylene derivatives exhibita facile rotational motion of the phenylene group in the
crystalline state, the dynamics of each derivative was observed
to be different. The reason for this difference is ascribed to thedifference in the bulkiness between the fluorine and hydrogenatoms in the rotor. (Figure 2, paper #1).

Figure 4. Structural formula of molecular gyrotops with aheterocyclic rotor (paper #3).
2. Novel Molecular Bevel Gears
Since a triptycene has a wheel-like structure, their combinatedstructures would be candidates as molecular based gear system.
Construction of hydrogen-bonded networks among hydroxyl
groups has often been utilized to synthesize specific structureson the basis of supramolecular chemistry. In this study,
resorcyltriptycene was designed as a possible component of acrystalline molecular gear, because the molecule has a triptycyl
wheel and a resorcyl linker which can be involved in

10

Reports from Research Groupsintermolecular alignments in a crystal, as mediated by hydrogenbonded networks. The synthesis and crystal structure ofresorcyltriptycene are reported here. The gear alignment among
triptycyls in a crystalline state was achieved in a crystal structureof resorcyltriptycene containing water in the intermolecularspaces. However, rotations of triptycyls in the crystalline state
was suppressed by steric interaction with the water molecules.
This crystal structure was stabilized by O–H···Cπ(phenyl)interactions between triptycyl and the hydrated water. Moreover,single crystals without solvent and with methanol were obtained
from a dry toluene solution and a methanol solution, respectively.
Transformations among the single crystals were observed byheating or drying or soaking in a solvent. It is significant thatvarious crystal structures dependent on the condition wereobserved. The observed phenomena should aid the design offunctional crystals. (Figure 5, paper #4).

4.

5.

6.

7.

8.

9.
Figure 5. Crystal structure of resolcyltriptycene hydrate.
10.

■Papers with Peer Review
1.

2.

3.

4.

Structure and Dynamics of Crystalline Molecular Gyrotops
with a Difluorophenylene Rotor, Taro Tsuchiya, Yusuke
Inagaki, Kentaro Yamaguchi, and Wataru Setaka*, J. Org.
Chem. 2021, 86(3), 2423–2430.
DOI: 10.1021/acs.joc.0c02571N
Solid-State 2H NMR Study for Deuterated Phenylene
Dynamics in a Crystalline Gyroscope-Like Molecule,
Wataru Setaka*, Kentaro Yamaguchi, Mitsuo Kira,
Chemistry 2021, 3(1), 49, 39–44. (A Special Issue inHonor of Professor J. Michl)
DOI: 10.3390/chemistry3010004
A Furan-2,5-diyl Bridged Macrocage as a Highly Distorted
Molecular Gyrotop, Y. Inagaki, S. Ueda, K. Yamaguchi,
and W. Setaka*, Chem. Lett. 2020, 49, 49, 1291–1293.
DOI: 10.1246/cl.200533
Gear Alignments due to Hydrogen-Bonded Networks in a
Crystal Structure of Resorcyltriptycene Hydrate and its
Transformation to a non-Gearing Anhydrate Crystal by
Heating, N. Tanaka, Y. Inagaki, K. Yamaguchi, and W.
Setaka*, Cryst. Growth Des. 2020, 20(2), 1097–1102.
DOI:10.1021/acs.cgd.9b01424

11.

12.

13.

14.

Japanese)
Syuuto Ohyama, Yusuke Inagaki, Wataru Setaka, Synthesis
and Crystal Structure of Di(resorcylethynyl)triptycene as a
Candidate for Solid-state Molecular Gear, The 101st CSJ
Annual Meeting Chemistry 2021, 2021.3.19-22(Online).(3/19 A08-1pm-14)(oral, in Japanese)
Daichi Kurimoto, Yusuke Inagaki, Wataru Setaka,
Oxidation
Properties
ofFerrocene
Substituted
Spirosilabifluorene, The 101st CSJ Annual Meeting
Chemistry 2021, 2021.3.19-22 (Online).(3/21 P02-3yn05)(poster, in Japanese)
Keita Nobuhara, Yusuke Inagaki, Wataru Setaka, Synthesis
and CT Fluorescence of Benzo[b]thiophene-1,1-dioxide
Bridged Macrocage, The 47th Symposium on Main Group
Element Chemistry, 2020.12.3-5. (Online).(12/4 O27)(oral, in Japanese)
Keita Nobuhara, Yusuke Inagaki, Wataru Setaka, Silyl
Effectson
Fluorescence
Properties
ofSilylbenzo[b]thiophene-1,1-dioxides,
The
24th
Symposium of the Society of Silicon Chemistry, Japan,
2020.11.6. (Online).(11/6 1B)(oral, in Japanese)
Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka,
Facile Synthesis and Structures of Silyl-substituted
Acediynes, The 24th Symposium of the Society of Silicon
Chemistry, Japan, 2020.11.6. (Online).(11/6 12B)(oral, inJapanese)
Syuuto Ohyama, Yusuke Inagaki, Wataru Setaka, Crystal
Structures of Isophthalyltriptycene, 10th CSJ ChemistryFesta,
OnlineREMO,
2019.10.15-17(Tokyo,Japan).(10/22 P7-030)(poster, in Japanese)
Yutto Ikeda, Yusuke Inagaki, Wataru Setaka, Synthesis of
Disilabicyclo[14.14.14]alkane as a Huge Macrocage, 10th
CSJ Chemistry Festa, Online REMO, 2019.10.15-17(Tokyo, Japan).(10/21 P6-039)(poster, in Japanese)
Hazuki Inami, Yusuke Inagaki, Wataru Setaka, Substituent
Ecffects on Structure of Phenyltriptycene, 10th CSJ
Chemistry Festa, Online REMO, 2019.10.15-17 (Tokyo,
Japan).(10/21 P5-042)(poster, in Japanese)
Uyou To, Yusuke Inagaki, Wataru Setaka, Synthesis ofMacrocyclic Diethynylenephenylene by Coupling ofSilyldiethynylbenzene, 10th CSJ Chemistry Festa, Online
REMO, 2019.10.15-17 (Tokyo, Japan).(10/21
P5043)(poster, in Japanese)
Daichi Kurimoto, Yusuke Inagaki, Wataru Setaka, Redox
Properties of a Silicon-containing Spirolinker, 10th CSJ
Chemistry Festa, Online REMO, 2019.10.15-17 (Tokyo,
Japan).(10/21 P4-055)(poster, in Japanese)
Keita Nobuhara, Yusuke Inagaki, Wataru Setaka, Synthesis
and Fluorescence Properties of Benzo[b]thiophene-1,1dioxide Bridged Macrocages, 10th CSJ Chemistry Festa,
Online REMO, 2019.10.15-17 (Tokyo, Japan).(10/20 P2046)(poster, in Japanese)■Awards
1. Yusuke Inagaki, Leading Scientists Award, Faculty ofEnviromental Sciences, Tokyo Metropolitan University, 2021.01.

■Academic Meeting＊Domestic
1. Uyou To, Yusuke Inagaki, Wataru Setaka, Synthesis of
Dihydroxybenzene-bridged Macrocyclic Disilaalkanes
The 101st CSJ Annual Meeting Chemistry 2021,
2021.3.19-22 (Online).(3/19 A17-1pm-02)(oral, inJapanese)
2. Hazuki Inami, Yusuke Inagaki, Wataru Setaka, Observationof Restricted Rotation of the Phenylene Rotor in
Phenyltriptycene Derivartive, The 101st CSJ Annual
Meeting Chemistry 2021, 2021.3.19-22 (Online).(3/19
A17-1pm-03)(oral, in Japanese)
3. Yuto Ikeda, Yusuke Inagaki, Wataru Setaka, Synthesis ofMacrocyclic Disilabicycloalkanes from Caged Siloxanes,
The 101st CSJ Annual Meeting Chemistry 2021,
2021.3.19-22 (Online).(3/19 A17-1pm-04)(oral, in

11

Reports from Research Groups
Kanamura Laboratory
succeeded in improving the reversibility and stability of lithiumsulfur batteries (Fig. 2).

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

EnergyChemistry,Previous

Improved

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 -3
Master’s course -13
Bachelor 4 -7

■Outlines of the Research

Fig. 2 The charge and discharge curves of a lithium-sulfur
battery with a Li+-ion conduciting solid electrolyte membrane.

1. Research on next-generation rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of rechargeable lithium batteries with lithiummetal anode was carrired out in order to realize high energy
density. Lithium-metal anode has about ten times larger
gravimetric capacity than currently-used graphite anode.
However, its practical use requires the improvement of cycle
performance with the suppression of needle-like deposition oflithium metal in the charge process. The cycle performance oflithium-metal anode, namely the coulombic efficiency of its
deposition and dissoliution was greatly improved by applying athree-dimensionally ordered macriporous separator and a highly
concentrated electrolyte solution. The advantage of thiscombination was also confirmed in the full cell combined withlithium-metal anode and high-capacity cathode (Fig. 1).

3. Research on fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
In order to improve energy conversion efficiency and waste heatutilization, it is necessary to raise the operating temperature offuel cells to about 200 °C. So far, we have focused on phosphoricacid / ionic liquid mixtures as electrolytes suitable to theintermediate temperature operation of fuel cells. In this FY, theelectrochemical activity and stability of catalysts in the mixed
electrolytes were investigated and improved via optimization ofphosphoric acid / ionic liquid mixing ratio. In addition, wedeveloped OH--conducting ionic liquid for the intermediate
temperature operation of alkaline-type fuel cells. As shown in
Fig. 3, it was found that a glassy carbon (GC) electrode has ahigher activity of electrochemical oxygen reduction reaction
than Pt electrode in this ionic liquid (Fig. 3). This result suggests
the feasibility of fuel cells without using precious metals as
catalyst.

Pt electrodePt electrodeoxygenoxygenreduction
reduction
current
current

Glassy carbon
Glassycarbonelectrodeelectrode

120 °C120°C
O2 atmosphereO2 atmosphere

Fig. 1 The charge and discharge curves of a rechargeable
lithium-metal battery with a high capacity cathode.

Fig. 3 The comparison of electrochemical oxygen reduction
reaction activity between Pt and GC electrodes.

We also worked on the development of lithium-sulfur batteries,
which can use low-cost sulfur as the cathode. Lithium-sulfur
compounds that are formed at the cathode during the chargedischarge process easily dissolve into an electrolyte solution anddiffuse to lithium-metal anode, resulting in self-discharge oflithium-sulfur batteries. To solve this problem, we applied a Li+ion conduciting solid electrolyte membrane. In addition, we
designed a sulfur cathode suitable for solid electrolytes, and■Papers with Peer Review
1.

12

Yosuke Goto, Shota Nakanishi, Yusuke Nakai, Takeshi
Mito, Akira Miura, Chikako Moriyoshi, Yoshihiro
Kuroiwa, Hidetomo Usui, Tatsuma D. Matsuda, Yuji Aoki,
Yoshifumi Nakacho, Yuto Yamada, Kiyoshi Kanamura andYoshikazu Mizuguchi, The crystal structure andelectrical/thermal transport properties of Li1-xSn2+xP2 andReports from Research Groups

2.

3.

4.

5.

6.

7.

its performance as a Li-ion battery anode material, JournalofMaterials
ChemistryA(2021)
DOI:
10.1039/d0ta11045k.
Zengqi Zhang, Beibei Zhao, Shu Zhang Jianjun Zhang,
Pengxian Han, Xiaogang Wang, Furui Ma, Deye Sun,
Yongcheng Jin, Kiyoshi Kanamura, Ganglei Cui, A
mixed electron/ion conducting interlayer enabling ultrastable cycle performance for solid state lithium sulfur
batteries, Journal of Power Sources, 487 (2021) 229428.
Ryosuke Nakazato, Yoki Kou, Daisuke Yamamoto,Tetsuya Shimada, Tamao Ishida, Shinsuke Takagi,
Hirokazu Munakata, Kiyoshi Kanamura, Hiroshi
Tachibana, and Haruo Inoue, Effect of Li ions Doping intop-type Semiconductor NiO as a Hole Injection/Transfer
Medium in the CO2 Reduction Sensitized/Catalyzed byZn-porphyrin/Re-complex upon Visible Light Irradiation,
Research on Chemical Intermediates, 47 (2021) 269–285.
Feilure Tuerxun, Kentaro Yamamoto, Toshihiko Mandai,
Yoshitaka Tateyama, Koji Nakanishi, Tomoki Uchiyama,
Toshiki Watanabe, Yusuke Tamenori, Kiyoshi Kanamura,
Yoshiharu Uchimoto, Effect of Interaction among
Magnesium Ions, Anion and Solvent on Kinetics ofMagnesium Deposition Process, J. Phys. Chem. C, 124(2020) 28510–28519.
Kohei Shimokawa, Taruto Atsumi, Norihiko L. Okamoto,
Tomoya Kawaguchi, Susumu Imashuku, Kazuaki
Wagatsuma, Masanobu Nakayama, Kiyoshi Kanamura,
Tetsu Ichitsubo, Structure Design of Long-Life SpinelOxide Cathode Materials for Magnesium Rechargeable
Batteries, Adv. Mater. (2020) 2007539.
Koichi KAJIHARA, Keiichi HIRUTA and Kiyoshi
KANAMURA, Cosolvent-free sol gel dip-coating of silica
ﬁlms from tetraalkoxysilanewater binary systems:
precursor solutions of long pot life and theircharacterization by nuclear magnetic resonancespectroscopy, Journal of the Ceramic Society of Japan, 128(2020) pp.772-782.
Koichi Kajihara, Hirohiko Kato, Ryo Takahashi, Kiyoshi
Kanamura, Hiroshi Mizoguchi, Yukiko Namatame,
Hiroyasu Sato, Twinning by Merohedry and Thermal
Expansion of Zeolitic Clathrasil Deca-dodecasil 3R,
Inorganic Chemistry, 59 (2020) pp.5600−5609.

■Books and reviews
See the annual report in Japanese (5 articles)■Invited Lectures＊International
1. Kiyoshi kanamura, Next Generation Batteries of EVs for
CO2 Reduction, The 2nd Japan-China Forum on Power
Batteries for New Energy Vehicles, October 2020, online
presentation.
＊Domestic
See the annual report in Japanese (4 articles including 2
requested lecture)■Academic Meeting＊Domestic
See the annual report in Japanese (10 articles)

13

Reports from Research Groups
Kajihara Laboratory■Members

life as long as 30 days at room temperature. We also found thatsilica-(Tb,Ce)PO4 transparent glass-ceramics prepared bycosolvent-free sol-gel mehod became consentration-quenchingfree green phosphors with internal quantum efficiency close tounity (Fig. 3), although the (Tb,Ce)PO4 nanocrystals containrare-earth ions at high concentrations (1.45×1022 cm−3).

Koichi KAJIHARA
Associate 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
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

Fig. 2 Bonding states of silica oligomers and residual wateramount in solutions prepared by cosolvent-free hydrolytic
polycondensation at various water to alkoxide ratios.

Master’s course -10
Bachelor 4 -7

■Outlines of the Research
1. Studies on inorganic materials and energy devices
Koichi KAJIHARA
Silica is a ubiquitous material and its utilization is inaccordance with SDGs.
Rhombohedral particles of silica zeolite deca-dodecasil 3R(DDR) seem single crystalline. We found that these crystals areof twinning by merohedry, and succeeded the structure analysis(Fig. 1). We also found that this twinning does not dislupt theconnectivity of micropores, and this makes it possible to thesmooth adsorption and desorption of gas molecules in thesetwinned crystals.

Fig. 3 A silica-(Tb,Ce)PO4 transparent glass-ceramic
concentration-quenching-free green phosphor illuminated by an
UV LED at 290 nm.
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.
3. Fabrication of Nanofilters by Electrochemical Process
Takashi YANAGISHITAFor the fabrication of ordered nanofilere membranes, we haveinvestigated anodization process of Al. The size and interval ofholes could be controlled by adjusting the anodization conditions.
Metal and semiconductor nanohole array structures have been
also fabricated using an anodic porous alumina as a template.
For the replacement of the ordered hole-array structure withother materials we developed a two-step replication process inwhich formation of a replicated negative and subsequentpreparation of a replicated positive give the nanohole structure
identical to that of mother structure of anodic orous alumina.
Metal (Au, Pt, Ni) and semiconductor (TiO2, ZnO, CdS)
nanohole arrays have been fabricated using the two-step process.
Detailed conditions for the precise replication were examined

Fig. 1 Crystal structure of silica zeolite DDR of twinning by
merohedry.
We are studying cosolvent-free sol-gel method to form silcabased materials only from silicon alkoxides and water without
using cosolvents. NMR investigation of reaction mixture
indicated that solutions prepared at water to alkoxide less than 2
contain negligible amount of water, wheras contain a lot of SiOH
goups with low reactivities when tetraethoxysilane (TEOS) as
the silicon source (Fig. 2). The solution prepared at the water toalkoxide ratio of 1.7 became a silica coating solutions of a pot

14

Reports from Research Groups
experimentally, and new applications, such as optical devices
and detector for low energy ions, have been developed

13. S. Kadoya, F. Kimura, T. Yanagishita, T. Kajihara,
Structure size effect on polymer infiltration in injection
mold direct joining. Precision Engineering, 67, 100 (2021).
14. T. Yanagishita, M. Ozaki, R. Kawato, A. Kato, T. Kondo,
H. Masuda, Preparation of ordered porous alumina
through-hole membranes with large hole periods by twolayer anodization. J. Electrochem. Soc., 167, 163502(2020).
15. T. Yanagishita, H. Hirose, T. Kondo, P. Schmuki, H.
Masuda. Fabrication of ideally ordered TiO2 through-holemembranes by two-layer anodization. RSC Adv., 10, 37657(2020).
16. T. Yanagishita, R. Sato, T. Kondo, H. Masuda, Preparationof multilayered porous alumina hollow spheres byanodization of Al particles. Electrochem. Commun., 120,
106848 (2020).
17. T. Yanagishita, A. Kato, H. Masuda, Preparation offreestanding tubular alumina through-hole membranes by
two-layer anodization. Jpn. J. Appl. Phys., 59, 038002(2020).

4. Preparation of Ordered Nanostructures by Nanoimprinting
Using Ordered Anodic Porous Alumina Molds
Takashi YANAGISHITA
Ordered pillar array and hole array patterns were fabricated bynanoimprinting using anodic porous alumina. Patterned surface
prepared by this process could be used for the antirefrection
surface and surper hydrophobic surface.

■Papers with Peer Review
1. R. Iwasaki, K. Kajihara, Negligible concentration quenchingin photoluminescent nanocrystals with high photoactive
rare-earth concentrations: silica–(Tb,Ce)PO4 transparent
glass-ceramic green phosphors, J. Mater. Chem. C,
published online, DOI: 10.1039/d0tc06043g
2. K. Kajihara, K. Hiruta, K. Kanamura, Cosolvent-free sol–gel dip-coating of silica films from tetraalkoxysilane–water
binary systems: precursor solutions of long pot life andtheir characterization by nuclear magnetic resonancespectroscopy, J. Ceram. Soc. Jpn. 128, 772-782 (2020).
3. L. Skuja, N. Ollier, K. Kajihara, Luminescence of nonbridging oxygen hole centers as a marker of particle
irradiation of α-quartz, Radiat. Meas. 135, 106373 (2020).
4. K. Kajihara, H. Kato, R. Takahashi, K. Kanamura, H.
Mizoguchi, Y. Namatame, H. Sato, Twinning by merohedry
and thermal expansion of zeolitic clathrasil deca-dodecasil
3R. Inorg. Chem. 59, 5600-5609 (2020).
5. T. Yanagishita, R. Asami, H. Masuda, Monodisperse
albumin particles fabricated by membrane emulsification
using anodic porous alumina Mater. Res.Express, 8,025003 (2021).
6. T. Kondo, T. Tamura, T. Yanagishita, H. Masuda.
Formation of Ideally Ordered Anodic Porous Zirconia by
Anodization of Vacuum-Deposited Zr on Molds. J.Vaccum.
Sci. Technol. B, in press
7. T. Yanagishita, R. Moriyasu, T. Ishii, H. Masuda,
Self-Ordered Anodic Porous Alumina with Inter-Hole
Spacing Over 1.5 µm. RSC Adv., 11, 3777 (2021).
[2021 RSC Advances HOT Article]
8. T. Yanagishita, A. Kato, T. Nakamura, H. Masuda. Highly
Ordered Alumina Through-Hole Membranes Having
Reduced Hole Intervals: 30–50 nm. ECS J. Solid State Sci.
Technol., 10, 013007 (2021)
9. T. Yanagishita, T. Masuda, T. Kondo, H. Masuda, Highlyordered anodic porous oxide of transition metals fabricatedby anodization combined with pretexturing process.
Electrochem. Commun., 123, 106916 (2021).
10. T. Yanagishita, T. Hayakawa, T. Kondo, H. Masuda.
Preparation of Ni Micropillar Arrays with High Aspect
Ratios Using Anodic Porous Alumina Template and Their
Application to Molds for Imprinting. RSC Adv., 11, 2096
(2021).
11. T. Kondo, H. Miyazaki, T. Yanagishita, H. Masuda.
Fabrication of Metal Nanorod Arrays Using Anodic Porous
Alumina Mask with Elliptical Apertures Prepared by Lattice
Conversion Process. Jpn. J. Appl. Phys., 60, 010907 (2021).
12. T. Yanagishita, H. Takai, T. Kondo, and H. Masuda. SnO2
Nanofibers Prepared by Wet Spinning Using an Ordered
Porous Alumina Spinneret. Nanotechnology, 32, 145603(2021).

■Reviews and Books
See the annual report in Japanese ( 4 articles)■Invited Lectures＊Internationa
1. T. Yanagishita , H. Masuda,Semiconductor Through-Hole
Membranes with Controlled Geometrical Structures by
Anodization Processes,237th Meeting of the Electrochemical
Society, 2020/5, online.
2. T. Yanagishita , H. Masuda,Preparation of Ordered Throughhole membranes with controlled geometrical structures by
two-layer, anodization process. PRiME2020, 2020/10,
online＊Domestic
See the annual report in Japanese (1 articles)■Academic Meeting＊International
1. K. Kajihara, R, Seto, K. Kanamura, S. Yoshida.
Poly(phenyl-co-n-alkylsilsesquioxane) and poly(phenylcovinylsilsesquioxane)glasses
withlowmelting
temperatures prepared by cosolvent-free hydrolytic
polycondensation of organotrimethoxysilanes. GLASSMEETING 2020，2020/12，online＊Domestic
See the annual report in Japanese (27 articles)■Patents
See the annual report in Japanese ( 2 articles)■Awards
See the annual report in Japanese ( 1 articles)

15

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

Chemistry,

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

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

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

Tetsuya SHIMADA
Assistant Prof. / Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Visiting researcher 4
Doctor’s course 5
Master’s course 10
Bachelor 8■Outlines of the Research
Our group challenges to control photochemical reactions suchas electron and energy transfer, by controlling the orientation andalignment of dyes on the inorganic surfaces.
Recently,organic/inorganic hybrids composed of porphyrins and layeredmaterials have been the subject of intensive investigations to
explore their novel properties and functionalities. We foundout that a precise matching of distances between the negatively
charged sites on the clay mineral layers and that between thepositively charged sites in the dye molecule is one of the mostimportant factors to determine the structure of the clay–dye
complex. We have termed this the “Size-Matching Rule”. Our
goal is finding out a new methodology to control molecularassembly structure and realizing functionalized photochemical
reaction systems such as an artificial light harvesting system.
1. Research on Artificial light harvesting system
Shinsuke TAKAGI, Tetsuya SHIMADA
The quantitative excited energy transfer reaction between
cationic porphyrins on an anionic clay surface was successfully
achieved. The efficiency reached up to ca. 100% owing to the“Size- Matching Rule” that is our original technique. It was
revealed that the important factors for the efficient energy
transfer reaction are (i) suppression of the self-quenching
between adjacent dyes, and (ii) suppression of the segregatedadsorption structure of two kinds of dyes on the clay surface.
These findings indicate that the clay/porphyrin complexes arepromising and prospective candidates to be used for constructionof an efficient artificial light-harvesting system. Especially when
phthalocyanine was used as energy acceptor, light harvesting
type energy transfer was realized.
In addition to these,hydrogen evlution systems using sunlight as an energy source
has been developed. Especially, photochemical hydrogen andhydroperoxide formation were examined as an energy related
subject this year.

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

3. Unique Enzyme Activity of Peroxidase on a Clay Nanosheet
Shinsuke TAKAGI, Tetsuya SHIMADA
The adsorption behavior and enzyme activity of horseradish
peroxidase (HRP) was examined on a synthetic clay nanosheet,
whose surface is flat at the atomic level and is negatively charged.
The results showed that HRP is adsorbed effectively (adsorption
equilibrium constant, K = 1.61 x107 L mol−1) and that thestructure of HRP was altered on the clay surface. The enzyme
activity of HRP on the clay surface was evaluated by using H2O2
and tert-BuOOH as a substrate. As a result, HRP on the clay
surface was able to work for tert-BuOOH, while HRP in solution
did not show any activity. In addition, HRP on SSA showed
reactivity even under the high-temperature conditions. These
results indicate that the clay nanosheet can be a unique modifier
for enzyme activity of HRP.

16

Reports from Research Groups
high surface area and ordered anioninc charges on the surfaces
when the layered materials are exfoliated. In this year, gold
nanoparticles (Au NPs) were deposited on SSA by depositionreduction (DR) using Au(en)2Cl3 as a precursor and by sol
immobilization (SI). The sizes of Au NPs prepared by DR and
SI were estimated to be 6.7 and 2.1 nm, respectively. Catalytic
activity of Au/SSA was evaluated by aerobic oxidation of 4hydroxybenzyl alcohol. The major product was 4hydroxybenzaldehyde. Au NPs on completely exfoliated SSA
showed higher catalytic activity than did Au on stacked SSA.
This was probably due to the aggregation of Au/SSA wasaccelerated during the reaction in the case of Au on stacked SSA
compared to Au on exfoliated SSA. These findings willcontribute to devlop new Au catalysts using nanosheet materials.
Hydroxyapatite (HAP) supported Au catalysts have been
known to show inverse strong metal-support interaction (SMSI)
in which Au NPs are covered by HAP under oxidative conditions,
reported by J. Wang et al. Au atoms at the perimeter interface
became cationic under inverse SMSI. Therefore, Au/HAPs seemto be a promising candidate as soft Lewis acid catalysts foralkene activation. Au/HAPs were prepared under oxidative andreductive conditions and were abbreviated as Au/HAP_O2 and
Au/HAP_H2, respectively. Although the mean diameters of Au
NPs were almost similar (ca. 2 nm), Au/HAP_O2 exhibited
higher catalytic activity for alkene isomerization reation than did
Au/HAP_H2. This result suggests that the electronic interaction
between Au and HAP thin layer of Au/HAP_O2 with SMSI
enhaces the soft Lewis acidity, resulting in high catalytic activity.

Fig. 3. Unique enzyme activity of peroxidase on a clay nanosheet.
（Langmuir 2020, 36, 29, 8384–8388）

4. Surface – Fixation Induced Emission on the nanosheets
Shinsuke TAKAGI, Tetsuya SHIMADA
We investigated the fluorescence enhancement behavior of
AIE (Aggregation Induced Emission) – active dyes on the clay
nanosheet. Judging from their adsorption observation on the clay
in water, the factor for the fluorescence enhancement is turned
out not to be AIE, but is to be Surface - Fixation Induced
Emission (S - FIE) mechanism. While the effect of AIE
depended on the molecular structure of dye in water-dioxane, S- FIE worked even for the dye that has bulky substituent. In
this year, not only fluorescence but also phosphorescence was
examined as a photochemical behavior. As a result, theenhancement of phosphorescence on clay surface was found put.

Fig. 4. Surface – Induced Emission on the nanosheets.
nanosheet, Right: with nanosheet..

■Papers with Peer Review
1. Adsorption Behavior of Mono-Cationic Pyridinium Salts on
the Clay Surface, T. Takigawa, Y. Yoshida, T. Fujimura, T.
Ishida, T. Shimada, S. Takagi, Bull. Chem. Soc. Jpn., 93,
1046-1049 (2020).
2. Unique Enzyme Activity of Peroxidase on the ClayNanosheet, T. Arai, M. Tabuchi, Y. Sato, T. Ishida, T.
Shimada, S. Takagi, Langmuir, 36, 8384–8388 (2020).
3. Thermodynamic Study of the Adsorption of Acridinium
Derivatives on the Clay Surface, Y. Yoshida, T. Shimada, T.
Ishida, S. Takagi, RSC Adv., 10, 21360-21368 (2020).
4. Anisotropic Energy Transfer in the Clay-Porphyrin Layered
System with Environment-Responsiveness, H. Nishina, S.
Hoshino, Y. Ohtani, T. Ishida, T. Shimada, S. Takagi, Phys.
Chem. Chem. Phys., 22, 14261-14267 (2020).
5. Two-Electron Oxidation of Water to Form Hydrogen
Peroxide Initiated by One-Electron Oxidation of Tin (IV)Porphyrins, Y. Ohsaki, A. Thomas, F. Kuttassery, S. Mathew,
S. Remello, T. Shimada, T. Ishida, S. Takagi, H. Tachibana,H. Inoue, J. Photoch. Photobio. A, 401, 112732-112740(2020).
6. Optically Transparent Colloidal Dispersion of TiO2
Nanoparticles Storable for Longer Than One Year Preparedby Sol / Gel Progressive Hydrolysis / Condensation, K. Sano,
F. Kuttassery, T. Shimada, T. Ishida, S. Takagi, B. Ohtani, A.
Yamakata, T. Honma, H. Tachibana, H. Inoue, ACS Appl.
Mater. Interfaces, 12, 44743–44753 (2020).
7. Adsorption Orientation Control of Di-Cationic Porphyrin on
Titania-Nanosheet, S. Tominaga, K. Sano, Y. Hirade, T.
Shimada, T. Ishida, S. Takagi, Tetrahedron Lett., 61,
152494-152497 (2020).
8. Elucidation of Active Sites of Gold Nanoparticles on Acidic
Ta2O5 Supports for CO Oxidation, M. Lin, C. Mochizuki, B.
An, Y. Inomata, T. Ishida, M. Haruta, T. Murayama, ACS
Catal., 10, 9328-9335(2020).
9. Oxidation of β-Nicotinamide Adenine Dinucleotide(NADH) by Au
Cluster and Nanoparticle Catalysts

Left: without

Fig. 5. Electron injection from Dye to semiconductor nanosheet.

5. Research on Gold Nanoparticle-Catalyzed Organic Reactions
Tamao, ISHIDA
Nanosheet materals, such as clay (Sumecton SA, SSA), areregarded as potential supports for metal nanoparticles because of17

Reports from Research Groups
Aiming for Coenzyme Regeneration in Enzymatic Glucose
Oxidation, J. Nishigaki, T. Ishida, T. Honma, M. Haruta,
ACS Sustainable Chem. Eng., 8, 10413-10422(2020).
10. Ligand Effect of Gold Colloid in the Preparation of
Au/Nb2O5 for CO Oxidation, M. Lin, C. Mochizuki, B. An,
T. Honma, M. Haruta, T. Ishida, T. Murayama, J. Catal., 389,
9-18(2020).
11. Features of Nb2O5 as a Metal Oxide Support of Pt and Pd
Catalysts for Selective Catalytic Oxidation of NH3 withHigh N2 Selectivity, M. Lin, B. An, T. Takei, T. Shishido, T.
Ishida, M. Haruta, T. Murayama, J. Catal., 389, 366374(2020).
12. Influence of the Support in Aqueous Phase Oxidation of
Ethanol on Gold/Metal Oxide Catalysts Studied by ATR-IR
Spectroscopy Under Working Conditions, A. Waheed, X.
Wang, N. Maeda, D. M. Meier, T. Ishida, T. Murayama, M.
Haruta, A. Baiker, Catal. Commun., 148, 106183(2021).

■Academic Meeting＊International
1. Adsorption behavior and photochemical properties oftetravalent porphyrins on clay and titania-nanosheet, Y.
Hirade, T. Shimada, T. Ishida, S. Takagi, The 4th Asian
Clay Conference (ACC-2020), Online (Thailand), June,2020.
2. Effects of clay surface on the aldehyde-diol equilibrium,
K. Arakawa, T. Shimada, T. Ishida, S. Takagi, The 4th
Asian Clay Conference (ACC-2020), Online (Thailand),
June, 2020.
＊Domestic
See the annual report in Japanese (20 articles)■Awards
1.

2.

3.

The Clay Science Society of Japan Promotion Fund Award,
The Clay Science Society of Japan, Kyosuke ARAKAWA(D1)Best Online Presentation Award, The 71st Divisional
Meeting of Division of Colloid and Surface Chemistry,
Kyosuke ARAKAWA (D1), September, 2020.
Excellent Poster Awards, The 10th CSJ Chemistry Festa,
Akihiro NAKAYAMA (M1), October, 2020.

18

Reports from Research Groups
Uchiyama Laboratory■Members

Katsumi UCHIYAMA, Sifeng MAO
We report a novel approach for selective fabrication of
conductive nanowires on a solid surface via diffusion mixing
reaction system formed by a chemical pen. The nanoscalemixing region was achieved by appropriately adjusting theviscosity of the solution and other parameters with the aid ofdyes functioned as a flow boundary indicator. Under the optimal
parameters, high aspect ratio silver nanowires (aspect ratio ≈1800) were obtained. Silver nanowire arrays with uniform width,
gradient width and complex patterns were successfully
fabricated. The theoretical value of the temperature coefficientof resistance (TCR) for silver was 0.0038 Ω/°C. A single silver
wire temperature sensor with 7-fold increase in temperature
coefficient resistance (0.0261 Ω/°C) was fabricated to show theadvantages of the chemical pen in the fabrication of nanosensors.

Katsumi UCHIYAMA
Professor / Dr. Pharmacol.
Analytical Chemistry, Nano/Micro Chemical Fabrication,
Micro Droplet
room: 9-339
TEL: +81-42-677-1111 Ext.4877
e-mail: uchiyama-katsumi@tmu.ac.jp
Hizuru NAKAJIMA
Associate Prof. / Dr.Eng.
Analytical Chemistry, Micro-TAS, Chromatography,
Electrophoresis, Chemical sensor, Bio sensor
room: 9-343
TEL: +81-42-677-1111 Ext.4882
e-mail: nakajima-hizuru @tmu.ac.jp
Shungo KATO
Associate Prof. / Dr.Eng.
Atmospheric Chemistry, Analytical Chemistry, Geochemistryroom: 9-338
TEL: +81-42-677-1111 Ext.4875
e-mail: shungo @tmu.ac.jp
Sifeng MAO
Assistant Prof. / Dr.Eng
Analytical Chemistry, Micro-TAS
room: 9-344
TEL: +81-42-677-1111 Ext.4883
e-mail: maosifeng @tmu.ac.jp
Hidetaka NORITOMIAssistant Prof. / Dr.Eng.
Enzyme Technology, Nanomaterial，Bioprocess
room: 9-148
TEL: +81-42-677-1111 Ext.4838
e-mail: noritomi @tmu.ac.jp

1-2 Nanowire sensor fabricated by chemical pen for
ultrasensitive protein detection
Katsumi UCHIYAMA, Sifeng MAO
In this study, a new strategy for label-free ultrasensitive
protein detection by nanowire sensor (NWs) was developed. The
nanowire was controllably fabricated by a hydrodynamic-flowconfinement pattern growth assembly system (HFCPGA). The
construction of NWs was achieved by a width of 100~700 nm
polycrystalline position-designate direction-aligned sliver
nanowire bridging across two independent indium tin oxide(ITO) electrodes. The limit of detection (LOD) for IgA and IgGmeasurement were 0.089 fg/mL and 0.93 fg/mL, respectively.
Quantitative detection of protein by NWs was available at a large
range of concentration (from 100 ag/mL to 100 μg/mL) and wassensitive especially to low concentration of protein. A feasible
principle for protein detection by NWs was proposed.

Sueo KAGAWA
Tech. Assistantroom: 9-290
TEL: +81-42-677-1111 Ext.4872
e-mail: kagawa @tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistantroom: 9-291
TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp
Doctor’s course -3
Master’s course -12
Bachelor 4 -8
Dissertion Ph.D. supporting by JSPS-1(Tsinghua University)■Outlines of the Research
1. Development of microchemical pen and its applications
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 had not been investigated.
For a nanowire to be used in a sensor, long nanowires would be
more competitive. The selective fabrication of highly ordered
nanowires with high aspect ratios was of low reproducibility,
which remained a challenge for laboratory research. In this study,
these issues were boldly challenged.
1-1 Selective fabrication of nanowires with high aspect ratios
for applications in temperature sensing

19

Reports from Research Groups
1-3 Development of Clean-phase Assisted Chemical Pen for
ultra-long metallic nanowire fabrication
Katsumi UCHIYAMA, Sifeng MAO
Although 3-poles MCP exhibited its competence in fabricationof long nanowire, the lifetime of MCP was its weakness in
preparing nanowire. An improved construction of MCP wasproposed, which was defined as clean phase-assisted four-poles
MCP. Various concentration of nitric acid served as clean phase
was investigated its ability for eliminate blocking particles toextend the lifetime of MCP. The clean phase-assisted four-poles
MCP has excellent stability and is suitable for longer nanowire
fabrication. Besides, a new templet-assisted assembly strategy of
MCP has been developed to increase the reproducibility ofnanowire fabrication by MCP.

3. Open microfluid control for single cell operation
Katsumi UCHIYAMA, Sifeng MAO
Accurate and precise information from single cells will
uncover the mechanisms of cell behaviors and cell heterogeneity.
Substantial methods for single cell analysis were by single-cellarray or by single-cell droplet which combined withfluorescence analysis, electrophoresis and/or mass spectrometry.
However, nearly none of the current methods can carry out
single-cell measurement in suspension, which not only destroys
extracellular context but also may perturb the intracellular
metabolites. Our purpose is to develop new tools for surgery on
single cell to understand transport of organelles and cellwound/repair mechanism. We believe this approach will be a
new avenue for single cell operations and subcellular operations.
4. Development of Micro Total Analysis System Using a
Compact Disk-type Microfluidic Device
Hizuru NAKAJIMA
We have developed a flow-based ELISA system using a
microfluidic device. However, many pumps and valves are
required for multiple immunoassays, which affect total size ofthe analytical system. In this study, we developed a solution
sending method based on the centrifugal force generated byrotating a compact disk-type microfluidic device. A portable
fluorescence detection system, electrochemical detection systemand surface plasmon resonance sensor using the compact disktype microfluidic device were developed. Since these systems do
not need pumps and valves, these systems would be useful foron-site analysis, such as environmental monitoring, food safety
testing and point-of-care testing.

2. Push-pull nozzle system for electrochemical detection of
lactate from single cell
Katsumi UCHIYAMA, Sifeng MAO
The immediate response of single cell described in this study
is a liquid-transfer-based approach for the real-timeelectrochemical detection. A cell was stimulated by glucose andsecreted lactate in microfluidic, Lactate was then decomposedby coupled enzyme reactions in nozzle system. The push-pull
nozzle system using a layer-by-layer enzyme assembly
technique showed a high sensitivity, specificity and spatialtemporal resolution due to large reaction area of accessible
enzymes and the high transduction capacity of the osmium
polymer that was used in the study. This work provides a novel
approach for detecting lactate response from a single cell by
noninvasive measurements and would permit individual
differences in cells to be explored in the diagnosis and treatmentof cancer as well as in many other situations.

5. Development of Portable ELISA System Using Pipette
Tips
Hizuru NAKAJIMA
Enzyme-linked immunosorbent assay (ELISA) is an
immunological assay commonly used to measure antibodies,
antigens, proteins and glycoproteins in biological samples.
However, the conventional ELISA method relatively needs 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.

20

Reports from Research Groups
Atmospheric carbon monoxide, ozone, various volatileorganic compounds, and hydrogen were continuously observedat remote sites: cape Hedo in Okinawa, Suzu in Ishikawa.

6. Development of Portable Genetic Testing System Based on
LAMP
Hizuru NAKAJIMA
A genetic amplification method using polymerase chain
reaction (PCR) is commonly used in the genetic test. However,the PCR method is not suitable for on-site genetic test since themethod needs large-sized and expensive assay devices such as athermal cycler, an electrophoresis equipment and an absorption/ fluorescence detector. To overcome these drawbacks, a portable
genetic testing system based on LAMP was developed using
LEDs, photodiodes a transparent glass heater and so on. The
genetic testing system was successfully used in the variety
identification of rice.

10. Measurements of atmospheric pollutants at mountainsites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide were observed at
the foot of Mt. Fuji (Tarobo observation site). Clear diurnal cycle
caused by air motion were observed.
11. Atmospheric trace gas measurements using small gas
sensorShungo KATO
Realtime measurement of gas at the top of Mt. Fuji during
winter without commercial electric power was donducted withlow power gase sensor and LPWA ELTRES (SONY). Also,
measuremnent of volcanic gases using a portable system wasconducted at Owakudani, Hakone volcano.
12. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen concentration in suburban, urban, and remote sites
were observed.

7.

Development of Multichannel ISFET Sensor for
Measuring pH Distribution of Interstitial Water inMarine Sediment
Hizuru NAKAJIMA
Recentry, marine acidification is progressing with increasing
the concentration of CO2 in atmosphere. Since the marine
acidification causes the dissolution of sandy soil in coral reefarea, the effect of ocean acidification on marine organisms livingin there is apprehended. Therefore, the measurement of pH
distribution of interstitial water in marine sediment is importanttask for evaluating the effect of marine acidification on
ecosystem. In general, the pH value of interstitial water in marine
sediment is measured by diver using the pH meter with glass
electrode. However, the measurement work is very hard, theglass electrode is fragile, and the pH distribution of interstitialwater could not be measured at same time. To overcome thesedrawbacks, a novel multichannel ISFET sensor using Ta2O5 as
an ion sensitive membrane was developed for measureing the pH
distribution of interstitial water in marine sediment.

13. Application of biochar to stress tolerance of enzymes
Hidetaka NORITOMI
To reduce greenhouse gas emissions, biochar was preparedfrom forestry residues, which are carbon neutral, and was used
as a enzyme carrier. We found that biochar imparts high heatstress tolerance and organic solvent stress tolerance toenzymes. This result would be expected to the applications tobioprocesses such as bioreactors, biosensors, and biofuel cells.
8. 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.

■Papers with Peer Review
1. K. Morioka, H. Sato, K. Morita, A. Hemmi, H. Nakajima,
A. Shoji, A. Yanagida
Development of an on-chip sample injection system with a 6port valve incorporated in a microchip
Royal Society of Chemistry (RSC), Vol.10, No.59, pp.3584835855
2. J. Li, T. Fujii, K. Matsuoka, M. Takemura, J. Zhou, Y.
Sakamoto, N. Kohno, M. Nakagawa, K. Murano, Y. Sadanaga,

9. Atmospheric trace species measurements at remote sites
Shungo KATO

21

Reports from Research Groups
18-27 (2020).
3. Hidetaka Noritomi
Study on efficient protein refolding using surfactants at highfinal protein concentration, Emerging Trends in Engineering
Research and Technology Vol. 9, Ed by Suraya Hani Bt Adnan,Book Publisher International, London, United Kingdom,
Chapter 4, 28-36 (2020).
4. Hidetaka Noritomi
Experimental study on preparation of highly concentrated silver
nanoparticles in reverse micelles of sucrose fatty acid esters
through solid-liquid extraction method, Emerging Trends inEngineering Research and Technology Vol. 9, Ed by Suraya Hani
Bt Adnan, Book Publisher International, London, United
Kingdom, Chapter 5, 37-45 (2020).
5. Hidetaka Noritomi
Effect of solvent on catalysis of protease adsorbed on biochar inorganic media, New Advances in Materials Science andEngineering Vol.2, Ed by Yong X. Gan, Book Publisher
International, London, United Kingdom, Chapter 10, 124-132(2020).
6. Hidetaka Noritomi
Thermal stabilization of HEWL by adsorption on biochar, New
Advances in Materials Science and Engineering Vol.2, Ed by
Yong X. Gan, Book Publisher International, London, United
Kingdom, Chapter 11, 133-141 (2020).
■Awards

Y. Nakashima, K. Sato, A. Takami, A. Yoshino, T. Nakayama, S.
Kato, Y. Kajii
Total hydroxyl radical reactivity measurements in a suburban
area during AQUAS-Tsukuba campaign in summer 2017
Science of the Total Environment, 740 139897, 2020.
3. H. Noritomi, S. Kurihara, N. Endo, S. Kato, K. Uchiyama
Enhancement of lytic activity of HEWL adsorbed on biochar by
the optimization of adsorption conditions
International Journal of Chemistry, Vol.12, No.2, pp.45-53
4. Y. Noritomi, T. Kuboki, H. Noritomi
Estimation of immobilized horseradish peroxidase in a low salt
concentration for an irreversible electrochemical system, Resultsin Chemistry, Vol.2, pp.1-7
5. Z. Wu, S. Mao, Y. Zheng, L. Lin, S. Mao, Z. Li, J. M. Lin,
Controllable Synthesis of Multicompartmental Particles Using
3D Microfluidics, Angewandte Chemie-International Edition,
2020, 59, 2225-2229.
6. N. Xu, H. Li, S. Lin, W. Zhang, S. Han, H. Nakjima, S. Mao,J. M. Lin, A fluidic isolation-assisted homogeneous-flowpressure chip-solid phase extraction-mass spectrometry systemfor online dynamic monitoring of 25-hydroxyvitamin d3
biotransformation in cells, Analytial Chemistry, 2021, 93, 22732280.
7. Q. Zhang, S. Mao, W. W. Li, Q. S. Huang, S. Feng, Z. Y. Hong,J. M. Lin, Microfluidic adhesion analysis of single glioma cells
for evaluating the effect of drugs, Science China-Chemistry,
2020, 63, 862-870.
8. Q. S. Huang, S. F. Mao, M. Khan, W. W. Li, Q. Zhang, J. M.
Lin, Single-cell identification by microfluidic-based in situ
extracting and online mass spectrometric analysis ofphospholipids expression. Chemcial Science, 2020, 11, 253-256.
9. J. X. Dou, S. Mao, H. F. Li, J. M. Lin, Combination stiffness
gradient with chemical stimulation directs glioma cell migration
on a microfluidic chip, Analytical Chemistry, 2020, 92, 892-898.
10. T. Z. Xie, N. Li, S. Mao, Q. Zhang, J. M. Lin, Cell
heterogeneity revealed by on-chip angiogenic endothelial cell
migration, Acs Omega, 2020, 5, 3857-3862.

■Invited Lectures■Academic Meeting＊International＊Domestic
Sifeng Mao, Haifeng Lin, Nahoka Kasai, Shungo Kato, Hizuru
Nakajima, Local Fabrication of Nanowires with High AspectRatios using a Diffusion Mixing Reaction System for
Temperature Sensing, The 68th JSAP Spring Meeting 2021,
2021/3/16-19.

■Books
1. Hidetaka Noritomi
Experiments on the formation and solubilization property ofwater-in-oil microemulsions of alkyl glucosides, Emerging
Trends in Engineering Research and Technology Vol. 9, Ed by
Suraya Hani Bt Adnan, Book Publisher International, London,
United Kingdom, Chapter 2, 10-17 (2020).
2. Hidetaka Noritomi
Experimental study on adsorption of α-chymotrypsin on plantbiomass charcoal, Emerging Trends in Engineering Research
and Technology Vol. 9, Ed by Suraya Hani Bt Adnan, Book
Publisher International, London, United Kingdom, Chapter 3,

22

Reports from Research Groups
Shishido Laboratory■Members

give corresponding organoboron compounds in good yields.
Kinetic reaction mechanism analysis corroborated that theformation of carbocations on Au nanoparticles is the key for theefficient sp3 C–O bond borylation.

Tetsuya Shishido
Professor /Dr. Eng.
Catalyst Science, Surface chemistry, Solid acid-base, Selective
oxidation, in-situ observation
room:9-551 TEL: +81-42-677-2852 (Ext. 4961)
e-mail: shishido-tetsuya@tmu.ac.jp
Hiroki Miura
Assistant Professor /Dr. Eng.
Catalysis Science, Solid acid-base, Organic
Organometallic chemistryroom:9-550 TEL: +81-42-677-2851 (Ext. 4962)
e-mail: miura-hiroki@tmu.ac.jp

chemistry,
3. Dehydration of glycerol to acrorein by metal oxide catalysts

PD -2
Doctor’s course -2
Master’s course -12
Bachelor 4 -7

Acrolein is an important synthetic intermediate used in thesynthesis of various chemical products such as pharmaceuticals.
Since glycerol is oversupplied during biodiesel production, thedevelopment of efficient catalytic system for selective
conversion of glycerol to acrolein by a dehydration is required.
In this study, we found that a WO3/Al2O3 catalyst showed higher
activity and durability toward glycerol dehydration. Furthermore,
WO3/Al2O3 catalysts were effective for dehydration of various
polyols to affored unsaturated organic molecules.

■Outlines of the Research
1. Selective oxidation of glycerol by supported Pt-Bi catalysts
Convertsion of biomass-derived materials into value-added
compounds is of significant importance from a carbon-neutral
point of view. In order to selectively convert glycerol produced
as a by-product during biodiesel production to dihydroxyacetone,
highly selective idenfication and oxidation of the secondary
alcoholic moiety. In this study, the investigation of the effect ofaddition of Bi to the supported Pt catalyst on the selective
oxidation of dihydroxyacetone from glycerol revealed that theaddition of Bi enhanced the selectivity for the oxidation of
secondary alcohols. Theoretical calculations also revealed thatthe coordination of primary alcohols to Bi enabled selective
oxidation of secondary alcohols, and that Bi promotes theisomerization of glyceraldehyde to hydroxyacetone.

■Papers with Peer Review
1.

2.

3.
2. Efficient borylation of sp3 C–O bonds by supported Au
catalysts
Borylation of sp3 C–O bonds by transition metal catalysts is a
useful technique for synthesizing organoboron compounds,
which
are
ubiquitoussynthetic
intermediatesforpharmaceuticals and agrochemicals. Although the application ofvarious homogeneous catalystic systems has been reported so far,the application of a heterogeneous catalyst with highenvironmentally-friendly nature has not been appeared so far. In
this study, we developed efficient supported gold catalysts forthe borylization of sp3 C–O bonds of a series of allyl esters. The
supported Au catalysts showed high activity not only for allyl
esters but also for benzyl esters and propargyl esters, and the to

4.

5.

6.

23

“Concerted Catalysis of Pd and Au on Alloy Nanoparticles
for Efficient Heterogeneous Molecular Transformations”
Miura, H.; Shishido, T. Chem. Lett. 2021, 50, 346–352.
(Highlight Review)“Practical Synthesis of Allyl, Allenyl and Benzyl
Boronates through SN1’-Type Borylation under
Heterogeneous Gold Catalysis” Miura, H.; Hachiya, Y.;
Nishio, Y. Fukuta, T. Toyomasu, H.; Kobayashi, K.;
Masaki, Y.; Shishido, T. ACS Catal. 2021, 11, 758–766.
“Diels-Alder Conversion of Acrylic Acid and 2,5Dimethylfuran to para-Xylene Over Heterogeneous
Bi-BTC Metal-Organic Framework Catalysts Under
Mild Conditions”, Yeh, J. Y.; Chen, S. S.; Li, S.-C.;
Chen, C. H.; Shishido, T.; Tsang, D. C. W.; Yamauchi,
Y.; Li, Y.-P.; Wu, Kevin C.-W. Angew. Chem. Int. Ed.,
2021,60, 624-629. 【Featured as a Supplementary
Cover】“Selective Dehydration of Glycerol to Acrolein overAl2O3-supported WO3 catalysts” Aihara, T.; Asazuma, K.;
Miura, H.; Shishido, T. RSC Adv. 2020, 10, 37538–37544.
“Behavior of active species on Pt-Sn/SiO2 catalyst
during the dehydrogenation of propane andregeneration”, Lidan, D.; Zhou, Z.; Shishido, T., Appl.
Catal. A: General, 2020, 606, 117826.
“Features of Nb2O5 as a Metal Oxide Support of Pt
and Pd Catalysts for Selective Catalytic Oxidation ofReports from Research Groups

7.

8.

9.

10.

11.

12.

13.

NH3 with High N2 Selectivity”, Lin, M.; An, B.; Takei,T.; Shishido, T.; Ishida, T.; Haruta, M., Murayama,T., J. Catal., 2020, 389, 366-374.
“Experimental and theoretical investigation of the role ofbismuth in promoting the selective oxidation of glycerol
over supported Pt-Bi catalyst under mild conditions” Feng,
S.; Yi, J.; Miura, H.; Nakatani, N.; Hada, M.; Shishido, T.
ACS Catal. 2020, 10, 6071–6083.
“Silylation of Aryl Chlorides by Bimetallic Catalysis of
Palladium and Gold on Alloy Nanoparticles” Miura, H.;
Masaki, Y.; Fukuta, Y.; Shishido, T. Adv. Synth. Catal.
2020, 362, 2642–2650 【 Selected as a Very Important
Publication】“Brønsted Acid Property of Alumina-Based Mixed Oxides
Supported Tungsten Oxide” Saito, M.; Aihara, T.; Miura,
H.; Shishido, T. Catal. Today 2020, in press.
“Importance of the Pd and Surrounding Sites inHydrosilylation of Internal Alkynes by Palladium-Gold
Alloy Catalyst” Sadhukhan, T.; Junkaew, A.; Zhao, P.;
Miura, H.; Shishido, T.; Ehara, M. Organometallics 2020,
39, 528–537.【Featured as a Supplementary Cover】“Investigation of the mechanism of the selectivehydrogenolysis of C-O bonds over a Pt/WO3/Al2O3
catalyst” Aihara, T.; Miura, H.; Shishido, T. Catal. Today
2020, 352, 73–79.
“One-pot synthesis of lactic acid from glycerol over Pt/LNb2O5 catalyst under base-free conditions” Shixiang, F.;
Takahashi, K.; Miura, H.; Shishido, T. Fuel Process.
Technol. 2020, 197, 106202“Reductive Cycloisomerization of Diynes by Supported
Palladium Catalysts and Subsequent [4+2] Cycloaddition
Leading to Cyclohexene Derivatives” Miura, H.; Tanaka,Y.; Nakahara, K.; Shishido, T. ChemCatChem 2020, 12,455–458.

8.

9.

■Academic Meeting＊Domestic
See the annual report in Japanese (20 articles)■Awards1.

2.

3.

■Invited Lectures
1.

2.

3.

4.

5.

6.

7.

“Supported palladium-gold alloy catalysts for highly
efficient hydrogen storage system” T. Shishido, The 1st
International Conference (Virtual) of Sustainable Energy
and Catalysis 2021 (ICSEC, 2021) (zoom) Feb 16-17,
2021. (Keynote Lecture)“Design of alloy nanoparticle catalysts for highly efficienthydrogen storage and evolution” Tetsuya Shishido, The
101st CSJ Annual Meeting March 19-22, 2021, Online“Organic Transformations by Concerted Catalysis of Pd
and Au on Alloy Nanoparticles” Hiroki Miura，126th
CatSJ Meeting (16-18 September 2020, online).
“Supported palladium-gold alloy catalysts for highly
efficient hydrogen storage system“ T. Shishido, 2nd JapanChina Forum on Power Batteries for New Energy Vehicles(zoom) Oct 28, 2020. (Invited Lecture)“Organic Transformations by Concerted Catalysis of Pd
and Au on Alloy Nanoparticles” Hiroki Miura，2020 年
度触媒学会・触媒工業協会 Exchange salon of CatSJ andCMAJ 2020 (11, December, 2020, online)“Identification, quantitative analysis, and design of active
sites on solid acid catalysts for selective conversion ofpolyols”T. Shishido, T. Aihara, H. Miura, The 7th seminarseries in Bioenergy and Catalysis (zoom, Thammasat
University), Dec 8, 2020. (Invited Lecture).
“Efficient heterogeneous molecular transformation by
concerted catalysis of Au nanoparticles and other elements”
Hiroki Miura ， Academic sympojium in a researchlaboratory in Institute of Innovative Research “Structureand function of organic complexes and inorganic materials”(16, December, 2020, online)“Acid sites formed on monolayer oxides” Tetsuya
Shishido, Seminar for design and function of solid acids
and bases (20, December, 2020, online)“Selective conversion by supported alloy catalysts”
Tetsuya Shishido, Symposium of research group for highly
selective oxidation, (22, january, 2021, online)

24

Poster Award "Effect of surface hydrophobic
modification of sulfo-functionalized siloxane gels on theiracid catalysis " Gen Kato 126th CatSJ Meeting (16-18
September 2020, online).
Poster Award "Conversion of glyceric acid to alanine overRu/TiO2 catalysts" Siro Saito 126th CatSJ Meeting (16-18
September, 2020, online).
ICAT Young Lectureship Azuma Award “Organic
Transformations by Concerted Catalysis of Pd and Au on
Alloy Nanoparticles” Hiroki Miura, January 6th 2021,

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 -3

■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.
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.

■Book Chapter
See the annual report in Japanese■Invitted speech
See the annual report in Japanese■Academic Meeting＊Domestic
See the annual report in Japanese■Awards
See the annual report in Japanese25Applied Chemistry Colloquium

392th

2020/12/18
Masaaki Haneda (Nagoya Institute of Technology)”Enhancement of catalytic functions for automotive exhaust gas purification
by hybridization of precious metals”

26Annual Report 2020
Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry for Environmental Sciences
April 1, 2021

27