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

Annual Report 2021

IndexReports from Research Groups
Kawakami Laboratory

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1

Asayama Laboratory

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7

Kubo Laboratory

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9

Setaka Laboratory

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12

Kanamura Laboratory

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14

Kajihara Laboratory

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16

Takagi Laboratory

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18

Analytical Chemistry Laboratory

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21

Shishido Laboratory

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25

Shudo Laboratory

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27

Colloquium

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28

Reports from Research Groups
Kawakami Laboratory■Members
Hiroyoshi KAWAKAMI
Professor / Dr. Eng.
Polymer Chemistry, Functional Polymers, Nanofiber
Engineering, Biomaterials, Epigenetics Engineering, Cell
Engineering
Rm. 9-638, +81-42-677-1111 Ext. 4972
kawakami-hiroyoshi@tmu.ac.jp
Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-ScienceRm. 9-137, +81-42-677-1111 Ext. 4837
yamato-masafumi@tmu.ac.jp

Figure 1. Schematic drawing of nanoparticle/PIM-1 composite
membrane.
2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA, Toyotaka NAKAE

Kiyoshi SATO
Associate Professor / Dr. Eng.
Synthetic Organic Chemistry, Molecular Recognition,
Heterocyclic Chemistry, Physical Organic ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
sato-kiyoshi@tmu.ac.jp

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 synthesized sulfonated polymers veeringhigh ion exchange capacities. The novel polymer composite
membranes containing proton conductive acid-base blend
polymer nanofibers showed improved 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 and metal-air secondary
batteries using anion exchange membranes were also carried out.

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
Toyotaka NAKAE
Research Assistant Professor / Dr. Sci.
Organometalic Chemistry, Coordination Chemistry, Inorganic
ChemistryRm. 9-349, +81-42-677-1111 Ext. 4886
nakae-toyotaka@tmu.ac.jp
Doctor’s course - 2
Master’s course - 16
Bachelor 4 - 10
Researcher - 1

Figure 2. Novel proton conductive blend nanofiber composite
membrane.

■Outlines of the Research
1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO

3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA

Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO2). Recently, we
have reported that novel composite membranes composed of thefluorinated polyimide or polymers of intrinsic microporosity(PIM) and surface-modified silica nanoparticles exhibit high gas
permeability and selectivity.
In this year, we evaluated the gas permeation characteristics
of PIM-1 and silica particle / PIM-1 composite membranes at theexhaust gas temperature of thermal power plants. It was clarified
that the gas permeability coefficient of PIM-1 significantly
decreased above 80 ° C. On the other hand, the silica particle /PIM-1 composite membrane also showed a tendency to decrease
the gas permeability coefficient at high temperature due to thetemperature characteristics of PIM-1, but the gas permeability
coefficient was significantly improved by the addition ofparticles.

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 good secondary battery performances at low
temperatures by modifying the interfaces between the electrolyte
and electrodes.

1Reports from Research Groups

Figure 3. Schematic illustration of the lithium ion battery using
the lithium ion conductive polymer nanofiber composite
membrane.
4. Design of Multi-electron Redox Catalysts
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Toyotaka NAKAE

Figure 5. Epigenetic gene expression control by chromatin
conformations.

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 tandem catalyst-modified
electrodes
fabricatedbydrop-castdepositionof
metalloporphyrins bearing phenolic OH substituents spatiallyarranged around the metal center onto copper nanocrystals. The
tandem catalyst-modified electrodes improve the C2/C1 productselectivity due to persistent elevation of the local COconcentration on Cu surface for promoting C-C coupling.
Further improvement of the catalytic activity and the productselectivity is under investigation

HO

6. Suppression of Cellular Senescence
Hiroyoshi KAWAKAMI, Kiyoshi SATO,
While cellular senescence acts as a tumor suppressor, theaccumulation of senescent cells causes diabetes and Alzheimer's
disease, and also develop a senescence-associated secretory
phenotype (SASP) that can adversely affect the behavior ofneighboring cells. Cellular senescence is also a major factor in
the deterioration of cell quality during in vitro cell expansion ofmultifunctional cells for regenerative medicine and cell therapy.
Therefore, suppression of cellular senescence of stem cells andimmune cells is one of the most important issues for regenerative
medicine and cell therapy.
In this year, we investigated the suppression of replicative
senescence of mesenchymal stem cells and NK cells by
mitophagy-induced liposome nanocarriers (M-NC). The
administration of M-NC was found to restore the cellproliferation ability and cell function by removing dysfunctional
mitochondria from senescent cells via mitophagy reactivation.
Moreover, M-NC can act not only suppress cellular senescencebut also rejuvenate long-term cultured cells from the senescencestate. Thus, M-NC will provide new strategies for the ex vivo cell
expansion of the cell source for regenerative medicine and celltherapy.

OH
HO

OH

N

N

M
N

N

HO

OH
HO

OH

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

Liposome

Mn Porphyrin (MnP)

DOTMA + DOPE (1:1)

5. Epigenetics Engineering for Cancer Therapy
Hiroyoshi KAWAKAMI, Kiyoshi SATON

p53 inhibitor(pifithrin-a)

N

Mn
N

N

N

N

O
H 3C

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 a novel therapeutic treatment of cancer. The
EpC carriers that transport three types of epigenetic agentssimultaneously into a target cell successfully mediate theapoptosis induction, cellular senescence induction, andepithelial-to-mesenchymal transition (EMT) suppression in
HCT116 human colorectal carcinoma cells by the combined
effect of the carrier-encapsulated epigenetic drugs.

CH3

N

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

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

NH

CH3

S

Figure 6. Mitophagy-induced liposomal nanocarrier.
7. Processing of feeble magnetic materials under a magnetic
field
Masafumi YAMATO
Controls of higher-order structure of feeble magnetic
materials by using a magnetic field have been studied in order toimprove some properties and to reveal new functions of thematerials.
In this year, we discovered a lyotropic liquid crystal consistingof nanosheets and ionic liquids. The formation of the liquid2

Reports from Research Groups
crystal significantly improved the magnetic field response. We
also succeeded in immobilizing the liquid crystal structure by insitu polymerization after adding the monomer.

9.

10.

11.

Figure 7. Photo images of (a) the transparent layer and (b) the
turbid layer of ionic liquid dispersion of montmorillonite undercross-Nicol condition.
■Papers with Peer Review
1.
Takahiro Ogura, Kazuto Suzuki, Manabu Tanaka,
Hiroyoshi Kawakami, “Fabrication and Characterizationsof Polymer Electrolyte Composite Membranes Consistedof Polymer Nanofiber Framework Bearing ConnectedProton Conductive Pathways”, Journal of Photopolymer
Science and Technology, 34, 5, 463-468 (2021).
2.
Takeru Wakiya, Manabu Tanaka, Hiroyoshi Kawakami,“Fabrication and Electrolyte Characterizations of
Nanofiber Framework-Based Polymer Composite
Membranes with Continuous Proton Conductive
Pathways”, Membranes, 11, 90 (2021).
3.
Shun Nakazawa, Yu Matsuda, Mitsuki Ochiai, Yuta
Inafune, Masafumi Yamato, Manabu Tanaka, Hiroyoshi
Kawakami, “Enhancing Lithium Ion Conductivity and AllSolid-State Secondary Battery Performance in Polymer
Composite Electrolyte Membranes with -Crystalline-richPoly(vinylidene fluoride) Nanofibers”, Electrochimica
Acta, 394, 139114 (2021).
4.
Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, Solvated Ionic-Liquid Incorporated Soft
Flexible Cross-Linked Network Polymer Electrolytes for
Safer Lithium Ion Secondary Batteries, Macromolecular
Chemistry and Physics, in press (2022).
5.
Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami“Effect of Phase Separation due to Solvent Evaporation on
Particle Aggregation in the Skin Layer of the Gas
Separation Membrane”, Journal of Photopolymer Scienceand Technology, 34, 449-456 (2021).
6.
Takeru Yamazaki, Kohe Arima, Riku Kubota, Kiyoshi
Sato, Hiroyoshi Kawakami, "Preparation of Mitochondriaand Epigenetics-Targeting Nanoparticles for Suppressionof Cancer Metastasis", Part. Part. Syst. Charact., 38 (8),2100003 (2021).
7.
Takahiro Miyazaki, Kazuma Komine, Takashi Nakaoji,
Kohki Takahashi and Masafumi Yamato, Magnetic
birefringence of montmorillonite dispersion, The Japanese
Journal of Applied Physics, Accepted January 2022.
8.
Urano Chisato, Masatoshi Onuki, Yuuta Uchida, Risa
Suzuki, Kiyoshi Sato, Dai Masui, Motowo Yamaguchi,
Takamichi Yamagishi, “Asymmetric allylic substitution bychiral palladium catalysts: Which is more reactive, major
pi-allyl Pd(II) species or minor pi-allyl species?”,
Molecular Catalysis, 499, 111221 (2021).

Bofan Zhang, Mutian Zhang, Liang Zhang, Paul A.
Bingham,ManabuTanaka,
Wen
Li,
Shiro
Kubuki, ”BiOBr/MoS2 catalyst as heterogenous
peroxymonosulfate activator toward organic pollutant
removal: Energy band alignment and mechanism insight”,
Journal of Colloid and Interface Science, 594, 635-649(2021)
Shogo Mamada, Tatsuya Ohta, Masafumi Yamato, “Theelasticity and the piezoelectricity of thick composites ofsilicone rubber matrix and aligned piezoelectric ceramicparticles”, Plastics Rubber and Composites, 50, 455-463(2021).
Kazushi Enomoto, Kotaro Takeda, Naoto Iwata, Kiyohiro
Adachi, Tomoka Kikitsu, Yasuhiro Ishida, Daisuke
Hashizume, Manabu Tanaka, Hiroyoshi Kawakami, YongJin Pu, “Colloidal CdS Quantum Dot Fibers Prepared byElectrospinning of Their Wet Gel for Quantum
Nanowires”, ACS Applied Nano Materials, accepted■Books
1. Kazuma Komine, Masafumi Yamana, “NMR Analysis oforganic adsorption on clay”, Technical Information Institute,
September 2021.
2. Manabu Tanaka, Hiroyoshi Kawakami, "Development of
Polymer Nanofiber-based Electrolyte Membranes for
PEFCs", Electrochemistry, in press (2021)
3. Masafumi Yamato，Hiroyoshi Kawakami, ” Development ofpolymeric gas separation membrane complexed withsurface-modified nanoparticles “, The latest technology forCO2 separation, recovery, and storage, NTS(Tokyo, Japan),in press. (in Japanese)■Invited Lectures
1. Hiroyoshi Kawakami, Development of electrolyte
membranes for fuel cells required after 2030, Special lecture
at Iwate University (Morioka), October 2021, (in Japanese).
2. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2021 Basic seminar of polymer science for young
engineers, Nov. 2021, Online (in Japanese).
3. Hiroyoshi Kawakami, Scientific (chemical) approachagainst COVID-19 in the present and future, Special lecturein Miyako festival at Tokyo Metropolitan University,
November 2021, Online (in Japanese).
4. Hiroyoshi Kawakami, Cell rejuvenation by nanocarrier,Cosme Tech 2022 Tokyo (Tokyo), January 2022 (inJapanese).
5. Hiroyoshi Kawakami, Development of ultra-high CO2
permeable separation membrane required for CCS and CCU,SPSJ, January 2022, Online (in Japanese).
6. Hiroyoshi Kawakami, Fuel cell technology development
roadmap, 7th FC-Cubic symposium, March 2022, Online (inJapanese).
7. Hiroyoshi Kawakami, Development of innovative ultra-high
CO2 permeable separation membrane required by CCUS,
SPSJ, March 2022, Online (in Japanese).
8. Hiroyoshi Kawakami, Development of ultra-high CO2
permeable separation membrane required by CCUS, The
Membrane Society of Japan,, March 2022, Online (inJapanese).
■Academic Meeting
1. Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami,

3

Reports from Research Groups
Preparation of asymmetric membranes containing surfacemodified silica nanoparticles and the gas permeation
properties, 70th SPSI Annual Meeting (Online Virtual
Meeting), 1Pa045, May 2021.
2. Nakaoji Takashi, Masafumi Yamato, and Kawakami
Hiroyoshi, Application of fluorinated hectorite / hectorite
lyotropic liquid crystals to nanocomposite hydrogels, 70th
SPSJ Annual meating, Online, 2F23, May 2021 (inJapanese)
3. Kazuto Suzuki, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and characterizations of acid / base blend
polymer nanofiber composite membranes for hightemperature and low humidity fuel cell operation, The 70th
SPSJ Annual Meeting (Online), 3Pe063 May 2021 (inJapanese)
4. Yuri Nara, Manabu Tanaka, Hiroyoshi Kawawaki,
Fabrication and evaluation of anion conductive polymer
electrolyte membranes for water electrolysis., The 70th
SPSJ Annual Meeting, 3Pb066, May 2021 (in Japanese)
5. Kazuto Suzuki, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and evaluation of polymer blend nanofiber
composite membranes for wide temperature and low
humidity fuel cell operation, The 28th Fuel Cell
Symposium (Online), No.17 May 2021 (in Japanese)
6. Kiyioshi Sato, Keisuke Ashiba, Hiroyoshi Kawakami,
Mitophagy Reactivation and Rejuvenation of Senescent
Stem Cells by Liposome Nano Carriers, Joint Meeting of
the 74th Annual Meeting of Society for Free Radical
Research JAPAN and the 21st Nitric Oxide Society ofJAPAN, (Sendai International Center, Live-Web) 10043(May, 2021). (in Japanease).
7. Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Evaluation of their lithium-ion conductivity of high saltconcentrated solid polymer electrolyte membranes with
nanofiber frameworks, 43th The Membrane Society ofJapan, June 2021 (Online) (in Japanease)
8. Takumu Morita, Masafumi Yamato, Hiroyoshi Kawakami,
Fabrication and gas permeation property of PIM-1/PIMCTC blend membrane to improve gas., 43st annual
meeting of membrane science of Japan, June 2021, E-307,(Online). (in Japanease)
9. Nana Terasoba, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and evaluation of lithium salt-containing
polycarbonate-based composite electrolyte membranecomposed of nanofibers with polarized crystals, 43st
annual meeting of membrane science of Japan, June 2021
(Online). (in Japanease)
10. Kazuto Suzuki, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and characterization of acid-doped blend
nanofiber composite membranes for high temperature andlow humidity fuel cell operation, The Annual Meeting of
the Society of Fiber Science and Technology (Online),
1PB208 June 2021 (in Japanese)
11. Yuri Nara, Manabu Tanaka, Hiroyoshi Kawakami.
Synthesis and Electrolyte Evaluation of Anion Conductive
Polymers Bearing No Heteroatoms in the Polymer Main
Chains., The Annual Meeting of the society of fiber scienceand technology Japan, 1PA209, June 2021 (in Japanese)
12. Yuri Nara, Tanaka Manabu, Hiroyoshi Kawakami.
Fabrication and Electrolyte Evaluation of Novel Anion
Exchange Membranes for Water Electrolysis., The Annual

13.

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15.

16.

17.

18.

19.

20.

21.

22.

23.

4

Meeting of the society of fiber science and technology
Japan, 2C13 June 2021 (in Japanese)
Takahiro Ogura, Kazuto Suzuki, Manabu Tanaka,
Hiroyoshi Kawakami, Fabrication and Characterizations ofPolymer Electrolyte Composite Membranes Consisted ofPolymer Nanofiber Framework Bearing Connected Proton
Conductive Pathways, ICPST-38 (Online), B1-11 June
2021 (in Japanese)
Koki Mino, Takeru Yamazaki, Keisuke Ashiba, Kiyoshi
Sato,
Hiroyoshi
Kawakami,
Mitophagy-inducing
nanocarrier for functional recovery of senescentmesenchymal stem cells, The 37th Annual Meeting of theJapanese Society of Drug Delivery System (Makuhari
Messe), 2-B-07, (June 2021)
Shiori Higashi, Masafumi Yamato, Hiroyoshi Kawakami,
Effect of Phase Separation due to Solvent Evaporation on
Particle Aggregation in the Skin Layer of the Gas
Separation Membrane, The 38th International Conferenceof Photopolymer Science and Technology, (Online Virtual
Meeting), B1-8, June 2021.
Keisuke Ashiba, Takeru Yamazaki, Kiyoshi Sato,
Hiroyoshi Kawakami, Suppression senescence inmesenchymal stem cells by mitophagy-inducing liposome
nanocarrier. 50th Medical macromolecular symposium(On-line), 7 (July, 2021)
Yokota Nohara, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Characterizations of Solid Polymer
Electrolyte in High-Salt Concentration Region for AllSolid-State Batteries, 4th G'L'owing Polymer Symposiumin KANTO, July 2021 (Online).
Yuri Nara, Manabu Tanaka, Hiroyoshi Kawakami,
Synthesis and Evaluation of Anion Conductive Polymers
for Water Electrolysis Application., 4th G'L'owing
Polymer Symposium in KANTO (GPS-K 2021), (Online),
A20, July 2021.
Manabu Tanaka, Yuu Matsuda, Hiroyoshi Kawakami,
Fabrication and Characterization of Lithium-Air Battery
Consisted of Nanofiber Composite Electrolyte Membranewith Suppressed Water Vapor Permeability, 70th Polymer
Symposium in Japan, September 2021 (Online) (inJapanease)
Nohara Yokota, Manabu Tanaka, Hiroyoshi Kawakami,
Lithium-ion conductive characteristics of polarizable
polymer nanofiber-based composite solid polymer
electrolytes bearing high salt concentrations, 70th Polymer
Symposium in Japan, September 2021 (Online) (inJapanease)
Takumi Kobayashi, Kiyoshi Sato, Hiroyoshi Kawakami,
Analysis of Electrochemical CO2 Reduction Products ofMetal Porphyrin-Modified Electrodes by Rotating RingDisk Electrode Method, Electrochemistry Autumn
Meeting 2021 (Online Conference), 1A15 (September2021).
Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Development of Lyotropic Liquid Crystal
comprising Ionic Liquid and Clay Nanosheet., the 82th
JSAP autumn Meeting, (Online Virtual Meeting), 12aN324-9, September 2021.
Shuntarou Kimura, Risa Mitsuhashi, Kiyoshi Sato,
Hiroyoshi Kawakami, Epigenetics control nanoparticle
inducing cellular senescence for cancer cells, The 43rd

Reports from Research Groups

24.

25.

26.

27.

28.

29.

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31.

32.

33.

34.

35.

Annual Meeting of the Japanese Society for Biomaterials（Nagoya Congress Center）, JO-2H07（November 2021)
Koki Mino, Keisuke Ashiba, Kiyoshi Sato, Hiroyoshi
Kawakami, Mitophagy-inducing nanocarriers forfunctional recovery of senescent mesenchymal stem cells,
59th Annual Meeting of the Japanese Society for Artificial
Organs, Hilton Tokyo Bay, YP2-4 (Nov. 2021)
Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Magnetic orientation of Liquid Crystal
comprising Clay and Ionic Liquid and its characteristics.,
15th Magneto-Science Society of Japan , Online, P-06,
November 2021 (in Japanese)
Nakaoji Takashi, Masafumi Yamato, and Kawakami
Hiroyoshi, Magnetic orientation of clay using liquid crystal
phase formed by nanosheets, 15th Magneto-Science
Society of Japan , Online, P-05, November 2021 (inJapanese)
Shuntarou Kimura, Risa Mitsuhashi, Kiyoshi Sato,
Hiroyoshi Kawakami, Induction of cellular senescence incancer cells by epigenetics control carrier, The 44th Annual
Meeting of the Molecular Biology Society of Japan（PACIFICO Yokohama), 3P-0562 (December 2021)
Haruka Nishimura, Keisuke Ashiba, Kiyoshi Sato,
Hiroyoshi Kawakami, Restoration of senescentmesenchymal stem cells using mitophagy inducing
nanocarriers, The 44 th Annual Meeting of the Molecular
Biology Society of Japan (PACIFICO Yokohama),
December 2021
Yokota Nohara, Manabu Tanaka, Hiroyoshi Kawakami,
Polymer nanofiber-based high-salt concentration PEO
composite electrolytes and their lithium ion conductivity
evaluation, 62nd Battery Conference, November 2021 (inJapanease)
Keisuke Ashiba, Takeru Yamazaki, Koki Mino, Kiyoshi
Sato, Hiroyoshi Kawakami, Rejuvenation of mesenchymal
stem cells by liposome nanocarrier inducing mitophagy,
TERMIS 6TH WORLD CONGRESS 2021 (On-line),2017 (November 2021)
Kazuto Suzuki, Manabu Tanaka, Hiroyoshi Kawakami,
Functional Nanofiber Reinforcement Layer that Assists
Proton Transport under High Temperature and Low
Humidity, The 62 th Battery Symposium (Hybrid), 3C03
December 2021 (in Japanese)
Yasutaka Kuwahara, Kazuma Komine, Hiroyoshi
Kawakami, Fabrication and evaluation of proton
conductive crosslinked PVA nanofibers. The 59th researchGroup on the Interaction between Polymer and Water and
Separation Science, PB2, December 2021 (in Japanese)
Yuri Nara, Manabu Tanaka, Kensaku Nagawsawa,
Yoshiyuki Kuroda, Shigenori Mitsushima, Hiroyoshi
Kawakami, Fabrication and Water Electrolysis Evaluationof Anion Exchange Membranes with High Alkaline
Stability., The 59th Symposium on the Interaction
between Polymer and Water and Separation Science, PB3,
December 2021
Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Fabrication of anisotropic ionic gel containing
Clays., 93th Musashino area polymer association, Online,
P14, December 2021 (in Japanese)
Honomi Miyashita, Masafumi Yamato, Hiroyoshi
Kawakami, Higher-order structure of iPP / VGCF

36.

37.

38.

39.

40.

composite material, The 93rd Musashino district polymer
social gathering, (Online Virtual Meeting), December 2021.
Nakaoji Takashi, Masafumi Yamato, and Kawakami
Hiroyoshi, Application of liquid crystal phase formed byclay nanosheets to nanocomposite gel, 93th Musashinoarea polymer association, Online, P15, December 2021 (inJapanese)
Honomi Miyashita, Masafumi Yamato, Hiroyoshi
Kawakami, Structural analysis of iPP / VGCF composites
oriented by magnetic field, The Magneto-Science Societyof Japan, The 29th research society, (Online Virtual
Meeting), December 2021.
Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Magnetic orientation of ionic liquid-clay
nanosheet liquid crystal., 29th Meeting of JSAP- MagnetoScience Society of Japan 2021, Online, P, December 2021
(in Japanese)
Nakaoji Takashi, Masafumi Yamato, and Kawakami
Hiroyoshi, Magnetic field orientation of lyotropic liquid
crystal consisting of different clay, 29th Meeting of JSAPMagneto-Science Society of Japan 2021, Online, P-2A,
December 2021 (in Japanese)
Kazuma Komine, Masafumi Yamato, and Kawakami
Hiroyoshi, Fabrication of anisotropic ion gel using
magnetic orientation of clay nanosheet liquid crystal., the69th JSAP Spring Meeting, ( Online Virtual Meeting), 22aE205-12, March 2022.

■Patents
1.

2.

JP2021-185233,A “Hyperbranch polymer- or dendrimer
polymer-added silica nanoparticle and composite”,(published 2021. 12. 9)
JP2021-24852,A “Cmposite for decompose dysfunctional
mitochondria and composite for scell enescence inhibition”(published 2021. 2. 22)■Awards
1.

2.

3.

4.

5.

5

43st annual meeting of membrane science of Japan,
Student Award, Nana Terasoba, Manabu Tanaka,
Hiroyoshi Kawakami, “Fabrication and evaluation oflithium salt-containing polycarbonate-based composite
electrolyte membrane composed of nanofibers withpolarized crystals”.
The Annual Meeting of the society of fiber science andtechnology Japan, Excellent Poster Award, Yuri NARA,
Manabu Tanaka, Hiroyoshi Kawakami. “Synthesis andElectrolyte Evaluation of Anion Conductive Polymers
Bearing No Heteroatoms in the Polymer Main Chains”.
The 70th SPSJ Annual Meeting, Excellent poster award,
Kazuto Suzuki, Manabu Tanaka, Hiroyoshi Kawakami,“Fabrication and characterizations of acid / base blend
polymer nanofiber composite membranes for hightemperature and low humidity fuel cell operation”.
The 59th Symposium on the Interaction between Polymer
and Water and Separation Science, Excellent Poster Award,
Yuri Nara, Manabu TANAKA, Kensaku NAGASAWA,
Yoshiyuki KURODA, Shigenori MITSUSHIMA,
Hiroyoshi Kawakami, “Fabrication and Water Electrolysis
Evaluation of Anion Exchange Membranes with HighAlkaline Stability”.
The 10th Excellent Research Award of the Magneto-

Reports from Research Groups

6.

7.

Science Society of Japan, Masafumi Yamato, "Research on
polymeric material control using magnetic process".
The 70th Polymer Symposium in Japan, Publicity Award,
Manabu Tanaka, Yu Matsuda, Hiroyoshi Kawakami,“Fabrication and Characterization of Lithium-Air Battery
Consisted of Nanofiber Composite Electrolyte Membranewith Suppressed Water Vapor Permeability”
59th Annual Meeting of the Japanese Society for Artificial
Organs, Poster Award, Koki Mino, Keisuke Ashiba,
Kiyoshi Sato, Hiroyoshi Kawakami, “Mitophagy-inducing
nanocarriers for functional recovery of senescentmesenchymal stem cells”.

6Reports from Research Groups
Asayama Laboratory■Members

To give DDS carrier the ability for definitive
treatment,
wehavedesigned
pH-sensitive
polyvinylimidazole (PVIm) derivateives as intelligent
materials to change their structure and function in
respons to external stimuli. Recently, Zn2+ delivery toliver 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

Master’s course -9
Bachelor 4 -3

Survival insulin
to whole bodyZn 2+

InsulinPancreas

Liver

H
C CH2

■Outlines of the ResearchN

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

Delivery toUnexplored
Space

O
H2N

Mono-Ion Complex【MIC】
C(CH2)n

N

N

1-x-y

Zn2+

n

In this year, we have synthesized hepatocyte-specificZn-porphyrin-carbohydrate conjugates (ZnP-Am-Lac).
These molecules have a porphyrin backbone to becapable of stably coordinating Zn2+ in vivo and have fourβ-galactose residues, which allows it to be recognized by
the asialoglycoprotein receptor (ASGP-R) expressed on
hepatocytes in a multivalent manner, and to beefficiently uptaken by hepatocytes. The inhibition
experiment of the intracellular uptake of ZnP-Am-Lac
proves that the hepatocyte-specific recognition via
ASGP-R is attributed to the nonionic amide spacer
between ZnP and Lac. Furthermore, the resulting
Zn2+ delivery by the ZnP-Am-Lac has suppressed
insulin degradation in human hepatocytes.

As water-soluble (liquid-phase) biomaterials, thecarriers of nucleic acid as a macromolecular drug havebeen designed for unmet medical needs. Recently, themono-ion complex (MIC) to make plasmid DNA (pDNA),
as a gene, highly condensed has been formed for+N

Figure 2. Remote control of hypoglycemic hormone inblood.

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

+

N

H
C CH2

y

+
N
N
(CH2) CH3

N

Protein

H
C CH2

x

PEG

3. Biomaterials with Funtional Surface
Shoichiro ASAYAMA
As water-insoluble (splid-phase) biomaterials, todesign medical devices working in vivo or ex vivo withefficient biocompatibility, we have recently appliedcholesterol end-modified poly(ethylene glycol), that is,
Chol-PEG, as DDS carrier to the non-covalentmodification of solid surface (Figure 3).

Diseasedelivery to in vivo unexplored space (Figure 1).
Figure 1. Delivery to in vivo unexplored space by themono-ion complex (MIC).
In this year, we have synthesized diethylamino (DEA)
end-modified PEG with imine spacer (DEA=PEG) to
improve the formation stability of MICs and to achieve
more significant in vivo gene expression. The DEA
group is expected to stabilize the electrostaticinteraction as a highly hydrophobic cationic moiety.
And, an imine group has been selected as a spacer for
PEG chain dissociation by hydrolysis, as well as apartial cationic moiety to be iminium ion or neutral
imine at physiological pH.

H3C

Most Simple
Noncovalent
PEGylation
CH3O

CH2CH2O

n

CH3
H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

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

CH3

H3C

Insulin

7

7

8

9
10
11
Elution volume / mL

12

Reports from Research Groups
Figure 3. Development of novel bio-function by CholPEG.
In this year, manganese or iron tetrakis(4carboxyphenyl)porphyrin(Mn,
Fe-TCPP)andmethylated poly(1-vinylimidazole) (PVIm-Me) or
octylated poly(1-vinylimidazole) (PVIm-Oc) weremodified on the dialysis membrane by a non-covalentbond using the layer-by-layer method. Thus, we have
prepared a functional hemodialysis membrane withcatalase pseudo-active center on the surface for aunique device that can decompose hydrogen peroxideduring hemodialysis.

■Papers with Peer Review
1. Akito Endo and Shoichiro Asayama, Hepatocytespecific co-delivery of zinc ions and plasmid DNA bylactosylated poly(1-vinylimidazole) for suppression of
insulin receptor internalization, Pharmaceutics, 13,
2084-2093 (2021).
2. Haibo Qiao and Shoichiro Asayama, Guanidinopropyl
end-modified poly(ethylene glycol) to form highly
compact plasmid DNA mono-ion complexes by thermal
treatment, Polymers for Advanced Technologies, 33,
484-491 (2022).
■Reviews
1. Shoichiro Asayama, Noncovalent PEGylation ofprotein and plasmid DNA fo the delivery system,
Feature Articles “Biomaterials for Good Health andWell-Being”, Journal of Japanese Society for
Biomaterials, Vol. 39, No. 4, 222-227 (2021).
■Academic Meeting
See the annual report in Japanese (18 articles)■Patents
See the annual report in Japanese (1 patent).

8

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

Chemistry,
Figure 2. Arylselanyl-substituted BOPHYs as triplet
sensitizers.
3. 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.

Doctor’s course -2
Master’s course -9
Bachelor -5■Outlines of the Research
1. Organic room-temperature phosphorescence materials
Yuji Kubo
Abstract
Considering low-cost, abundant resources and low
environmental pollution compared to precious metal-containing
inorganic materials, organic room-temperature phosphorescence(RTP) materials with improvement of intersystem crossing (ISC)
channel and minimization of vibration-based and oxygenmediated quenching have attracted considerable attention. In thiscontext, boronate particles prepared by dehydration reaction ofbenzene-1,4-diboronic acid with pentaerythritol, which showed
RTP behavior with a green afterglow in water. The long-lived
lifetime has motivated us to develop afterglow materials forapplication in chemseonesors.

Figure 3. Dye-sensitized photocatalytic hydrogen production.
3. Visually chiral recognition using aggregation-induced
emission
Yuji Kubo
Abstract
Detection of chirality is analytically significant because theenantio-purity of products is essential for various applications in
the pharmaceutical, agrochemical, and food industry.
Florescence sensing for chirality is a highly sensitive, facile, andcost-effective method for determining enantiomer purity. In thisstudy, we focused on boronate ensembles with aggregationinduced emission (AIE) units because enantio-dependent
aggregation modes provide the system with chiral sensors.
However, the accuracy and repeatability of the change in the
fluorescence signal as a function of the enantiomer excess ofanalytes are not high because self-assembly is used as anamplification method for molecular recognition events. We
succeeded quantitative sensing chirality by applying
chemometrics. Notably, calibration and prediction of the % ee ofchiral CHDA was successfully achieved with the ANN
technique.

Figure 1. Metal ion-responsive afterglow martials.
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 2- and 7- positionofbis(difluoroboron)1,2-bis((1H-pyrrol-2-yl)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 withlarge anti-Stokes shift of 94 nm and UC quantum yield (ФUC) of
3.9% in toluene when excited with 524 nm laser (50 mW).

9

Reports from Research Groups

Figure 4. Chiral recognition coupled with chemometrics.
5. Sensor array based on cross reactivity using relay
recognition
Yuji Kubo, Pavel Anzenbacher Jr
The prepared fluorescent carboxyamidoquinolines and their
Zn(II) complexes were used to bind and sense various phosphateanions utilizing a relay mechanism, in which the Zn(II) ion
migrates from the complex to the phosphate, namely adenosine
5’-triphosphate (ATP) and pyrophosphate (PPi), a processaccompanied by a dramatic change in fluorescence. The crossreactive nature of the carboxyamidoquinolines-Zn(II) sensors inconjunction with linear discriminant analysis (LDA) was utilized
in a simple fluorescence chemosensor array that allows for theidentification of ATP, ADP, PPi, and Pi from 8 other anions
including adenosine 5’-monophosphate (AMP) with 100%
correct classification. Furthermore, the support vector machine
algorithm, a machine learning method, allowed for highly
accurate quantitation of ATP in unknown samples with error <2.5%.

Figure 6. a) Moleculer structures of a near-infrared luminescentdye with a narrow band width and b) a stimuli-responsive red
emissive dye.

■Papers with Peer Review
1. M. Kanakubo, Y. Yamamoto, and 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., 2021, 94, 1204-1209. DOI:10.1246/bcsj.20210004
2. R. Hasegawa, S. Iwakiri, Y. Kubo, Synthesis and triplet
sensitization of bis(arylselanyl)BOPHYs; potential applicationin triplet-triplet annihilation upconversion, New J. Chem., 2021,
45, 6091-6099. DOI: 10.1039/D1NJ00721A
3. M. Ito, M. Sakai, N. Ando, S. Yamaguchi, Electron-deficientheteroacenes that contain two boron atoms: near-infrared
fluorescence based on a push–pull effect, Angew. Chem. Int.
Ed., 2021, 60, 21853-21859. DOI: 10.1002/anie.202106642
4. M. Pushina, S. Farshbaf, W. Mochida, M. Kanakubo, Ryuhei
Nishiyabu, Yuji Kubo, and P. Anzenbacher, Jr., A fluorescencesensor array based on zinc(II)-carboxyamidoquinolines: Toward
quantitative detection of ATP, Chem. Eur. J., 2021, 27, 1134411351. DOI: 10.1002/chem.202100896

Figure 5. Graphical output of the qualitative linear discriminant
analysis

5. K. Makino, T. I, and Y. Kubo, A benzofuran[b]-fused BODIPY
as an efficient sensitizer for photocatalytic hydrogen production,
Sustain. Energy Fuels, 2021, 5, 3676-3686. DOI:
10.1039/D1SE00387A

6. Synthesis of boron-containing molecules for applicationin functional materials.
Masato Ito
Abstract
By the incorporation of main group elements into a p-conjugatedskeleton, the main group element moieties can alter the pskeleton sterically and electronically. Group 13 boron atom is ofparticularly interest, as its incorporation results in the low-lying
LUMO through the p–p* interaction between a vacant p orbitalof the boron atom and a p* orbital of a p-conjugated skeleton.
Consequently, boron-containing p-conjugated skeletons exhibit
the electron-accepting character together with high Lewis acidity.
In this study, by taking advantage of these characteristics, wehave achieved the development of a near-infrared luminescentdye with a narrow band width and a stimuli-responsive red
emissive dye with the aim of constructing promising functional
materials.

6. K. Kawaguchi, A. Moro, S. Kojima and Y. Kubo, Chiralrecognition coupled with chemometrics using boronate
ensembles containing D-π-A cyanostilbenes, Chem. Commun.,
2021,57, 12952-12955. DOI:10.1039/D1CC05492A.
7. S. Farshbaf, K. Dey, W. Mochida, M. Kanakubo, R. Nishiyabu,
Y. Kubo, and P. Anzenbacher Jr.,Detection of phosphates inwater utilizing a Eu3+- mediated relay mechanism, New J. Chem.,
2022, 46, 1839-1844, DOI: 10.1039/d1nj04578d
8. H. Narita, H. Choi, M. Ito, N. Ando, S. Ogi, S. Yamaguchi,
Fully fused boron-doped polycyclic aromatic hydrocarbons:
their synthesis, structure–property relationships, and selfassembly behavior in aqueous media, H. Narita, H. Choi, M. Ito,

10

Reports from Research Groups
N. Ando, S. Ogi, S. Yamaguchi, Chem. Sci., 2022, 13, 1484–
1491. DOI: 10.1039/D1SC06710A■Books
1. White-Light Emissive Materials Based on Supramolecular
Approach, Yuji Kubo, Progress in the Science of FunctionalDyes, Editors ； Yousuke Ooyama 、 Shigeyuki Yagi, 2021,
Springer, Pages 409-443.

■Invited Lectures
See the annual report in Japanese (1) article.

■Academic Meeting＊International
1. Electron push–pull effect on the properties of two boroncontaining electron-deficient heteroacenes, Masato Ito, Mika
Sakai, Naoki Ando, Shigehiro Yamaguchi, Beyond Telluride
Forum (online), Apr. 13, 2021.
2. Accurate pattern recognition for chiral amines from just asingle chemosensor, Yui Sasaki, Soya Kojima, Vahid
Hamedpour, Riku Kubota, Shin-ya Takizawa, Isao Yoshikawa,
Hirohiko Houjou, Yuji Kubo, Tsuyoshi Minami, Pacifichem
2021, Optical Cross-Reactive Sensor Arrays, Artificial Noses
and Tongues (#352), Dec.18, 2021.
3. Boron-stabilized radicals: fluorescence properties andapplication to organic light-emitting diodes, Masato Ito, Yongfa
Xie, Naoki Ando, Tomokatsu Kushida, Shunsuke Shirai, Hiroki
Soutome, Kenichi Tabata, Yasuo Miyata, Hiroshi Kita,
Shigehiro Yamaguchi, Pacifichem 2021, Designed pi-Electronic
Systems: Synthesis, Properties, Theory and Function (#359),
Dec. 19, 2021.
4. Boron-doped polycyclic aromatic hydrocarbons with
unsymmetric structures, Hiroki Narita, Masato Ito, Naoki Ando,
Soichiro Ogi, Shigehiro Yamaguchi, Pacifichem 2021, Designed
pi-Electronic Systems: Synthesis, Properties, Theory andFunction (#359), Dec. 19, 2021.
＊Domestic
See the annual report in Japanese (15) articles.

■Awards
See the annual report in Japanese.

11

Reports from Research Groups
Setaka Laboratory■Members
Wataru Setaka
Professor /Dr. Sci.
Physical Organic Chemistry, Functional Organic Chemistryroom: 9-542 TEL: +81-42-677-1111 (Ext.4955)
e-mail: wsetaka@tmu.ac.jp
Yusuke Inagaki
Assistant Professor / Dr. Sci.
Main-group Chemistry, Functional Organic Chemistryroom: 9-545 TEL: +81-42-677-1111 (Ext.4957)
e-mail: yinagaki@tmu.ac.jp

Figure 2. Structural formulas, X-ray structures ofthienothiophene dioxide bridged molecular gyrotops, andphotographs of fluorescence of their powder samples (paper #3).

Doctor’s course -0
Master’s course -7
Bachelor 9

Intramolecular charge transfer (ICT) fluorescence has been
widely investigated and exploited in sensor molecules. However,steric effects on the ICT fluorescence properties have rarely beenreported so far, although research in this area would promote anunderstanding of the basics of solvation. Herein, we report thedetailed
fluorescence
propertiesofbis(trimethylsilyl)benzo[b]thiophene-1,1-dioxide (TMSBTO2)
and its caged cyclophanes and non-cage isomers, which
demonstrate ICT fluorescence in various solutions. The
fluorescence band maxima for these benzo[b]thiophene-1,1dioxides (BTO2s) showed a red-shift with increasing solvent
polarity, confirming ICT fluorescence characteristics. The
linearity of the Lippert–Mataga plots was confirmed for all ICT
fluorescence measured in hexane, toluene, AcOEt, CH2Cl2, and
EtOH. The slopes of the plots decreased in the following order:
TMSBTO2, non-cage isomers, and caged BTO2s. It is
concluded that the Onsager radii for these BTO2s were increasedin the abovementioned order, assuming that the difference in the
dipole moments between the excited and ground states for these
BTO2s was identical. (Figure 3, paper #2).

■Outlines of the Research
Development of Highly Designed Organic Molecules
Development of organic molecules of which strucrure andfunctions are highly designed would improve our daily life withrespect to energy saving and environmental consequence. Ourinterest lies in the design and synthesis of organic molecules withnew structures that incorporate silicon to develop molecules withnew functions. Specifically, we are studying the relationshipbetween molecular structure and molecular functionalities ofnovel organosilicon compounds.
1. 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. Order of Onsagar radii for ICT fluorescence in silyl
substituted benzothiophene dioxides (paper #2).
2. Novel Flexible Macrocycles
A facile and novel template synthesis of flexible
disilamacrocyclic compounds via a ring-closing metathesis
coupling was achieved. The structures of the macrocycles were
determined by X-ray crystallography, and two conformers withsimilar stabilization energies were observed and characterized.
(Figure 5, paper #4).

Figure 1. molecular gyrotop.
In this year, following papers were published.
Fluorescent dielectric materials that show solid-state
fluorescence and dielectric relaxation in the crystalline state
were realized using crystals of thienothiophene-dioxide-bridged
macrocage compounds C14TTO2 and C18TTO2, in which thefirst number indicates the length of the alkyl chains in the cage.
In these molecules, the fluorophore can rotate even in the
crystalline state because the fluorophore is encased in themacrocage frame. Therefore, they are called molecular gyrotops.
The rotational dynamics of the fluorophore in the crystalline
state were observed by temperature-dependent dielectricrelaxation, and the fluorophore was found to be static in
C14TTO2, while restricted rotation was observed for C18TTO2.
The solid-state fluorescence quantum yield decreased with theincreasing alkyl chain length, indicating that the fluorescenceintensity clearly depends on the dynamics of the fluorophore.
(Figure 2, paper #3).

Figure 5. Structure of disilamacrocycles in a crystalline state(paper #4).

12

Reports from Research Groups

Facileandsimultaneous
synthesisofdiphenyldisilabicyclo[14.14.14]alkane in/out-isomers was achieved byusing organosilicon chemistry. Although the formation ofseveral in/out-isomers would be conceivable, only two
diastereomers, i.e. the (traditional-)out,out-isomer and the twistout,out-isomer, could be isolated because of homeomorphic
isomerization. Crystal structures of the diastereomers wereconfirmed (Figure 6, paper #1).

Figure 6. Structural formulas of disilabicycloalkanes (paper#1).

■Papers with Peer Review
1.

2.

3.

4.

5.

6.

Simultaneous Synthesis and Characterization of in/outIsomers of Disilabicyclo[14.14.14]alkanes, Yuto Ikeda,
Yusuke Inagaki, and Wataru Setaka*, Chem. Commun.
2021, 57, 7838-7841.
Steric effects on the intramolecular charge transfer
fluorescence of benzo[b]thiophene-1,1-dioxide bridged
macrocages, Keita Nobuhara, Yusuke Inagaki, and Wataru
Setaka*, Org. Biomol. Chem. 2021, 19, 6328-6333.
Crystalline Thieno[3,2-b]thiophene-dioxide-diyl bridged
Molecular Gyrotops as Fluorescent Dielectric Materials,
Daiki Hayashi, Yusuke Inagaki, and Wataru Setaka*, J.
Mater. Chem. C 2021, 9, 8220-2225.
Structure and Dynamics of Crystalline Molecular Gyrotops
with a Difluorophenylene Rotor, Yuyang Tu, Yusuke
Inagaki, Eunsang Kwon, and Wataru Setaka*, Chem. Lett.
2021, 50(7), 1397-1399.
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)■Invited Lectures
1.

Yusuke Inagaki,
Substituent Effect as a New Phospher in Silylfuryl
Substituted Fluorobenzene
The 25st Symposium on Silicon Chemistry, Online,
2021.10.28 (Japan).(oral, in Japanese)2.

Wataru Setaka,
Chemistry of Molecular Gyrotops as Molecular Machines
Special Lec. for Graduate School Students (1), Tokyo
University of Science, 2021.7.7. (oral, in Japanese)■Academic Meeting＊Domestic
See the annual report in Japanese (13 articles)

13

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

EnergyChemistry,

Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-246 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp
Doctor’s course - 1
Master’s course - 13
Bachelor 4 - 0

Fig. 2 Capacity retention of laminate type rechargeable lithium
metal batteries composed of NCM523 composite cathode and 20µm lithium metal anode including different amounts of FEC in
1 mol dm-3 LiPF6 / EC electrolyte solution.

■Outlines of the Research
1. Research on next-generation rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of rechargeable lithium batteries withlithium-metal anode was carried out to realize higher energy
density than that of currently-used lithium-ion batteries.
Lithium-metal anode has about ten times larger gravimetriccapacity than graphite anode used in lithium-ion batteries.
However, its morphology changes to needle-like forms during
charge-discharge cycles, resulting in internal short circuit ofbatteries by the penetration of a separator. Low Coulombic
efficiency due to easy decomposition of electrolyte solutions onlithium metal is also a problem to be solved. In this year, theoptimization of electrolyte composition and separator structure
were mainly carried out to solve those problems. In addition,
laminate type cells were constructed and tested instead of cointype ones to extract issues on practical cell design.
From the pressure visualization measurement, laminate typecells showed more uniform pressure distribution than coin typecells, improving the uniformity of lithium deposition
morphology. The laminate type cells with LiNi0.5Co0.2Mn0.3O2(NCM523) composite cathode and 20 µm lithium metal anodewere fabricated using 1 mol dm-3 LiPF6 / ethylene carbonate(EC) electrolyte solution including different amounts offluoroethylene carbonate (FEC) as an electrolyte additive (Fig.
1). The cell without FEC showed a decrease in the capacity
retention after about 30th charge-dsicahrge cycle. On the other
hand, the improved capacity retention was observed for all thecells including FEC, and the highest cycleability was obtained inthat with 3 wt.% FEC (Fig. 2).

2. Research on fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
To improve the energy conversion efficiency of fuel cells, theoperation at higher temperatures is basically needed, whichenables to use waste heat more effectively in addition to theactivity improvement and poisoning suppression of fuel cell
catalysts. We have focused on H+-conducting ionic liquids andtheir mixtures with phosphoric acid as new electrolytes usable ataround 200 °C, and been developing the intermediate
temperature fuel cells.
To achieve better fuel cell performance, we focused and tried
to improve the electrochemical oxygen reduction reaction(ORR) of catalysts in the ionic liquid-based electrolytes
continuously in this year. By using nitrogen-doped graphene as
Pt catalyst support instead of conventionally used Ketjen black,
we succeeded to improve ORR activity and durability of Pt
catalyst in those electrolytes (Fig. 3). In addition, we focused on
the application of OH--conducting ionic liquids as newelectrolytes for intermediate temperature operation of alkalinetype fuel cells, and revealed that carbon-based materials havehigher ORR activity than Pt catalyst in those OH--conducting
ionic liquids.

Fig. 3 ORR activity and durability of Pt/C (left) and Pt/nitrogendoped graphene (right) in H+-conducting ionic liquid composedof N,N-diethylmethylamine and trifluoromethanesulfonic acid(black lines: N2 atmosphere before durability test, red lines: O2
atmosphere before durability test, blue lines: O2 atmosphere after
durability test) at 120 °C. The durability test was performed by2000 cycles of potential sweep at 500 mV s-1 in a potential rangeof 1.0~1.5 V vs. RHE.

Fig. 1 A laminate type rechargeable lithium-metal battery
prepared in this study.

14

Reports from Research Groups■Papers with Peer Review
1.

2.

3.

4.

5.

6.

7.

8.

9.

■Requested Lectures

Mayu Saito, Hidechika Arima, Mao Shoji, Yota Kizuki,
Hirokazu Munakata, Kiyoshi Kanamura, Koichi Kajihara,
Solid-State Rechargeable Lithium Metal Battery with
Li4B4Al3O12Cl-based
Water-ResistantLithium-IonConducting Oxychloride Glass-Ceramic Electrolyte,
Journal of The Electrochemical Society, 168 (2021)
040524.
Dong Ding, Yuta Maeyoshi, Masaaki Kubota, Jungo
Wakasugi, Koshin Takemoto, Kiyoshi Kanamura,
Hidetoshi Abe, Li-ion conducting glass ceramic(LICGC)/reduced graphene oxide sandwich-like structurecomposite for high-performance lithium-ion batteries,
Journal of Power Sources, 500 (2021) 229976.
Dong Ding, Yuta Maeyoshi, Masaaki Kubota, Jungo
Wakasugi, Kiyoshi Kanamura, Hidetoshi Abe, Nonflammable super-concentrated polymer electrolyte with“solvated ionic liquid” for lithium-ion batteries, Journal ofPower Sources, 506 (2021) 230099.
Koichi Kajihara, Daisuke Takahashi, Hiroaki Kobayashi,
Toshihiko Mandai, Hiroaki Imai, Kiyoshi Kanamura,
Phenylphosphonate surface functionalisation of MgMn2O4
with 3D open-channel nanostructures for composite
slurry-coated cathodes of rechargeable magnesium
batteries operated at room temperature, RSC Advances, 11(2021) 19076-19082.
Jik Soo Kim, Seonghyeon Lim, Hirokazu Munakata,Sung-Soo Kim, Kiyoshi Kanamura, Understanding therelationship of electrochemical properties and structure of
microstructure-controlled core shell gradient type Ni-richcathode material by single particle measurement,
Electrochimica Acta, 390 (2021) 138813-138818.
Toshiki Tsuchiya, Yuko Fukuda, Kiyoshi Kanamura,
Koichi Kajihara, Low-Refractive-Index Deep-Ultraviolet
Transparent Poly(fluoroalkyl-co-methylsilsesquioxane)
Resins Synthesized by Cosolvent-Free Hydrolytic
Polycondensation of Organotrimethoxysilanes, Journal of
Physical Chemistry B, 125 (2021) 8238-8242.
Eric Jianfeng Cheng, Mengyue Liu, Ying Li, Takeshi Abe,
Kiyoshi Kanamura, Effects of porosity and ionic liquid
impregnation on ionic conductivity of garnet-based
flexible sheet electrolytes, Journal of Power Sources, 517(2022) 230705.
Sagane Fumihiro, Ogi Kenta, Konno Akinori, Kanamura
Kiyoshi, The effect of the coordination ability on the Mg
plating/stripping behavior in Mg(N(CF3SO2)2)2/glyme
based electrolytes, Journal of The Electrochemical Society,
168 (2021) 120528.
Hossein Davoodi, Nurdiana Nordin, Hirokazu Munakata,
Jan G. Korvink, Neil MacKinnon, Vlad Badilita, Untuned
broadband spiral micro‑coils achieve sensitive
multi‑nuclear NMR TX/RX from microfluidic samples,
Scientific reports, 11 (2021) article number 7798.

＊Domestic
See the annual report in Japanese (3 articles)■Academic Meeting＊Domestic
See the annual report in Japanese (32 articles)■Books and reviews
See the annual report in Japanese (4 articles)■Invited Lectures＊Domestic
See the annual report in Japanese (1 article)

15

Reports from Research Groups
Kajihara Laboratory■Members

Silica is a ubiquitous material and its utilization is inaccordance with SDGs. We are studying cosolvent-free sol-gel
method to form silca-based materials only from silicon alkoxides
and water without using cosolvents. Using this method we
prepared fluorine-containing low-refractive-index and deepultraviolet-transparent resins and achived a refractive index of~1.35 at 589 nm (Fig. 3) We also found that silica-(Tb,Ce)PO4
transparent glass-ceramics prepared by a cosolvent-free sol-gel
mehodexhibitconsentration-quenching-freegreen
photoluminescene with internal quantum efficiency close tounity, whereas that of (Tb,Ce)–Al-codoped silica glasses, inwhich rare-earth ions are rather disersed, is much lower. Theseobservations demonstrate that the control of the distribution of
rare-earth ions is crucial in increasing the photoluminescencequatum efficiency of rare-earth-doped silica glasses (Fig. 4).

Koichi KAJIHARA
Professor /Ph.D.
Inorganic Chemistry, Functional Material Chemistry,
Inorganic Materials/Physical Properties
Room:9-336 TEL: +81-42-677-2827
kkaji@tmu.ac.jp
Takashi TAKEI
Associate Professor/Dr. Eng.
Solid Surface Chemistry, Colloid and Interface Science
Room. 9-142 TEL:+81-42-677-2822
takei-takashi@tmu.ac.jp
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
Master’s course -11
Bachelor 4 -9

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

Fig. 3 Fluorine-containing low-refractive-index polysilsesquioxane resins prepared by a cosolvent-free method.

We are studying energy devices using oxides. A new lithium
chloroboracite Li4B4Al3O12Cl discovered in our lab. is stable incontact with lithium. It was found to be water-resistant andusable as solid electrolytes of solid rechargeable lithium metal
batteries (Fig. 1). We have also developed phenylphosphonate
surface functionalization of porous MgMn 2O4, a promisingcathode material for rechargeable magnesium batteries, andfound that this method is effective in suppressing side reactions
during charge and discharge, increasing Coulombic efficiency,
improving the quality of slurry-coated cathodes, and achiving
the room temperature operation of slurry-coated cathodes withhigh active material contents (Fig. 2).

Fig. 4 Concentration-quenching-free green photoluminescenceof a silica–(Tb,Ce)PO4 transparent glass-ceramic (left) and green
photoluminescence of a (Tb,Ce)–Al-codoped silica glass under
excitation with an UV LED at 290 nm.

Fig. 1 A coin-type solid-state rechargeable lithium metal battery
prepared using water-resistant glass-ceramic electrolyte of a newlithium boracite Li4B4Al3O12Cl.

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.

Fig. 2 Phenylphosphonate surface functionalization of porous
MgMn2O4 for rechargeable magnesium batteries and operationof slurry-coated cathodes with high active material contents atroom temperature.

3. Fabrication of Nanofilters by Electrochemical Process
Takashi YANAGISHITA

16

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

anodization of pretextured Ga. J. Vaccum. Sci. Technol. B,
40, 010603 (2022).
11. T. Yanagishita, K. Kato, N. Shirano, H. Masuda. Preparationof Ideally Ordered Anodic Porous Alumina by Prepatterning
Process Using a Flexible Mold. ECS J. Solid State Sci.
Technol., 11, 013001 (2022).
12. T. Yanagishita, K. Kikkawa, and H. Masuda. Ideally ordered
anodic porous alumina on Si substrate prepared byanodization of sputtered Al-Mg thin film. ECS J. Solid State
Sci. Technol., 10, 115002 (2021).
13. T. Yanagishita, Y. Nishioka, S. Miwa, H. Masuda, Y.
Komoda. Template-Free Preparation of Metal Nanowires by
Two-Phase Electrolysis Using Cells Composed of Water and
Oil Phases. J. Electrochem. Soc., 168, 093502 (2021).
14. T. Yanagishita, M. Yoshida, H. Masuda. Renewable
Superhydrophobic Surfaces Prepared by Nanoimprinting
Using Anodic Porous Alumina Molds. Langmuir, 37, 10573(2021).
15. T. Yanagishita, M. Otsuka, T. Takei, U. Seigo, H. Masuda.
Preparation of Ordered Anodic Porous Alumina with SingleNanometer-Order-Size Holes by Atomic Layer Deposition.
Langmuir, 37, 8331 (2021).
16. T. Kondo, M. Yoshida, T. Yanagishita, H. Masuda.
Fabrication of Li Nanohole Array by Replication Process
Using Anodic Porous Alumina Template. J. Electrochem.
Soc., 168, 032508 (2021).

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. K. Kajihara, S. Nakagawa, R. Iwasaki, Energy transfer andquenching in sol–gel-derived silica glass green phosphors
doped with Tb3+ and Ce3+ ions: Distinct difference between
P- and Al-codoped glasses. Phys. Status Solidi A 219,
2100494 (2022)
2. T. Tsuchiya, Y. Fukuda, K. Kanamura, K. Kajihara. Lowrefractive-index
deep-ultraviolet
transparentpoly(fluoroalkyl-co-methyl-silsesquioxane)
resinssynthesized by cosolvent-free hydrolytic polycondensationof organotrimethoxysilanes. J. Phys. Chem. B 125, 82388242 (2021).
3. K. Kajihara, D. Takahashi, H. Kobayashi, T. Mandai, H. Imai,
K. Kanamura. Phenylphosphonate surface functionalisationof MgMn2O4 with 3D open-channel nanostructures forcomposite slurry-coated cathodes of rechargeable
magnesium batteries operated at room temperature. RSC
Adv. 11, 19076-19082 (2021). Open Access
4. L. Skuja, N. Ollier, K. Kajihara, I. Bite, M. Leimane, K.
Smits, A. Silins. Optical absorption of excimer laser-induced
dichlorine monoxide in silica glass and excitation of singlet
oxygen luminescence by energy transfer from chlorine
molecules. Phys. Status Solidi A 218, 2100009 (2021).
5. M. Saito, H. Arima, M. Shoji, Y. Kizuki, H. Munakata, K.
Kanamura, K. Kajihara. Solid-state rechargeable lithium
metal battery with Li4B4Al3O12Cl-based water-resistantlithium-ion-conducting
oxychloride
glass-ceramicelectrolyte. J. Electrochem. Soc. 168, 040524 (2021).
6. T. Yanagishita, T. Masuda, H. Masuda. Preparation ofOrdered Nanohole Array Structures by Anodization of
Prepatterned Cu, Zn, and Ni. RSC Adv., in press.
7. T. Yanagishita, M. Omata, H. Masuda. Preparation of MothEye Structures on Curved Surfaces by Nanoimprinting
Using Anodic Porous Alumina Molds.Jpn. J. Appl. Phys., inpress.
8. D. Linklater, S. Saita,T. Murata, T. Yanagishita, C.
Dekiwadia, R. Crawford, H. Masuda, H. Kusaka, E. Ivanova.
Nanopillar Polymer Films as Antibacterial Packaging
Materials. ACS Applied Nano Materials, in press.
9. T. Yanagishita, H. Itoh, and H. Masuda. Efficient Fabricationof Ordered Alumina Through-Hole Membranes Using TiO2
Protective Layer Prepared by Atomic Layer Deposition.
RSC Adv., 12, 3662 (2022).
10. T. Kondo, Y. Kuroda, T. Shichijo, T. Yanagishita, H. Masuda.
Formation of ideally ordered porous Ga oxide by■Reviews and Books
See the annual report in Japanese ( 2 articles)■Invited Lectures＊Internationa
1. K. Kajihara, Acid-catalyzed tetraalkoxysilane-water binary
solutions: liquid-state NMR characterization and silica thinfilm processing. PACRIM14, 2021/12, online.
＊Domestic
See the annual report in Japanese (4 articles)■Academic Meeting＊International
1. K. Kajihara, R. Iwasaki, Negligible concentration quenchingin sol–gel-derived silica–(Tb,Ce)PO4 transparent glassceramic green phosphors. SiO2 2021(Lille France), 2021/6，
online.
2．M. Martínez-Viademonte, S. T. Abrahami, T. Yanagishita, K.
Thiel, M. D. Havigh, B. Wouters, T. Hack, M. Burchardt, H.
Terryn．Modification of porous anodic layers on AA2024 cladby atomic layer deposition and its effect on coating adhesion
and oxide stability．EUROCORR 2021，2021/6，online＊Domestic
See the annual report in Japanese (28 articles)■Patents
See the annual report in Japanese ( 1 articles)■Awards
See the annual report in Japanese ( 3 articles)

17

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

Chemistry,

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

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

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

Tetsuya SHIMADA
Assistant Prof. / Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Visiting researcher 4
Doctor’s course 7
Master’s course 13
Bachelor 8
Research student 1■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.
4. Surface – Fixation Induced Emission on the nanosheets

18

Reports from Research Groups
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. 5. The equilibrium between aldehyde (MQu+-Aldehyde) anddiol (MQu+-Diol) in water without and with clay nanosheet.

7. Research on supported gold catalysts
Tamao ISHIDA
Hydroxyapatite (HAP)-supported gold nanoparticle (Au NP)
catalysts exhibit a strong metal-support interaction (SMSI), in
which a thin layer of HAP covers the surface of Au NPs by heat
treatment under oxidative atmosphere. In addition, the electronic
properties of Au tend to be cationic by the expression of SMSI.
We investigated whether this oxidative SMSI occurs in cationand anion-substituted HAPs (sHAPs), and how the electronic
state of Au NPs changes. Utilizing the SMSI-induced cationicproperties of Au, the isomerization of 3,4-diacetoxybut-1-ene(34DABE) to 1,4-diacetoxybut-2-ene (14DABE) was examined.
For all the Au/sHAP catalysts treated at 300 °C under O2(Au/sHAP_300_O2), the surface of Au particles was partiallycovered by thin sHAP layers, confirmed by high-resolution
transmission electron microscopy (HRTEM) (Fig. 6). Au NPs
with a mean diameter of ca. 2 nm were deposited on unsubstited
HAP (CaHAP, Ca10(PO4)6(OH)2) regardless of whether thethermal treatment atmosphere was O2 or H2, i.e., the presence orabsence of SMSI. On the other hand, when the hydroxy group of
CaHAP was replaced by a floride ion (CaFAP) and reduced in
H2, large Au NPs with a mean diameter of 9 nm were deposited,while the mean diameter of Au decreased to ca. 2 nm under O2.
It suggests that the aggregation of Au was suppressed by theformation of SMSI. When the phosphate in HAP was replacedby vanadate (VO4) (SrVAP), relatively large Au NPs (ca. 5 nm)
were deposited. These results suggest that phosphate andhydroxide groups play an important role for stabilizing Au
particles. When Ca was replaced by Sr (SrHAP), obviouos
difference in the Au particle size was not observed compared to
CaHAP, but a partial substitution of Ca with Mg or Ce was
effective for minimizing the Au particle size, giving Au clusters
with diameters of less than 2 nm. For all the Au/sHAPs, the sizesof Au NPs were almost the same between O2- and H2-treatedsamples except for Au/CaFAP.

Fig. 3. Surface – Induced Emission on the nanosheets. Left: without
nanosheet, Right: with nanosheet.

5. Research on Dye Sensitized Hydrogen Evolution Systemusing titania nanosheet
Shinsuke TAKAGI, Tetsuya SHIMADA
Visible light induced hydrogen evolution system wasconstructed by using Rh doped titania nanosheet (Rh-TNS) as anadsorbent, an electron accepter, and a photocatalyst for H2
production with 5.0% quantum yield. The action spectra forhydrogen production were well coincide with the absorption
spectra of Zn-porphyrin that was adsorbed on Rh-TNS.

Fig. 4. Electron injection from Dye to semiconductor nanosheet.

6. “In-water” Dehydration Reaction of an Aromatic Diol on an
Inorganic Surface
Shinsuke TAKAGI, Tetsuya SHIMADA
The effect of a synthetic saponite surface on the “inwater”
dehydration reaction of diol was examined using 4-formyl-1methylquinolinium salt (MQu+) as a substrate. The equilibrium
between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was
affected by the surrounding environment. The equilibrium
behavior was observed by 1H nuclear magnetic resonance(NMR) and UV−vis absorption measurements. Although MQu+
was completely in the form of MQu+-Diol in water, theequilibrium almost shifted to the MQu+-Aldehyde side when
MQu+ was adsorbed on the saponite surface in water. In addition,
the MQu+- Aldehyde ratio depended on the negative charge
density of saponite. The factors that determine MQu+-Aldehyde:
MQu+-Diol ratio were discussed from the thermodynamic
analysis of the system. These data indicate that the electrostaticinteraction between the charged saponite surface and MQu+
stabilized the aldehyde side enthalpically and destabilized it
entropically. The major reason for these results is considered tobe the difference in adsorption stabilization between MQu+Aldehyde and MQu+-Diol on saponite surfaces.

Fig. 6 HRTEM images of Au/CaHAP and Au/Mg0.1CaHAP heattreated at 300 °C under O2 (with SMSI) and H2 (without SMSI).

The electronic states of Au of Au/sHAPs_300_O2 andAu/sHAPs_300_H2 were evaluated by diffuse reflectance19

Reports from Research Groups
Murayama, J. Rabeah, M. Parlinska-Wojtan, A. Brückner, R.
J. Behm, ACS Catal., 11, 9022–9033(2021).
12. T. Fujita, M. Zysman, D. Elgrabli, T. Murayama, M. Haruta,
S. Lanone, T. Ishida, J. Boczkowski, Sci. Rep., 11, 2312923138(2021).
13. M. Oshima, K. Sano, Y. Hirade, R. Nakazato, T. Ishida, T.
Shimada, S. Takagi, J. Phys. Chem. Solids, 161, 110423110428(2022).
14. H. Takimoto, Y. Hirade, T. Shimada, T. Ishida, S. Takagi,
Results Chem., 4, 100271-100275(2022).
15. L. X. Dien, H. D. Chinh, N. K. Nga, R. Luque, S. M. Osman,
L. G. Voskressensky, T. D. Lam, T. Ishida, T. Murayama,
Mol. Catal., 518, 112053-112057(2022).

infrared Fourier transform (DRIFT) spectroscopy using CO as aprobe molecule. When compared the Au/sHAPs_300 catalysts
heat-treated under the same atmosphere (O2 or H2), the cationicproperties of Au were enhanced as the Au particle size decreased.
When compared with the same sHAP support, cationicproperties of Au were much more enhanced for
Au/sHAP_300_O2. It is likely that the electronic interaction
between Au and the support became stronger as the Au particle
size decreased and as the number of surface Au atoms in contact
with HAP increased due to SMSI.
We evaluated the catalytic activities of the obtained
Au/sHAP catalysts for the isomerization of 34DABE. Fig. 7
shows that the higher the cationic state of Au, the higher the
14DABE yield. In comparison with the same Au/sHAP,
Au/sHAP_300_O2 showed higher catalytic activity thanAu/sHAP_300_H2 despites the fact that the Au particle size was
not different. Generally, the formation of SMSI improves
thermal stability and durability of metal NP catalysts but shows
negative effect on catalytic activity due to a decrease in thenumber of exposed surface metal atoms. It is worth noting thatthe enhanced electronic effect of SMSI on Au surpassed thedisadvantage of the decrease in the number of active sites.
Moreover, the catalyst with SMSI showed no significant
deactivation after five recycling tests, indicating that the
durability of the catalysts was improved by SMSI.

■Reviews
1. C–H Bond Functiionalization Using Pd- and Au-Supported
Catalysts with Mechanistic Insights of the Active Species, T.
Ishida ・ Z. Zhang ・ H. Murayama ・ E. Yamamoto ・ M.
Tokunaga, Synthesis, 53, 3279–3289 (2021).
■BooksSee the annual report in Japanese (3 articles)■Invited Lectures
1. Nano-structure Controlled Nanosheet-dye Complexes andtheir Utilization for Photochemical Reactions, S. Takagi (T.
Shimada, T. Ishida), Asian photochemistry conference 2021,
Invited, Online, Octber-November, 2021.
2. Unique photochemical properties of dyes on the inorganic
nanosheets, S. Takagi, (K. Arakawa, T. Shimada, T. Ishida),
2021 International Chemical Congress of Pacific Basin
Societies (PACIFICHEM 2021), Invited, Online, December,2021.
3. The effect of flat inorganic surface on the photochemical
properties and reactions of molecules, S. Takagi (T. Shimada,T. Ishida), Saturday Seminar Series (Hosted by Professor V
Ramamurthy), Invited, Online, March, 2022.
■Academic Meeting＊International
1. “In-water” Dehydration reaction of Aromatic Diol on
Saponite Surface, K. Arakawa, T. Shimada, T. Ishida, S.
Takagi, Asian photochemistry conference 2021, Online,
Octber-November, 2021.

Fig. 7 Relationships between catalytic activity for the isomerizsation of
34DABE to 14DABE and cationic properties of Au for
Au/sHAP_300_O2 with SMSI and Au/sHAP_300_H2 without SMSI.

■Papers with Peer Review
1. Y. Hirade, T. Ishida, T. Shimada, S. Takagi, Colloids Surf. A
Physicochem. Eng. Asp., 624, 126747-126752(2021).
2. Y. Yoshida, T. Shimada, T. Ishida, S. Takagi, ACS Omega, 6,21702-21708 (2021).
3. K. Arakawa, T. Shimada, T. Ishida, S. Takagi, Langmuir, 37,
11978–11985 (2021).
4. R. Onishi, K. Sano, T. Shimada, T. Ishida, S. Takagi, Bull.
Chem. Soc. Jpn., 94, 937-942 (2021).
5. Y. Ohsaki, R. Shibatani, T. Shimada, T. Ishida, S. Takagi,
Chem. Lett., 50, 1983-1986 (2021).
6. S. Mathew, A. Sebastian, F. Kuttassery, S. Takagi, H.
Tachibana, H. Inoue, Inorg. Chim. Acta, 526, 120529120539 (2021).
7. K. Arakawa, K. Suzuki, R. Nakazato, Y. Hirade, T. Shimada,T. Ishida, T. Yui, S. Takagi, Clay Science, 25, 27-31 (2021).
8. R. Nakazato, Y. Kou, D. Yamamoto, T. Shimada, T. Ishida,
S. Takagi, H. Munakata, K. Kanamura, H. Tachibana, H.
Inoue, Res. Chem. Intermed., 47, 269–285 (2021).
9. A. Waheed, X. Wang, N. Maeda, D. M. Meier, T. Ishida, T.
Murayama, M. Haruta, A. Baiker, Catal. Commun., 148,
106183-106189 (2021).
10. S. Chen, A. M. Abdel-Mageed, A. Hauble, T. Ishida, T.
Murayama, M. Parlinska-Wojtan, R. J. Behm, Appl. Catal.
A: Gen., 624, 118318-118327(2021).
11. S. Chen, A. M. Abdel-Mageed, C. Mochizuki, T. Ishida, T.

＊Domestic
See the annual report in Japanese (40 articles)■Awards
1. The Best Presentation Award for Students, Annual
Meeting on Photochemistry 2021, Ryosuke NAKAZATO(D3), September, 2021.
2. Excellent Presentation Award, 64th Annual Meeting of
The Clay Society of Japan, Kyosuke ARAKAWA (D2),September, 2021.
3. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2021, Kensuke IIKURA (M2),
December, 2021.
4. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2021, Ryota SHIMADA (M1),
December, 2021.
5. The Best Presentation Award, Symposium on Molecular
Photo-Functionalities 2021, Emiko NAKAYAMA (B4),
December, 2021.

20

Reports from Research Groups
Analytical Chemistry Laboratory■Members
Hizuru NAKAJIMA
Associate Prof. / Dr.Eng.
Analytical Chemistry, Micro-TAS, Chromatography,
Electrophoresis, Chemical sensor, Bio sensor
room: 9-343
TEL: +81-42-677-1111 Ext.4882
e-mail: nakajima-hizuru @tmu.ac.jp
Shungo KATO
Associate Prof. / Dr.Eng.
Atmospheric Chemistry, Analytical Chemistry, Geochemistryroom: 9-338
TEL: +81-42-677-1111 Ext.4875
e-mail: shungo @tmu.ac.jp

2. Development of 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.

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.
Biotechnology, Chemical Engineering, Colloid Chemistryroom: 9-148
TEL: +81-42-677-1111 Ext.4838
e-mail: noritomi @tmu.ac.jp
Yoshinori INOUE
Tech. Assistantroom: 9-290
TEL: +81-42-677-1111 Ext.4872
e-mail: inoue-yoshinori @ jmj.tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistantroom: 9-291
TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp

3. Development of 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.

Doctor’s course -3
Master’s course -12
Bachelor 4 -7
Research student-2■Outlines of the Research
1. 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.

21

Reports from Research Groups
4.

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.

Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen concentration in suburban, urban, and remote sites
were observed. Measeruemts on tunnels to observe car exhaust
were conducted.
10. Development of microchemical pen and its applications
Sifeng MAO
Micro-chemical pen (MCP), developed by our research group,
represents a novel versatile tool for nanowires fabrication. MCP
has been proven successful in generating silver nanowires,
however, the performance of nanowire fabricated by MCP in
sensing chemical/biological species never been investigated.
them difficult to use in nano-sensors. For a nanowire to be used
in a sensor, long nanowires would be more competitive. The
selective fabrication of highly ordered nanowires with highaspect ratios was of low reproducibility, which remains achallenge for laboratory research. Moreover, the mechanism andthe fabrication of gold nanowires are still in progress.

Extended Gate electrodeIon sensitive membrane
Commercial FET

Gate
N
N-channel

SourceN
P-Silicon

イオン感応膜 (Ta2O5)

Drain

エポキシ樹脂11 Insight into micro-chemical pen: microfluidic mechanism
for high-resolution surface processing
Sifeng MAO
In this study, we have confirmed the existence of anintermediate layer when MCP is working, which provides MCP
with extra advantages in surface processing over theconventional open-space microfluidic systems. The variation of
the size of IL caused by adjusting relative parameters is further
proved to be an important factor for controlling the working area.
Although the relationship between the IL and mixing region has
not been constructed in fluorescence experiments, theconsistence we found between the proposed working principleof IL and the numerical simulation results is enough to explain
how much the IL plays a role in the outstanding works of MCP.

マルチチャンネル
ISFETセンサー

10 mm

海⽔

300 mm

間隙⽔100 mm堆積物

ISFET 回路基板

Id

沖縄県 恩納村

バッテリー

WQC [⽔質計](ガラスpH電極)

ISFETセンサー

ISFET回路基板

データロガーWQC

5. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
uburban site (Minamiosawa, Koto-ku, Kyoto). Emission sources,
contribution to ozone formation of each VOC were estimated.
Test measruemnts of ambient air by SIFT-MS was conducted.
6. Atmospheric trace species measurements at remote sites
Shungo KATO
Atmospheric carbon monoxide, ozone, various volatile organic
compounds, and hydrogen were continuously observed atremote sites: cape Hedo in Okinawa, Suzu in Ishikawa.
7. Measurements of atmospheric pollutants at mountain sites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide were observed at
the top of Mt. Fuji and the foot of Mt. Fuji (Tarobo observationsite). Clear diurnal cycle caused by air motion were observed.
Volcanic gas from Mt. Asama to Tarobo was observed.

12 Regioselective fabrication of gold nanowire using openspace laminar flow for attomolar protein detection
Sifeng MAO
We present an open-space laminar flow approach forfabricating single gold nanowire in a regioselective manner for
the first time. This method enabled us to fabricate gold
nanowires with the widths ranged of a tens of nanometer to a few
micrometers at targeted locations. The gold nanowires werecomposed of multiple nanoparticles aggregated into a wire-likestructure. Due to the structure, a highly sensitive biosensor was
successfully realized as sensitive as 1 aM IgA using this single

8. Development of volcanic gas monitoring system using
small gas sensor
Shungo KATO
Realtime measurement of volvanic gas at the top of Mt. Fuji
during winter without commercial electric power was donductedwith low power gase sensor and LPWA ELTRES (SONY). Also,
measuremnent of volcanic gases using a portable system wasconducted at trails of Mt. Fuji and Owakudani, Hakone volcano.
9. Hydrogen measurement in ambient aire22

Reports from Research Groups
gold nanowire. The high-performance IgA detection wasachieved using a single gold nanowire in this study, however, bychanging the modification of the gold nanowires according to
the target substance, we expect to develop a sensor that canmeasure various substances with high sensitivity in the field ofpharmacology, medical care, food analysis, environmental
analysis and even of infection diagnose.

calcium concentration cells by L-type calcium channel
stimulation to the connected cells. Thus, the open microfluidics
would provide a new method for cell-to-cell signaling studies,development study of networking, and can also be useful for
disease treatment.

13. Push-pull nozzle system for electrochemical detection of
lactate from single cell
Sifeng MAO
In this study, we have presented a new method for thenoninvasive, instant, high spatial resolution detection of lactate
from single cells. This work involved the use of an in situ
electrochemical detection system based on push-pull nozzle
system that was developed in this laboratory. Its unique flow
system and two-step enzyme transfer measurement enabled us tostably and accurately detect the release of lactate from a single
cell. Single cell heterogeneity was successfully monitored in realtime and in situ, without any invasive sample treatment. A
distinct difference in lactate concentration between single cells
was found, indicating that different pathways might be involvedin lactate metabolism, which was an often-neglected part ofprevious studies of tumor microenvironments. Our method
provides a new approach for analysing some of the components
from a single cell, is potential for understanding of cell
heterogeneity.

15. 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 wasused as an enzyme carrier. We found that biochar imparts
high heat stress tolerance and organic solvent stress
tolerance to enzymes. This result would be expected to theapplications to bioprocesses such as bioreactors, biosensors,and biofuel cells.

■Papers with Peer Review
1. Q. Zhang, S. Feng, L. Lin, S. Mao, Z. Li, J.-M. Lin
Emerging open microfluidics for cell manipulation
Chemical Society Reviews, 2021, 50, 5333-5348
2. Kenji Morita, Kazuhiro Morioka, Hizuru Nakajima, Katsumi
Uchiyama, Akio Yanagida, Atsushi Shoji
Film-Thickness-Controllable System for Preparing Silver
Nanofilms through Absorbance Monitoring of the Thickness
during a Silver-Mirror Reaction
Analytical Sciences, 2021,37,4,625-631
3. Zhou Lin, Kasai Nahoko, Nakajima Hizuru, Kato Shungo,
Mao Sifeng, Uchiyama, Katsumi
In situ single cell stimulation and real-timeelectrochemical
detection of lactate response using microfluidic probe
Analytical Chemistry 2021,93,8680-8686
4. Xinning He, Tsuguhiro Kaneko, Huan Luo, Hang Cong,
Hizuru Nakajima, Hulie Zeng
A simple and efficient approach to sensitize the fluorescence
detection to microwell plate
Sensors and Actuators B: Chemical, 343 130070-130070
5. Sifeng Mao, Xiaohong Hu, Yumi Tanaka, Lin Zhou, Chenhan
Peng, Nahoko Kasai, Hizuru Nakajima, Shungo Kato,
Katsumi Uchiyama
A chemo-mechanical switchable valve on microfluidic chip
based on a thermally responsive block copolymer
Chinese Chemical Letters, In press
6. Kojiro Shimada, Manatsu Mizukoshi, Chak K.Chan, Yong
Pyo Kim, Neng-Huei Lin, Kazuhide Matsuda, Syuichi
Itahashi, Yoshihiro Nakashima, Shungo Kato, Shiro
Hatakeyama
Disentangling the contribution of the transboundary out-flowfrom the Asian continent to Tokyo, Japan
Environmental Pollution, 286, 117280, 2021
7. J. Chen, S. Mao, Z. He, L. Yang, J. Zhang, J.-M. Lin, Z.-X.
Lin
Proteomic Distributions in CD34+ Microvascular Niche
Patterns of Glioblastoma

14. In situ subcellular processing program for single cell
analysis by open microfluidic probe
Sifeng MAO
In this study, a new open microfluidic probe was used to
explore the communication between cells by precise
manipulation of a part of the cell. By controlling the fluid
velocity at each nozzle, a thin effective region was formed in thecentral region of the probe. The fluid in the effective region was
stable and had high spatial resolutions enough to stimulate andoperate a limited region of a single cell without affecting theother parts. The calcium transport was observed from high23

Reports from Research Groups
Journal of Histochemistry & Cytochemistry, 2021, 70, 99-110
8. Jiaru Lia, Nanase Kohnoa, Yosuke Sakamoto, Yukiko
Fukusaki, Yuka Kousa, Yasuhiro Sadanaga, Yoshihiro
Nakashima, Kei Sato, Sathiyamurthi Ramasamy, Akinori
Takami, Ayako Yoshino, Tomoki Nakayama, Shungo Kato,
Natsuki Ono, Jun Zhoua, Yu Bai, Yoshizumi Kajii
A quantitative understanding of total OH reactivity and ozone
production analysis in a coastal industrial area during
AQUAS–Yokohama campaign in summer 2019
Atmospheric Environment, 267, 2021, 118754
9. Kazuhiro Morioka, Moeko Osashima, Nao Azuma, Kuizhi Qu,
Akihide Hemmi, Atsushi Shoji, Hiroya Murakami, Norio
Teshima, Tomonari Umemura, Katsumi Uchiyama, Hizuru
Nakajima
Development of a fluorescence microplate reader using anorganic photodiode array with a large light receiving area
Talanta, 238, 122994-122994
10. Ryo Ishii, Kazuhiro Morioka, Takuya Mizumoto, Natsumi
Yamasaki, Akihide Hemmi, Atsushi Shoji, Hiroya Murakami,
Norio Teshima, Tomonari Umemura, Katsumi Uchiyama,
Hizuru Nakajima
Development of Portable Fluorescence Microplate Reader
Equipped with Indium Tin Oxide Glass Heater for Loopmediated Isothermal Amplification
Sensors and Materials, Vol. 34, No. 3 (2022) 971–985
11. Atsushi Shoji, Miyu Nakajima, Kazuhiro Morioka, Eiji
Fujimori, Tomonari Umemura, Akio Yanagida, Akihide
Hemmi, Katsumi Uchiyama, Hizuru Nakajima
Development of a surface plasmon resonance sensor using an
optical fiber prepared by electroless displacement gold plating
and its application to immunoassay
Talanta, 240, 123162-123162

See the annual report in Japanese ( 2 articles)■Invited Lectures■Academic Meeting＊International＊Domestic■Books
1. Hidetaka Noritomi
Promotion in refolding and heat stress tolerance of proteins byadsorption immobilization to biochar
New Frontiers in Medicine and Medical Research Vol. 6, Ed by
Syed A. A. Rizvi
Book Publisher International, London, United Kingdom,
Chapter 3, (2021) 9-20
2. Hidetaka Noritomi
Application of ionic liquids to enzyme stabilizers for the heatstress tolerance of enzymes
Highlights on Medicine and Medical Research Vol. 11 Ed by
Dharmesh Chandra Sharma
Book Publisher International, London, United Kingdom,
Chapter 12, (2021) 92-103■Awards24

Reports from Research Groups
Shishido Laboratory■Members

activity, reusability and environmentally-friendly nature of theheterogeneous gold catalysts as well as the scalability of thereaction system realize the sustainable synthesis of aryl andheteroarylsilanes.

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

δ-chemistry,δ+• Reusable catalyst• Without any additives• Wide substrate scope: 38 samples

PD -2
Doctor’s course -1
Master’s course -12
Bachelor 4 -7

Lactic acid production from glucose over Y2O3-based catalysts
under base-free conditions■Outlines of the Research

Methods to catalytic conversion of glucose into lactic acid (LA),which is a versatile platform chemical, have been widely
investigated. Herein, a variety of metal oxide catalysts were used
for lactic acid (LA) production from glucose under strong
homogeneous base-free conditions. Among the metal oxides
tested, Y2O3 afforded LA in moderate yield together with trioses(dihydroxyacetone and glyceraldehyde) and fructose. It was
found that the Y2O3/SiO2 catalyst can effectively catalyze thetransformation of glucose into LA. Compared to Y2O3, the LA
yield was remarkably improved. The characterization results
showed that Y(OH)3 was highly dispersed on the Y2O3/SiO2
catalyst, acting as a Brønsted base and promoting LA formationfrom pyruvaldehyde (PA). Brønsted acid sites (hydroxyl groups)
located at the interface between Y(OH)3 and SiO2 promoted thedehydration of trioses to form PA. The acid and base sites on theY2O3/SiO2 catalyst functioned in concert to ensure that theoverall reaction proceeded efficiently.

Sstructural analysis of supported Pd-Te catalyst effective foroxidative diacetoxylization of olefins
1,4-butandiol (1,4-BDO) is used as a raw material for various
compounds and is industrially produced by diacetoxylation of
1,3-butadiene (1,3-BD) by supported Pd catalyst, followed byhydrogenation and hydrolysis. The most difficult step isdiacetoxylation of 1,3-BD, and thus novel catalyst withimproved activity and selectivity is required. In this study, thealloying effect of Te on Pd was investigated in detail. Various
characterizations revealed that changes in the structure of the
supported metal species affect the catalytic activity in addition
to the interaction between Pd and Te. It was found that the highly
active catalyst maintained the fcc structure of Pd and selectively
formed the PdTe alloy on the surface, which facilitated theinteraction with the substrate 1,3-BD, and stabilized theintermediate.

■Papers with Peer Review

High-efficiency silylation of sp2 C–H bonds with supported Au
catalysts

1.

Heterogeneous gold-catalyzed C(sp2)–H silylation is developed.
A variety of heteroarenes and electron-rich arenes participated ingold-catalyzed silylation to afford the corresponding heteroaryl
and arylsilanes in good to excellent yields. A detailed
mechanistic investigation corroborated that the cooperative
catalysis of ether and O2-activated gold nanoparticles realized
heterolysis of the Si–H bond to generate silyl cations, whichenabled subsequent electrophilic C–Si bond formation. The high

2.

3.

25

Gold-Catalyzed Thioetherification of Allyl Benzyl andPropargyl Phosphates Miura, H.; Toyomasu, T.; Nishio,
H.; Shishido, T. Catal. Sci. Technol. 2022, 12, DOI:
10.1039/D1CY02085D
Deposition of Highly Dispersed Gold Nanoparticles onto
Metal Phosphates by Deposition-Precipitation with
Aqueous Ammonia Nishio, H.; Miura, H.*; Kamata, K.;
Shishido, T. Catal. Sci. Technol. 2021, 11, 7141–7150.
Electrophilic C(sp2)-H Silylation by Supported Gold
Catalysts Miura, H.; Hirata, R.; Toyomasu, T.; Shishido,
T. ChemCatChem 2021, 13, 4705–4713.【Featured as a
Front Cover】【Highlighted in ChemistryViews 2021.】

Reports from Research Groups
4.

5.

6.

7.

8.

9.

Selective catalytic oxidation of ammonia to nitrogen overzeolite-supported Pt-Au catalysts: Effects of alloy
formation and acid sites Wang, H.; Lin, M.; Murayama, T.;
Feng, S.; Haruta, M.; Miura, H.; Shishido, T. J. Catal.
2021, 402, 101–113.
Ag size/structure-dependent effect on low-temperature
selective catalytic oxidation of NH3 over Ag/MnO2 Wang,
H.; Lin, M.; Murayama, T.; Feng, S.; Haruta, M.; Miura,
H.; Shishido, T. ACS Catal. 2021, 11, 8576–8584.
Lactic acid production from glucose over Y2O3-based
catalysts under base-free conditions Hata, D.; Aihara, T.;
Miura, H.; Shishido, T. J. Jpn. Petrol. Inst. 2021, 64, 280–
292.
High-density formation of metal/oxide interfacial catalytic
active sites through hybrid clustering, Hayashi, S.;
Shishido, T. ACS Applied Materials & Interfaces, 2021, 13,22332–22340.
Isotopic 18O/16O Substitution Study on the Direct Partial
Oxidation of CH4 to Dimethyl Ether over a Pt/Y2O3
Catalyst Using NO/O2 as an Oxidant, Ghampson, I. T.;
Lundin, S.-T. B.; Shishido, T.; Oyama, S. T. Catal. Sci.
Technol. 2021,11, 2708–2712.
Metal–support cooperation in Al(PO3)3-supported
platinum nanoparticles for the selective hydrogenolysis ofphenols to arenes Jin, X.; Tsukimura, R.; Aihara, T.; Miura,
H.; Shishido, T.; Nozaki, K. Nat. Catal. 2021, 4, 312–321.
【Featured as a Front Cover】■Invited Lectures
1.

2.

3.

4.

Switching the Selectivity of CO2 Hydrogenation OverSupported Rh Catalysts Tetsuya Shishido, Kazuma Fukuda,
Junpei Suzuki, Hiroki Miura, The Second International
Symposium of Young Scholar on Carbon Resources
Conversion, Oct. 15, 2021, Bangkok, Thailand
Design of supported palladium-gold alloy catalysts forhighly efficient hydrogen storage systems
Tetsuya Shishido, Hiroki Miura, The international
Chemical Congress of Pacific Basin Societies
2021(Pacifichem 2021, Virtual), Dec. 16-21, 2021, Online
Borylation of sp3 C-O bonds under heterogeneous gold
catalysis H. Miura, The 2nd International Electronic
Conference on Catalysis Sciences (ECCS2021), October27, 2021, Online
Switching the Selectivity of CO2 Hydrogenation OverSupported Rh Catalysts, Tetsuya Shishido, Kazuma
Fukuda, Junpei Suzuki, Hiroki Miura, , The international
Chemical Congress of Pacific Basin Societies
2021(Pacifichem 2021, Virtual)Dec. 16-21, 2021,
Online■Academic Meeting＊Domestic
See the annual report in Japanese (25 articles)■Awards
1.

2.

Poster Award "C-H silylation of indoles by supported Au
catalysts" Tomohiro Tanaka 18th Workshop on Catalysis
science (16-18 September 2021, online).
Poster Award "Effect of phosphrous addition on CO2hydrogenation by supported Rh catalysts" Kazuma Fukuda
18th Workshop on Catalysis science (16-18 September
2021, online).

26

Reports from Research Groups
ShudoLaboratory■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 -6
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 productremoval 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■Review
See the annual report in Japanese■Academic Meeting＊Domestic
See the annual report in Japanese■Awards
See the annual report in Japanese27

Applied Chemistry Colloquium

393rd

2021/9/14
Takeshi Serizawa (Tokyo Institute of Technology)” Functional polymer materials by biomimetic properties”

394th

2021/12/3
Toshio Kamiya (Tokyo Institute of Technology)” New material design utilizing chemistry and computational science”

395th

2021/12/7
Hideo Hosono (Tokyo Institute of Technology)” From molecular chemistry towards condensed matter science”

396th

2021/12/23
Masamichi Yamanaka (Meiji Pharmaceutical University)” Creation of supramolecules by molecular design of urea derivatives”

28

Annual Report 2021
Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry for Environmental Sciences
April 1, 2022