Faculty of Environmental Sciences
Division of Applied Chemistry
Graduate School of Environmental Sciences
Department of Applied Chemistry

Annual Report 2017

IndexReports from Research Groups
Kawakami Laboratory

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1

Masuda Laboratory

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8

Setaka Laboratory

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10

Haruta Laboratory

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12

Kanamura Laboratory

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17

Takagi Laboratory

▪▪▪▪▪

20

Yamaguchi Laboratory

▪▪▪▪▪

23

Uchiyama Laboratory

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25

Kubo Laboratory

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30

Shishido Laboratory

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33

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36

ColloquiumReports from Research Groups
Kawakami Laboratory■Members

membranes was analyzed by utilizing the 13C-NMR
spectroscopy with 13CO2 probe and gas adsorption
measurements.

Hiroyoshi KAWAKAMI
Professor / Dr. Eng.
Polymer Chemistry, Functional Polymers, Nanofiber
Engineering, Biomaterials, Epigenetics Engineering, Free
Radical ScienceRm. 9-638, +81-42-677-1111 Ext. 4972
kawakami-hiroyoshi@tmu.ac.jp
Shoichiro ASAYAMA
Associate Professor / Dr. Eng.
Biomaterials,
Biomedical
Polymers,
Biomolecular Engineering
Rm. 9-651, +81-42-677-1111 Ext. 4976
asayama-shoichiro@tmu.ac.jp

Biochemistry,
Figure 1. Schematic illustration of the polymer composite
membranes containing the surface-modified silica nanoparticles
with various shapes.

Masafumi YAMATO
Associate Professor / Dr. Eng.
Polymer Science, Magneto-ScienceRm. 9-137, +81-42-677-1111 Ext. 4837
yamato-masafumi@tmu.ac.jp

2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA

Manabu TANAKA
Assistant Professor / Dr. Eng.
Polymer Chemistry, Polymer Electrolytes, Nanofibers, Polymer
Membranes
Rm. 9-639, +81-42-677-1111 Ext. 4586
tanaka-manabu@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 fabricated novel electrospun polymer
nanofibers containing sulfonate and phosphonate groups thatcan form effective proton conductive pathway inside thenanofibers (Figure 2). The novel polymer composite
membranes composed of the blend or core/shell nanofibers
showed higher proton conductivity than the conventional
composite membranes, especially under low humidity
conditions, which are assumed as future fuel cell operation
conditions.

Riku KUBOTA
Specially-appointed Assistant Professor / Dr. Eng.
Supramolecular Chemistry, Complex Chemistry, Catalyst
ChemistryRm. 9-649, +81-42-677-1111 Ext. 4973
r-kubota@tmu.ac.jp
Manjit Singh GREWAL
Specially-appointed Assistant Professor / Ph.D.
Polymer Chemistry, Polymer Electrolyte
Rm. 9-649, +81-42-677-1111 Ext. 4973
m-grewal@tmu.ac.jp
Master’s course -17
Bachelor 4 -8

■Outlines of the Research
1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO,
Manabu TANAKA
Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO2). Recently, we
have reported that novel composite membranes composed of
the fluorinated polyimide or polymers of intrinsic
microporosity (PIM) and surface-modified silica nanoparticles
exhibit high gas permeability and selectivity.
In this year, we focused on new types of nanoparticles,
including pearl-necklace shaped and chain shaped silica
nanoparticles that have originally inter-connected structures(Figure 1). As a result, we achieved to demonstrate extremely
high CO2 permeability by using the composite membrane
containing surface-modified pearl-necklace shaped silica
nanoparticles. Furthermore, the mechanism for the
improvement of CO2 permeability in these composite

Figure 2. Schematic illustration of the novel polymer
electrolyte composite membranes based on the blend or
core/shell nanofibers.
3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA, Manjit Singh
GREWAL1

Reports from Research Groups
bimetallic complex.

Recently, nano-scale fibers prepared through an electricallycharged jet of polymer solution/melt (electrospinning) havereceived a lot of attention. Nanofibers have several inherent
characteristics including high surface area, unique optical andphysicochemical properties originated from the nano-size, andalignment of polymer chains in the nanofibers. The diameter ofnanofiber is one of the most important factors to effect on such
unique characteristics. Ultrafine nanofibers with their diameters
less than 50 nm were also obtained.
In this year, we mainly focused on the fabrication of lithium
ion conductive polymer nanofibers and their composite
membranes for the secondary battery applications (Figure 3).
The novel lithium ion conductive nanofiber composite
membranes showed higher lithium ion conductivity than thecorresponding membranes without the nanofibers, especially at
low temperatures. All solid state lithium ion batteries, including
a multi-stacked bipolar type, using the nanofiber composite
membranes were fabricated and evaluated.

5. Study of Epigenetics Engineering
Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA,
Riku KUBOTA
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
carrier (EpC) containing single chain lipid. The resulting EpC
carrier exhibited long-term stability. On the other hand,interestingly, the physicochemical properties of the EpC carrier
was dependent on pH. These advantages have lead to an ability
to control gene expression of the EpC carrier. Therefore, thenovel EpC carrier may be useful to re-activate the inactivatedgene expression which is involved in pathogenesis of severe
diseases.

Figure 5. Gene expression control by the epigenetics control(EpC) carrier.

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

6. Study of Free Radical Control by Artificial Enzyme
Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA,
Riku KUBOTA

4. Supramolecular system for multi-electron redox catalyst
Hiroyoshi KAWAKAMI, Riku KUBOTA,
Fidelis SIMANJUNTAKSuperoxide dismutase (SOD) or catalase (CAT) are wellknown to efficiently eliminate superoxide radicals or hydrogen
peroxide as the most important antioxidants.
We
demonstrated that a water-soluble cationic Mn-porphyrin with
SOD activity or catalase activity exhibited anticancer activity
as well as antioxidative activity.
In this year, we have prepared novel biodegradable
nanoparticle having capacity of gene expression andantioxidation(MnPD). The efficiency for intracellular
localization of MnPD was enhanced by EpC carrier.
Furthermore, the EpC carrier exhibited significant
anti-inflammatory effect in Chronic Obstructive Pulmonary
Disease (COPD) model in vitro.

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 novel supramolecular systemcomposed of dinuclear metalloporphyrin and Cucurbit[10]uril(CB[10]) for multi-electron catalysis. The resulting
supramolecular system electrochemically produced hydrogen
under weakly acidic conditions, Furthermore, thesupramolecular system produced hydrogen from glucose as amodel of hydrogen carrier.
Two-electron redox catalyst

Cucurbit[10]uril

Metallo-bisbipyridine

Metallo-porphyrins

M=Cu, Co, Fe etc

M=Mn, Fe, Co etc

Multifunctional＆ multifunctional redox catalyst
CO2 reduction

H2 production
2H+

CO, HCOOH,
CH3OH etc

H2

CO2

O2

Oxygen reduction

H2O

Figure 6. Mn-porphyrin (MnP) with anitioxidative activity and
MnP nano-carrier.

Figure 4. Multi-electron redox reactions by supramolecular2

Reports from Research Groups
The following was examined in this year. Mixing different clay
types made it possible to create a hybrid gel with anisotropy. In
addition, we estimated the amount of molecules adsorbed onclay from the water fraction dependence of the enthalpy of coil
- globule transition and clarified high density adsorption ofmolecules on the clay surface. When combined with the resultof birefringence of the hybrid gel prepared in the magnetic field,
it was suggested that the molecules are anisotropicallyadsorbed by hydrophobic interaction on the clay surface.

7. Materials for Drug Delivery System
Shoichiro ASAYAMA, Hiroyoshi KAWAKAMI
To improve human health and quality of life (QOL), we
have designed new biomaterials for drug delivery system(DDS). The resulting carriers for DDS such as nucleic acid
(pDNA, siRNA), protein, and Zn2+ are expected to satisfy
unmet medical needs.
In this year, to improve our original mono-ion complex(MIC : Figure 7), we have designed the in vivo gene delivery
system for sustainable expression by biodegradable MIC. By
use of the resulting MIC, diffusive and sustainable gene
expression after 2 week post-injection was achieved.
Furthermore, we have established the high-density modificationof biomaterial surface with cholesterol end-modifiedpoly(ethylene glycol). The nonspecific interaction of proteins
with the resulting poly(propylene) surface was suppressed.

■Papers with Peer Review
1. Genki Ito, Manabu Tanaka, Hiroyoshi Kawakami,“Sulfonated polyimide nanofiber framework: Evaluation of
intrinsic proton conductivity and application to composite
membranes for fuel cells”, Solid State Ionics (2018) in press.
2. Shoichiro Asayama, Kana Nagashima, Yoichi Negishi,
Hiroyoshi Kawakami, “By-product-free intact mofdification of
insulin by cholesterol end-modified poly(ethylene glycol) for invivo protein delivery”, Bioconjugate Chemistry, 29, 67-73(2018).
3. Masanari Nakayama, Satoshi Kajiyama, Akihito Kumamoto,
Tatsuya Nishimura, Yuichi Ikuhara, Masafumi Yamato, Takashi
Kato, “Stimuli-responsive hydroxyapatite liquid crystal withmacroscopically controllable ordering and magneto-optical
functions”, Nature Communications, 9, 568.1-9 (2018).
4. Shoichi Hasebe, Satoshi Aoyama, Manabu Tanaka,
Hiroyoshi Kawakami, "CO2 separation of polymer membranes
containing silica nanoparticles with gas permeable nano-space",
Journal of Membrane Science, 536, 148-155 (2017).
5. Manabu Tanaka, Yasushi Takeda, Takeru Wakiya, Yuta
Wakamoto, Kaori Harigaya, Tatsunori Ito, Takashi Tarao,
Hiroyoshi Kawakami, "Acid-doped polymer nanofiber
framework: Three-dimensional proton conductive network forhigh-performance fuel cells", Journal of Power Sources, 342,
125-134 (2017).
6. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi Kawakami“Improvement in characteristics of a Nafion membrane byproton conductive nanofibers for fuel cell applications”,
Journal of Membrane Science, 530, 65–72 (2017).
7. Tsukasa Watanabe, Manabu Tanaka, Hiroyoshi Kawakami,“Anion Conductive Polymer Nanofiber Composite Membrane:
Effects of Nanofibers on Polymer Electrolyte Characteristics”,
Polymer International, 66, 382-387 (2017).
8. Motoyuki Matsuho, Riku Kubota, Shoichiro Asayama,
Hiroyoshi Kawakami, “Lactoferrin-modified nanoparticles
loaded with potent antioxidant Mn-porphyrins exhibit enhanced
antioxidative activity in vitro intranasal brain delivery model”,
Journal of Materials Chemistry B, 5, 1765-1771 (2017).
9. Shoichiro Asayama, Kana Nagashima, Hiroyoshi Kawakami,“Facile method of protein PEGylation by a mono-ion complex”,
ACS Omega, 2, 2382-2386 (2017).
10. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,“Structure-activity
relationshipbetween
Zn2+-chelatedpoly(1-vinylimidazole) and gene transfection”, Journal of
Inorganic Biochemistry, 173, 120-125 (2017).

Figure 7. Delivery to in vivo unexplored space by themono-ion complex (MIC).
8. 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 to improvesome properties and to reveal new functions of the materials.

ΔH / J mol-gel-1

150
100
50
0

0.85

0.90
0.95
water mole fraction

1.00

Figure 8. Water fraction dependence ofenthalpy of coil-globule transition■Books
1. Shoichiro Asayama, Leading biomaterials, Journal for
Japanese Society of Biomaterials, 36, 10 (2018).
2. Shoichiro Asayama, See the annual report in Japanese(2017).
3. Masafumi Yamato, Kohki Takahashi, Kazuo Watanabe,

Figure 9. Schematic drawing of NIPAm
molecules adsorbed on clay.

3

Reports from Research Groups
Study in interacton between organic molecules and clay using
magnetic alignment, 2016 Annual report of high field
laboratory for superconducting materials in institute formaterials research at Tohoku university，p.p. 143-144 (2017)(in Japanese)
4. Atsushi Mori, Masafumi Yamato, Kohki Takahashi,
Structural anisotropy in silica gels prepared in magnetic fieldfrom viewpoint of alignment transition, 2016 Annual report ofhigh field laboratory for superconducting materials in institutefor materials research at Tohoku university，p.p.137-138 (2017)(in Japanese)
5. Manabu Tanaka, Gas separation using polymer membranes,
Chemistry & Education, 65, 630-631 (2017) (in Japanaese)■Academic Meeting
1. Shoichiro Asayama, See the annual report in Japanese(2017).
2. Manabu Tanaka, Yuki Kudo, Masafumi Yamato, Hiroyoshi
Kawakami, Analysis on the gas permeation mechanism of
PIM-1 composite membranes containing surface-modified
silica nanoparticles, 39th Annual Meeting on The Membrane
Society of Japan, Waseda University, 1B-02 (May 2017) (inJapanese)
3. Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and evaluation of bipolar stacked all-solid-state
secondary battery with lithium ion conductive nanofiber
composite electrolyte membranes, 39th Annual Meeting on The
Membrane Society of Japan, Waseda University, P-38S (May2017)
4. Takahiro Ogura, Manabu Tanaka, and Hiroyoshi Kawakami,
Fabrication and fuel cell characterizations of acid-doped
nanofiber composite membranes bearing the connective proton
conductive pathways, The 39th annual meeting of Japanesesociety for membrane,(Waseda university), P-35S (May, 2017)(in Japanese)
5. Risa Sakaguchi, Manabu Tanaka, Hiroyoshi Kawakami, Fuelcell characterization of acid/base blend polymer nanofiber
composite membranes, 39th The Membrane Society of Japan,(Waseda University), (May. 2017) (in Japanese)
6. Hiroto Mikami, Yuri
Kameyama, Manabu Tanaka,
Masafumi Yamato, Hiroyoshi kawakami, Analysis of the CO2
permeation mechanism of polyimide composite containing
mixture silica nanoparticles with different morphologies,
Symposium of Membranes, Waseda university, Japan, P-13S(May, 2017) (in Japanese)
7. Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and secondary battery characterizations of lithium
single-ion conducting nanofiber composite membrane., 39th
Annual Meeting on The Membrane Society of Japan, Waseda
University, P-37S (May 2017)
8. Shoichiro Asayama et al., See the annual report in Japanese(2017).
9. Shoichiro Asayama et al., See the annual report in Japanese(2017).
10. Ryosuke Shinohara, Riku Kubota, Shoichiro Asayama and
Hiroyoshi Kawakami, Preparation of alkyl amine coating
biodegradable nanocarrier with epigenetics controlling ability,
66th SPSJ Annual Meeting(Makuhari Messe) (May, 2017)
11. Yuma Yokokawa, Riku Kubota, Shoichiro Asayama,
Hiroyoshi Kawakami, Inhibition of Aβ aggregation by β-CD-modified anionic polymer, Polymer Preprints, Japan,
Vol.66, (Makuhari messe)2Pe101 (May, 2017) (in Japanese)
12. Yuri Kameyama, Yuki Kudo, Manabu Tanaka, andHiroyoshi Kawakami, Gas permeation property of polymer
composite membranes containing silica nanoparticles having
connected structures., 66th SPSJ Annual Meeting, Japan,(Makuhari Messe), 1Pb082 (May 2017) (in Japanese)
13. Riku KUBOTA, Taiga TAKABE, Hideaki TANIGUCHI,
Hiroyoshi KAWAKAMI, Catalytic activity of novel
water-soluble supramolecular system bearing four-electron
redox properties, The 66th SPSJ Annual Meeting(Makuhari
Messe), May 2017.
14. Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation of bipolar stacked all-solid-state secondary battery
by lithium ion conductive nanofiber composite electrolyte
membrane, 66th Annual meeting of society of polymer scienceof Japan (Makuhari Messe), 1Pe079 (May 2017)15. Yuta Inafune, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi Kawakami, Evaluation of all-solid-state secondary
battery using lithium conductive nanofiber composite
electrolyte membrane, 66th Annual meeting of society ofpolymer science of Japan (Makuhari Messe), 3G05 (May 2017)
16. Kohe Arima, Riku Kumota, Shoichiro Asayama and■Invited Lectures
1. Shoichiro Asayama, See the annual report in Japanese(2017).
2. Manabu Tanaka, Tsukasa Watanabe, Hiroyoshi Kawakami,
Ion Conductive Polymer Nanofiber Framework for
All-Solid-State Lithium Ion Battery, The 21st International
Conference on Solid-State Ionics(SSI-21), Padova, Italy (June,
2017)
3. Manabu Tanaka, Hiroyoshi Kawakami, Polymer Composite
Membranes based on Proton Conductive Nanofiber Framework
for Fuel Cell Applications The 17th IUPAC International
Symposium on MacroMolecular Complexes (MMC-17),
Waseda University (June, 2017)
4. Manabu Tanaka, Fuel cell and battery applications of ion
conductive nanofibers, TIRI Cross meeting 2017 (June, 2017)(in Japanese)
5. Shoichiro Asayama, Plasmid DNA delivery system based on
Zn2+ ions for up-regulation of gene expression, The 3rdInternational Forum on Applied Chemistry (September, 2017)
6. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2017 Basic seminar of polymer science for young
engineers, Oct. 2017, Hiratsuka, Japan (in Japanese)
7. Manabu Tanaka, Ion Conductive Polymer Nanofiber
Framework: Fabrication, Characterization and Application to
Polymer Electrolyte Fuel Cells, The 2nd International
Symposium on Hydrogen Energy‒based Society, ResearchCenter for Hydrogen Energy-based Society, Tokyo
Metropolitan University (November 2017)
8. Masafumi Yamato, Higher order structure analysis forpolymeric materials, Seminar of equipment analysis forpolymers, Dec. 2017, Tokyo, Japan (in Japanese).
9. Hiroyoshi Kawakami, Fuel cell application of polymer
electrolyte membrane composed of proton conductive
nanofiber, The Electrochemical Society of Japan, Tokyo (April2017) .
10. Hiroyoshi Kawakami, Novel all splidpolymer electrolyte
membranes composed of ion conductive nanofibers, The
Membrane Society of Japan, Tokyo (May 2017) .
11. Hiroyoshi Kawakami, Chemistry saves the earth, The 1st
Advanced Research Forum, Tokyo Metropolitan University(June 2017) .
12. Hiroyoshi Kawakami, Ultra-high CO2 separation membranewith nao-space, JTIC (Tokyo) , (August 2017) .
13. Hiroyoshi Kawakami, Innovative CO2 separation
membrane with nao-space, The society of polymer science ofJapan (Tokyo) , (March 2018) .
14. Hiroyoshi Kawakami, Big Ideas In Chemistry, Waseda
University (Tokyo) , (March 2018) .
4

Reports from Research Groups
Hiroyoshi Kawakami, Curative effect of liposome-coatednanoparticle having antioxidant activity / gene expression
capacity on oxidative stress disease, 65th SPSJ Annual Meeting,
Makuhari, Japan (May, 2017)
17. Takahiro Ogura, Manabu Tanaka, and Hiroyoshi
Kawakami, Fabrication and fuel cell characterizations ofacid-doped nanofiber composite membranes bearing theconnective proton conductive pathways, 66th SPSJ Annual
Meeting(Makuhari Messe), 1Pf088(May, 2017) (in Japanese)
18. Takahiro Ogura, Takahito Makinouchi, Manabu Tanaka,and Hiroyoshi Kawakami, Fuel cell characteristics of
acid-doped nanofiber composite membranes consisted ofdensified/multi-layer surface-modified nanofiber frameworks,
66th SPSJ Annual Meeting(Makuhari Messe), 3G12(May,2017) (in Japanese)
19. Eiko Ito, Yuki Kudo, Manabu Tanaka, Masafumi Yamato,
Hiroyoshi Kawakami, Analysis of nano-space in composite
membranes containing nanoparticles., 65th SPSJ Annual
Meeting, Japan(Makuhari Messe), 1P081 (May 2017) (inJapanese)
20. Masafumi Yamato, Shoma Mochizuki, Kotaro Oyama,
Hiroyoshi Kawakami, and Noriyuki Hirota, Development of
mixed-clay hybrid gel and its mechanical property, 66th SPSJ
Annual meating, Makuhari Messe, (2Pb046) (May, 2017) (inJapanese)
21. Takabe Taiga, Taniguchi Hideaki, Kubota Riku, Kawakami
Hiroyoshi, Functional evaluation of novel water-solublesupramolecular system with multi-electron oxidation-reduction
capability, The 66th Symposium on Macromolecules(Makuhari Messe), 1Pc091 (May, 2017) (in Japanese)
22. Risa Sakaguchi, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and fuel cell characterization of acid/base blend
polymer nanofiber composite membranes, SPSJ Annual
Meeting, (Makuhari Messe), (May. 2017) (in Japanese)
23. Hiroto Mikami, Yuki Kudo, Manabu Tanaka, Masafumi
yamato, Hiroyoshi kawakami, Analysis on the gas permeation
mechanism of high gas permeable composite membranes
containing surface-modified silica nanoparticles, 66th SPSJ
Annual Meeting , Makuhari Messe, Japan, 2F10 (May, 2017 )(in Japanese)
24. Hiroto Mikami, Yuri Kameyama, Manabu Tanaka,
Hiroyoshi kawakami, Analysis of the CO2 permeation
mechanism of polyimide composite containing mixed silica
nanoparticles with different morphologies, 66th SPSJ Annual
Meeting, Makuhari Messe, Japan, 1Pa083 (May, 2017 ) (inJapanese)
25. Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
Nanofiber fabrication and electrolyte characterizations oflithium
single-ion
conducting
polymers
bearingbis(sulfonyl)imide anion side groups, 66th Annual meeting ofsociety of polymer science of Japan (Makuhari Messe), 1Pe080(May 2017)26. Shun Nakazawa, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi
Kawakami,
Preparation
andconductive
characteristics of lithium single-ion conducting nanofiber
composite membranes, 66th Annual meeting of society ofpolymer science of Japan (Makuhari Messe), 3G06 (May 2017)27. Yushi Minami, Riku Kubota, Shoichiro Asayama,
Hiroyoshi Kawakami, “ONOO- disproportionation of novel
water-solublesupramolecularsystemcomposedofMn-porphyrin/bipyridine derivative /cucurbit[10], 66th SPSJ
Annual Meeting,(May,2017),(in Japanese)
28. Kosuke Chikuma, Misaki Ouchi, Kazuhiko Nakabayashi,
Riku Kubota, Shoichiro Asayama, Hiroyoshi Kwakami,
Intranuclear behavior and chromatin structural regulation of
cyclodextrin-modified anionic polymer, 66th Annual meeting ofsociety of polymer science of Japan, 1Pe109, May 2017, Chiba,
Japan (in Japanese)
29. Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and evaluation of multi stacked all-solid-state
secondary battery comprising of lithium conductive nanofiber

composite electrolyte membranes, The Annual Meeting of theSociety of Fiber Science and Technology, Japan(Tower Hall
Funabori), 2P213 (June 2017)30. Yuta Inafune, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi Kawakami, Fabrication and evaluation of
all-solid-state secondary battery using lithium ion conductive
nanofiber framework, The Annual Meeting of the Society ofFiber Science and Technology, Japan(Tower Hall Funabori),
2E10 (June 2017)31. Takahiro Ogura, Manabu Tanaka, and Hiroyoshi
Kawakami, Fabrication and fuel cell properties of nanofiber
framework composite membranes bearing continuous proton
conductive pathways, The Annual Meeting of the Society ofFiber Science and Technology, Japan, (Tower Hall Funabori),
1P236(June, 2017) (in Japanese)
32. Takahiro Ogura, Takahito Makinouchi, Manabu Tanaka,and Hiroyoshi Kawakami, Fabrication and fuel cellcharacteristics of nanofiber composite membranes bearing highproton conductive pathways at the interface, The Annual
Meeting of the Society of Fiber Science and Technology, Japan,(Tower Hall Funabori), 1F03(June, 2017) (in Japanese)
34. Hiroto Mikami, Yuri Kameyama, Manabu Tanaka,
H3royoshi kawakami, Analysis of the CO2 permeation
mechanism of polyimide composite containing mixture silica
nanoparticles with different morphologies, The Annual
Meeting of the Society of Fiber Science and Technology ,Tower Hall Funabori, Japan, 2P212 (June, 2017 ) (in Japanese)
35. Hiroto Mikami, Yuki Kudo, Manabu Tanaka, Hiroyoshi
k4wakami, Analysis on the gas permeation mechanism of highgaspermeable
compositemembranes
containing
surface-modified silica nanoparticles, The Annual Meeting of
the Society of Fiber Science and Technology, Tower Hall
Funabori, Japan, 2E05 (June, 2017) (in Japanese)
36. Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
Nanofiber fabrication from lithium single-ion conducting
polymers by electrospinning method and their electrolyte
application for secondary battery, The Annual Meeting of theSociety of Fiber Science and Technology, Japan (Tower Hall
Funabori), 2P214 (June 2017)36. Shun Nakazawa, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi
Kawakami,
Fabricationoflithium
single-ion-conducting nanofiber framework and theirapplication to secondary batteries, The Annual Meeting of theSociety of Fiber Science and Technology, Japan (Tower Hall
Funabori), 2E11 (June 2017)
37. Riku KUBOTA, Motoyuki MATSUHO, Shoichiro
ASAYAMA, Hiroyoshi KAWAKAMI, Antioxidative activityof novel lactoferrin-modified nanoparticles loaded with potent
antioxidant Mn-porphyrins in intranasal brain delivery model invitro(Tsukuba International Congress Cnnter ),June 2017.
38. Shoichiro Asayama et al., See the annual report in Japanese(2017).
39. Kohe Arima, Riku Kumota, Shoichiro Asayama, Curative
effect of liposome-coated nanoparticle on oxidative stressdisease, Biomedical Polymers, Odaiba, Japan (July, 2017)40. Shoichiro Asayama et al., See the annual report in Japanese(2017).
41. Shoichiro Asayama, Atsushi Nohara, Sakura Taneichi,
Yoichi Negishi, Hiroyoshi Kawakami, Design of mono-ion
complex for in vivo diffusive plasmid DNA delivery, 44th
Annual Meeting & Exposition of the Controlled Release
Society, P-436 (Boston, USA) (July, 2017)
42. Riku KUBOTA, Hiroyoshi KAWAKAMI, Novelsupramolecular approach for multicatalytic activity ofMn-porphyrin derivative, The 254th ACS National Meeting ＆Exposition (Washington, D. C., USA), August 2017.
43. Riku KUBOTA, Hiroyoshi KAWAKAMI, Bioinspired
water-soluble Mn-porphyrin complex as catalase mimic forantioxidative activity, The 254th ACS National Meeting ＆Exposition (Washington, D. C., USA), August 2017.
5

Reports from Research Groups
44. Ryosuke Shinohara, Riku Kubota, Shoichiro Asayama,
Hiroyoshi Kawakami, Single chain lipid-coated biodegradable
polymer nanoparticles having co-delivery activity of drugs /plasmid DNA, the 17th IUPAC International Symposium on
MacroMolecular Complexes (MMC-17) (Waseda Univesity),
P08(August 28-31, 2017)45. Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Characterization of Composite Electrolyte
Membranes composed of Lithium Ion Conductive Nanofiber
Framework, The 17th IUPAC International Symposium on
Macromolecular Complexes (MMC-17), Waseda University,
P-41 (August 2017)
46. Kohe Arima, Riku Kumota, Shoichiro Asayama, Effect ofliposome-coated nanoparticle possessing antioxidant activity
and gene expression capacity on oxidative stress disease,
Waseda, Japan, (August, 2017)
47. Takahiro Ogura, Takahito Makinouchi, Manabu Tanaka,and Hiroyoshi Kawakami, Fabrication and Fuel Cell
Application of Nafion Composite Membrane Containing
Proton Conductive Nanofiber Framework, The 17th IUPAC
International
SymposiumonMacroMolecularComplexes(WASEDA University), (August, 2017)
48. Mikami Hiroto, Shoich hasebe, Manabu Tanaka, Hiroyoshi
Kawakami, CO2 Separation Membranes Containing
Surface-modified Silica Nanoparticles with Gas Permeable
Nano-Space. IUPAC 17th International Symposium on Macro
Molecular Complexes (MMC-17), Waseda University, Japan,(August, 2017)
49. Riku KUBOTA, Hiroyoshi KAWAKAMI, Supramolecularsystem composed of Mn-porphyrin, imidazole andcucurbit[10]uril toward multielectron redox catalyst, The 17th
IUPAC International Symposium on MacroMolecularComplexes(Waseda University, Japan), August 201750. Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and electrolyte characterizations of nanofiber
composite membranes with lithium single-ion conductivity,
The 17th IUPAC International Symposium on MacromolecularComplexes (MMC-17), Japan (Waseda University), P-42
(August 2017)
51. Masafumi Yamato, Magnetic field control of low
dimensional nano interface array ， Meeting of TechnicalCommittee on Biomagnetic and Magnetic Field Effect Studies，Aug. 2017, Tokyo, Japan (in Japanese)
52. Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication of lithium ion conductive nanofiber composite
electrolyte membranes for all-solid-state lithium ion battery,
International Seminar on Green Energy Conversion 2017 ,Koumi, P55 (September, 2017)53. Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
FABRICATION AND EVALUATION OF LITHIUMSINGLE-ION CONDUCTING NANOFIBER COMPOSITEMEMBRANES, International Seminar on Green Energy
Conversion, Japan (Koumi), P-56 (September 2017)
54. Ryosuke Shinohara, Risa Shimazaki, Riku Kubota,
Shoichiro Asayama and Hiroyoshi Kawakami, Cell
differentiation by epigenetics control aiming diabetes therapy,
The 55th Annual Meeting of the Japanese Society for Artificial
Organs(Hosei University Ichigaya Campus), YP3-1(September,
2017)
55. Manabu Tanaka, Yuta Inafune, Shun Nakazawa, Kaito
Takenaka, Hiroyosi Kawakami, Design and secondary battery
application of solid polymer electrolyte based on nanofiber
framework, The 66th SPSP Symposium (Ehime University),
September 2017.
56. Riku KUBOTA, Hiroyoshi KAWAKAMI, Water-solublesupramolecular system for multielectron redox reaction, The
66th SPSP Symposium(Ehime University),September 2017.
57.
Riku
KUBOTA,
Hiroyoshi
KAWAKAMI,
Structure-activity relationship for multielectron redox reactionof water-soluble supramolecular system, The 66th SPSP
Symposium(Ehime University),September 2017.

58. Shoichiro Asayama et al., See the annual report in Japanese(2017).
59. Shoichiro Asayama, Atsushi Nohara, Sakura Taneichi,
Yoichi Negishi, Hiroyoshi Kawakami, Biocompatible highly
condensed plasmid DNA for in vivo diffusive delivery, The
25th Anniversary Congress of the European Society of Gene &Cell Therapy, P-380 (Berlin, Germany) (October, 2017)
60. Riku KUBOTA, Hiroyoshi KAWAKAMI, Mechanism ofoxygen reduction reaction of water-soluble supramolecularsystem composed of metalloporphyrin / metallobypiridine /Cucurbit[10]uril, The 67th Conference of Japan Society of
Coordination Chemistry(Hokkaido University),September 2017
61. Taiga Takabe, Hideaki Taniguchi, Riku Kubota, Hiroyoshi
Kawakami,
Structure-activity
relationshipofnovel
water-soluble supramolecules composed of metal porphyrin /metal bipyridine / cucurbit [10]，The 67th Japan Society of
Coordination Chemistry Symposium (Hokkaido university)，
1PF-032 (September, 2017) (in Japanese)
62. Manabu Tanaka, Tsukasa Watanabe, Yuta Inafune,
Hiroyoshi Kawakamia,Solid Polymer Electrolytes Based on Ion
Conductive Nanofiber Framework for Lithium Ion Battery,
232nd ECS MEETING (National Harbor, MD) A01-0064(October, 2017)
63. Takahiro Ogura, Manabu Tanaka, and Hiroyoshi
Kawakami, Fabrication of nanofiber framework composite
membranes suitable for low-humidified fuel cell operation,
53th symposium on Polymer and Water Japan(Tokyo Instituteof Technology), P8(November, 2017) (in Japanese)
64. Hiroto Mikami, Takuya Muramoto, Yuri Kameyama,
Masafumi Yamato, Manabu Tanaka, Hiroyoshi kawakami,
Influence of surface-modified nanoparticles on gas permeation
properties of polymer composite membranes. 55th symposiumof water and polymer, Tokyo Institute of Technology, Japan,
P7 (November, 2017 ) (in Japanese)
65.
KotaroOyama,
Masahumi
Yamato,Shoma
Mochizuki,Noriyuki Hirota,Hiroyoshi Kawakami, Anisotropic
swelling behavior of organic/inorganic hybrid gels prepared ina magnetic field, 55th Symposium on Polymer and Water,
Japan,p.23( November, 2017) (in Japanese)
66. Shoichiro Asayama et al., See the annual report in Japanese(2017).
67. Takahiro Ogura, Manabu Tanaka, and Hiroyoshi
Kawakami, Fabrication and characterization of acid-doped
polybenzimidazole nanofiber composite membranes, 25th
Japan Polyimide & Aromatic Polymer Conference(Tokyo
Polytechnic University), (November, 2017) (in Japanese)
68. Hiroto Mikami, Manabu Tanaka, Masafumi Yamato,
Hiroyoshi kawakami, Gas permeability evaluation of polyimide
composite membranes containing mixed silica nanoparticles
with different morphologies. 25th symposium of polyimide andAromatic polymer, Tokyo kougei University, Japan,(November, 2017) (in Japanese)
69. Masafumi Yamato, Shoma Mochizuki, Hiroyoshi
Kawakami, and Noriyuki Hirota, Mechanical properties ofnanocomposite gel prepared in magnetic field, 87th Musashinoarea polymer association, Tokyo University of Technology,
Poster(November, 2017)(in Japanese)
70. Kazuma Komine, Masafumi Yamato, Hiroyoshi
Kawakami,Phase transition enthalpy of nanocomposite gel withdifferent water content,87th Musashino area polymer
association, Tokyo University of Technology, Japan, poster(November, 2017) (in Japanese)
71. Masafumi Yamato, Shoma Mochizuki, Hiroyoshi
Kawakami, and Noriyuki Hirota, Mechanical properties ofnanocomposite gel prepared in magnetic field, 12th
Magneto-Science Society of Japan , Kyoto University, Abstractp.112-113 (P-31) (November, 2017) (in Japanese)
72. Masafumi Yamato, Shoma Mochizuki, Hiroyoshi
Kawakami, and Noriyuki Hirota, Mechanical properties ofnanocomposite gel polymerized in magnetic field,
6

Reports from Research Groups
JSAP-MSSJ-study group of fiscal 2017, Tokyo Metropolitan
University Akihabara satellite campus, (P-11) (November,2017) (in Japanese)
73. Kazuma Komine, Masafumi Yamato, hiroyoshi Kawakami,
Thermal analysis of nanocomposite gel, Applied Physics
Society The Magneto-Science Society of Japan2017, Tokyo
Metropolitan University Akihabara satellitecampus, P-4(November, 2017) (in Japanese)
74. Takahiro Ogura, Takahito Makinouchi, Manabu Tanaka,and Hiroyoshi Kawakami, Fabrication and Fuel Cell
Application of Nanofiber/Nafion Composite Membranebending proton conductive pathways, The 2nd International
Symposium on Hydrogen Energy‒based Society (Tokyo
Metropolitan University), (November, 2017)
75. Taiga Takabe, Riku Kubota, Hiroyoshi Kawakami,
Bioinspired water-soluble Mn-porphyrin complex for catalytic
activity ， The 2nd International Symposium on Hydrogen
Energy‒based Society (Tokyo Metropolitan university)，P-20(November, 2017) (in English)
76. Mikami Hiroto, Shoich hasebe, Manabu Tanaka, Hiroyoshi
Kawakami, CO2 Separation Membranes Containing
Surface-modified Silica Nanoparticles for High Gas
Permeation. The 2nd International Symposium on Hydrogen
Energy‒based Society. Tokyo Metropolitan University, Japan,(November, 2017)
77. Manabu Tanaka, Yuta Inafune, Shun Nakazawa, Kaito
Takenaka, Hiroyoshi Kawakami, Fabrication and Secondary
Battery Application of Solid Polymer Electrolytes Based on
Lithium Ion Conductive Nanofiber Framework, The 58th
Battery Symposium (Kyushu International Conference Center)3C05 (December, 2017)78. Shoichiro Asayama et al., See the annual report in Japanese(2017).
79. D. Katayama, R. Fujihara, T. Ando, N. Hirota, O.
Koike, R. Tatsumi, M. Yamato，Numerical simulation of
structure formation of magnetic particles in solvent undermagnetic fields toward development of anisotropic materials,
11th Annual Meeting of the Magneto-Science Society of Japan,
Nov. 2017, Kyoto, Japan (in Japanease)

3. Student Poster Award, The Annual Meeting of the Society ofFiber Science and Technology, Japan, Yuta Inafune, Manabu
Tanaka, Hiroyoshi Kawakami, Fabrication and evaluation ofmulti stacked all-solid-state secondary battery comprising oflithium conductive nanofiber composite electrolyte membranes
4. Most Excellent Poster Award, The 55th Annual Meeting of
the Japanese Society for Artificial Organs, Ryosuke Shinohara,
Risa Shimazaki, Riku Kubota, Shoichiro Asayama and
Hiroyoshi Kawakami, Cell differentiation by epigenetics
control aiming diabetes therapy
5.Hiroyoshi Kawakami, ACS Publication Awards, ACS.
6.Hiroyoshi Kawakami, 2018 Albert Nelson Marquis Lifetime
Achievement Award, MARQUIS WHOS WHO.

■Patents

1. P2017-63039, Polymer Electrolyte Membrane and Fuel Cell,
Hiroyoshi Kawakami, Manabu Tanaka, Tsukasa Watanabe
2. Hiroyoshi Kawakami, Shoichiro Asayama, Shohei
Yamaguchi, Motoyuki Matsuho, Yutaro Asaba, See the annual
report in Japanese.
3. P2017-216187, Blend Nanofiber and Their Composite
Membrane, Hiroyoshi Kawakami, Manabu Tanaka, Risa
Sakaguchi
4. WO/2017/179738, Fabrication Method of Gas Separation
Membrane, Hiroyoshi Kawakami, Manabu Tanaka, Yuri
Kameyama, Azusa Osawa, Tadayuki Isaji, Takamasa Kikuchi
5. Shoichiro Asayama, Hiroyoshi Kawakami, Kana Nagashima,
Yuya Sone, See the annual report in Japanese■Awards
1. Student Poster Award, 39th Annual Meeting on The
Membrane Society of Japan, Yuta Inafune, Manabu Tanaka,
Hiroyoshi Kawakami, Fabrication and evaluation of bipolar
stacked all-solid-state secondary battery with lithium ion
conductive nanofiber composite electrolyte membranes
2. Student Poster Award, 39th Annual Meeting on The
Membrane Society of Japan, Shun Nakazawa, Manabu Tanaka,
Hiroyoshi Kawakami, Preparation and secondary battery
characterizations of lithium single-ion conducting nanofiber
composite membrane7

Reports from Research Groups
Masuda Laboratory■Members
Hideki Masuda
Professor/ Dr. Eng.
Electrochemistry, Nano Fabrication, Functional ElectrodeRm. 9-147, +81 426 77 2843
masuda-hideki@tmu.ac.jp

surface prepared by this process could be used for theantirefrection surface and surper hydrophobic surface.
(3). Fabrication of Enagy Devices Based on Ordered Anodic
Porous Alumina
Hideki MASUDA, Takashi YANAGISHITAFor the preparation of uniform sized nanoparticles, we haveintroduced membrane emeulsification process using ordered
anodic porous alumina. The present process is simple and can beused as a high-throughput process for forming monodispersed
nanoparticles of metal oxides. The monodispersed nanoparticles
prepared by this process will be useful as electrode active
materials in the Li ion batteries to improve the properties.

Takashi Takei
Associate Professor /Dr. Eng.
Solid surface chemistry, interface and colloid scienceRm. 9-136, +81 426 77 2822
takei-takashi@tmu.ac.jp
Takashi Yanagisita
Associate Professor/ Dr. Eng.
Electrochemistry, Functional Metal Oxide FilmRm. 9-140,+81 426 77 1111 (Ext. 4931)
yanagish@tmu.ac.jp(4) Study of Self-ordering Mechanism of the Cell Arrangementof Anodic Porous Alumina
Hideki MASUDA, Toshiaki KONDO
Regularity of the holearray structure of the anodic porousalumina which is used as mother template is important toimprove the regularity of the obtained metal and semiconductor
nanohole arrays. To improve the regularity of the holearraystructure of the anodic porous alumina, anodizing conditions
were explored, and self-ordering of the anodic oxide film wasnewly discovered in sulfuric acid solution. The detailed
mechanism of the self-ordering of the anodic porous alumina iscurrently being investigated.

Toshiaki Kondo
Assistant Professor/ PhD.
Nanofablication, Applied optics
Rm. 9-238,+81 426 77 1111 (Ext. 4854)
kondo-toshiaki@tmu.ac.jp
Master’s course -14
Bachelor 4 -8(5)Evaluation of Pore Structures of Highly Ordered Porous
Alumina by Nitrogen Adsorption Method
Takashi Takei, Takashi Yanagishita, Hideki Masuda
The pore size distribution and surface area of highly ordered
porous alumina have been investigated by the nitrogen
adsorption method.

■Outlines of the Research(1) Fabrication of Nanofilters by Electrochemical Process
Hideki MASUDA, Takashi YANAGISHITAFor the fabrication of ordered nanofilere membranes, wehave investigated anodization process of Al. The size andinterval of holes could be controlled by adjusting the anodization
conditions. Metal and semiconductor nanohole array structures
have been also fabricated using an anodic porous alumina as atemplate. For the replacement of the ordered hole-array structurewith other materials we developed a two-step replication process
in which formation of a replicated negative and subsequentpreparation of a replicated positive give the nanohole structure
identical to that of mother structure of anodic orous alumina.
Metal (Au, Pt, Ni) and semiconductor (TiO2, ZnO, CdS)
nanohole arrays have been fabricated using the two-step process.
Detailed conditions for the precise replication were examined
experimentally, and new applications, such as optical devices
and detector for low energy ions, have been developed■Papers with Peer Review
1. Takashi Yanagishita, Masahiko Imaizumi, Toshiaki Kondo,
and Hideki Masuda
Preparation of Nanoporous Alumina Hollow Spheres with a
Highly Ordered Hole Arrangement
RSC Adv., 8, 2041 (2018).
2. Takashi Yanagishita, Toshiaki Kondo, and Hideki Masuda
Preparation of Renewable Antireflection Moth-Eye Surfaces
by Nanoimprinting Using Anodic Porous Alumina Molds
J. Vac. Sci. Technol. B, in press.
3. Takashi Yanagishita, Taito Inoue, Toshiaki Kondo, andHideki Masuda
Preparation of Monodisperse LiCoO2 Hollow Particles by
Membrane Emulsification Using Anodic Porous Alumina
Chem. Lett., in press.
4. Takashi Yanagishita, Masahiko Imaizumi, Toshiaki Kondo,
and Hideki Masuda
Formation of Porous Al Particles by Anisotoropic Etching
Electrochem. Commun., 78, 26 (2017).

SEM image of anodic porous alumina

5. Toshiaki Kondo, Hayato Miyazaki, Takashi Yanagishita, andHideki Masuda
Anodic Porous Alumina with Square Holes Through Lattice
Conversion of Naturally Occurring Ordered Structure
J. Vac. Sci. Technol. B, 35, 050602 (2017).

(2) Preparation of Ordered Nanostructures by Nanoimprinting
Using Ordered Anodic Porous Alumina Molds
Hideki MASUDA, Takashi YANAGISHITA
Ordered pillar array and hole array patterns were fabricatedby nanoimprinting using anodic porous alumina. Patterned
8Reports from Research Groups
Pretextured Metals
Electrochemistry 2017, 2017/11, Berlin

6. Toshiaki Kondo, Sanami Nagao, Takashi Yanagishita, andHideki Masuda
Tuning of Interval in Nanohole Array of Anodic Porous
Alumina through Deformation of Polymer Templates
RSC Adv., 7, 44799 (2017).

6. Toshiaki Kondo, Takashi Yanagishita, Hideki Masuda
Fabrication of Al Nanowires Based on Anodic Porous
Alumina and Its Plasmonic Properties
The 39th PIERS, 2017/11, Singapore

7. Nhat Truong Nguyen, Imgon Hwang, Toshiaki Kondo,
Takashi Yanagishita, Hideki Masuda, and Patrik Schmuki
Optimizing TiO2 Nanotube Morphology for Enhanced
Photocatalytic H2 Evolution Using Single-Walled andHighly Ordered TiO2 Nanotubes Decorated with Dewetted
Au Nanoparticles
Electrochem. Commun, 79, 46 (2017).

＊Domestic
See the annual report in Japanese (8 articles)■Academic Meeting＊International
1. Takashi Yanagishita, Atsushi Kato, Toshiaki Kondo, Hideki
Masuda,Fabrication of Ordered Porous Alumina Through-Hole
Membrane by Two-Layer Anodization2017 MRS Fall Meeting, 2016/11，Boston

8. Takashi Yanagishita, Atsushi Kato, and Hideki Masuda
Preparation of Ideally Ordered Through-Hole Anodic Porous
Alumina Membranes by Two-Layer Anodization
Jpn. J. Appl. Phys., 56, 035202 (2017).

2. Toshiaki Kondo, Taiga Sakamoto, Takashi Yanagishita, andHideki Masuda,
Fabrication of Ordered Array of ZnO Nanorods Using
Anodic Porous Alumina
2017 MRS Fall Meeting, 2016/11，Boston

9. Ryohei Takakura, Tomoya Oshikiri, Kosei Ueno, Xu Shi,
Toshiaki Kondo, Hideki Mausda, and Hiroaki Misawa
Water Splitting Using a Three-Dimensional Plasmonic
Photoanode with Titanium Dioxide Nano-Tunnels
Green Chem, 19, 2398 (2017).

＊Domestic
See the annual report in Japanese (23 articles)

10. A. Kawamura, S. Ueno, C. Takai, T. Takei, H.RazaviKhosroshahi, M. Fuji
Effect of steric hindrance on surface wettability of fine silica
powder modified by n- or t-butyl alcohol
Adv.Powder.Technol., 28, 2488 (2017)■Patents

See the annual report in Japanese (12 articles)■Awards

See the annual report in Japanese (1 articles)■Reviews and Books
See the annual report in Japanese (7 articles)■Invited Lectures＊International
1. Hideki Masuda, Toshiaki Kondo ,and Takashi Yanagishita
Synthesisi of Ordered Semiconductor Nanostructures forEnergy Conversion Using Anodic Porous Alumina
231th ECS Meeting, 2017/5，New Orleans，US.
2. Hideki Masuda, Toshiaki Kondo ,and Takashi Yanagishita
Highly Ordered Anodic Porous Alumina for Functioanl
Nanodevices
Anodizing it 2017 congress，2017/7，Toulouse, France
3. Hideki Masuda
Preparation of Ordered Micro- and Nanostructures for
Functional Devices by Using Anodic Porous Alumina
2nd Global Congress & Expo on Materials Science &Nanoscience，, 2017/9，Valencia, Spain
4. Takashi Yanagishita
Anodizing Process for Hydrogen Energy Synthesis
The 2nd International Symposium on Hydrogen Energybased Society，2017/11，Tokyo
5. Toshiaki Kondo, Takashi Yanagishita, Hideki Masuda
Ideally Ordered Nanohole Array Obtained by Anodizing

9

Reports from Research Groups
Setaka Laboratory■Members

investigate that the introduction of the clutch-declutchmechanism
into
a
new
gear
system,abis(9-triptycyl)difluorosilane derivative, is achieved by thereversible attachment of a fluoride ion.

Wataru Setaka
Associate Professor /Dr. Sci.
Physical Organic Chemistry, Functional Organic Chemistryroom: 9-336 TEL: +81-42-677-1111 (Ext.4874)
e-mail: wsetaka@tmu.ac.jp
Yusuke Inagaki
Assistant Professor / Dr. Sci.
Main-group Chemistry, Functional Organic Chemistryroom: 9-351 TEL: +81-42-677-1111 (Ext.4887)
e-mail: yinagaki@tmu.ac.jp

Figure. Cluch-decluch function in a novel molecular gear.

Doctor’s course -0
Master’s course -6
Bachelor 4 -4

3. Control of Intramolecular Charge-Transfer Fluorescence
Phenyldisilanes show unique intramolecular charge- transfer
fluorescence. To control of its fluorescence intensity withaddition of alkali metal cation, we synthesizedaminomethyl-substituted phenyldisilane 1. The fluorescence of
1 was quenched by photoinduced electron transfer (PET) frominternal nitrogen atom. However, the intense fluorescence of 1
was observed in the presence of Na+, because coordination of
Na+ to amino group prevents the quenching. These results
indicates that the controlling of the ICT fluorescence intensity
is achieved by utilizing PET mechanism.

■Outlines of the Research
Development of Highly Designed Organic Molecules
Wataru SETAKA, and Yusuke INAGAKIDevelopment of organic molecules of which strucrure andfunctions are highly designed would improve our daily life withrespect to energy saving and environmental consequence. Ourinterest lies in the design and synthesis of organic moleculeswith new structures that incorporate silicon to develop
molecules with new functions. Specifically, we are studying therelationship between molecular structure and molecularfunctionalities of novel organosilicon compounds.
1. Crystalline Molecular Gyrotop
A molecular machine has been defined as a discrete number ofmolecular components that perform mechanical─likemovements in response to specific stimuli. A macrocage
molecule with a bridged thiophene rotor was synthesized as amolecular gyrotop having a dipolar rotor, given that the dipole
derived from the thiophene can rotate even in the crystal. The
thermally induced change in the orientation of the dipolar
rotors (thiophene ring) inside the crystal, i.e., order-disordertransition, and the variation in the optical properties in the
crystalline state were observed.

Figure. A phenyldisilane which exhibits CT fluorescence.

■Papers with Peer Review

1. A Crystalline Molecular Gyrotop with a Biphenylene Dirotor
and its Temperature Dependent Birefringence, A. Fujiwara, Y.
Inagaki, H. Momma, E. Kwon, K. Yamaguchi, M. Kanno, H.
Kono, and W. Setaka, Cryst. Eng. Comm., 19, 6049-6056(2017).

■Account

1. Phenylene-bridged Macrocages as Molecular Gyrotops,
Wataru Setaka, Organosilicon Chemistry, 34, 19-26 (2017).

■Invited Lectures

1. Wataru Setaka, Phenylene-bridged Macrocages as
Crystalline Molecular Gyrotops, International Conference of
Natural and Artificial Molecular Machines, 2017.12.18-20, IIT
Bombay, India (IT11 12/19, invited)

Figure. Structure of molecular gyrotop and birefringencechange.

■Awards
1. Taro Tsuchiya received the excellent poster award at 7th CSJ
Chemistry Festa, the Chemical Society of Japan (17-19 October
2017, Funabori (Tokyo)). The title of her presentation was“Synthesis of a o-Difluorobenzene-bridged MolecularGyrotop".

2. Novel Molecular Bevel Gears
Bis(9-triptycyl)X systems (X= CH2, O, NH, SiH2, PH, etc.) are
known as well-designed bevel gear systems. To use the gearsystems as a molecular machine, it is desirable to introduce a
clutch-declutch mechanism controllable by external stimuli.
Silane-silicate interconversion using reversible attachment of afluoride ion may be a promising option for this purpose. We

10

Reports from Research Groups■Academic Meeting

11. Taro TSUCHIYA, Yusuke INAGAKI, Wataru SETAKA
a o-Difluorobenzene-bridged Molecular Gyrotop
7th Chemistry CSJ Fesrta, Tower Hall Fumabori, 10.17-19,
2017. (poster)*Best Poster Award

1. Noriyuki Tanaka, Yusuke Inagaki, Kentaro
Yamaguchi, Wataru Setaka
Synthesis
andCrystal
StructureofaResorcyltriptycene
The 98th CSJ Annual Meeting, Funabashi Campus,
Nihon University (Funabashi, Chiba) (oral)

12. Noriyuki Tanaka, Yusuke Inagaki, Kentaro Yamaguchi,
Wataru Setaka
Synthesis of a Resorcyltriptycene as a Novel Molecular Rotor
7th Chemistry CSJ Fesrta, Tower Hall Fumabori, 10.17-19,
2017. (poster)

2. Satoshi Hosono, Yusuke Inagaki, Wataru Setaka
Synthesis of Tin-linked Molecular Bevel Gears andObservation of Gear Slippage
The 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)

13. Masaya Ito, Yusuke Inagaki, Wataru Setaka
Synthesis of a Bipyridylene-bridged Molecular Gyrotop and its
Palladium Complex
7th Chemistry CSJ Fesrta, Tower Hall Fumabori, 10.17-19,
2017. (poster)

3. Masaya Ito, Yusuke Inagaki, Kentaro Yamaguchi, Wataru
SetakaSynthesis of a Bipyridylene-bridged Molecular Gyrotop andFormation of its Palladium Complex
The 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)

14. Miyako Tsurunaga, Junko ARASE, Yusuke INAGAKI,
Kentaro YAMAGUCHI, Wataru SETAKA
Dielectric Properties of Thiophene Dioxide Bridged MolecularGyrotop in a Crystalline State
28th Symposium on Physical Organic Chemistry, Kyusyu
University, 9.7, 2017. (oral)

4. Daiki Hayashi, Yusuke Inagaki, Wataru Setaka
Synthesis and Photophysical Properties of Silyl-substituted
Thieno[3,2-b]thiophenes
The 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)
5. Hikaru Hashimoto, Yusuke Inagaki, Wataru Setaka
Preparation and ESR observation of N-oxyl Carbazole bridged
Macrocages
The 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)
6. Kajiyama Kazuki, Inagaki Yusuke, Yamaguchi Kentarou,
Setaka Wataru
Synthesis of Phenylene-bridged Diazamacrocycles and their
Redox Property
The 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)
7. Taro TSUCHIYA, Yusuke INAGAKI, Kentaro
YAMAGUCHI, Wataru SETAKA
Synthesis of a o-Difluorobenzene-bridged Molecular Gyrotop
and its Rotational Dynamics in a Crystalline StateThe 98th CSJ Annual Meeting, Funabashi Campus, Nihon
University (Funabashi, Chiba) (oral)
8. Hikaru Hashimoto, Yusuke Inagaki, Kentaro Yamaguchi,
Wataru Setaka
Novel Functions of a Carbazole in Carbazole Bridged
Macrocages
The 44th Symposium on Main Group Element Chemistry,
Tokyo Inst. of Tech., 12.7-9, 2017 (oral)
9. Hideaki Takashima, Yusuke Inagaki, Kentaro Yamaguchi,
Wataru Setaka
Synthesis and Redox Properties of Ferrocene or Ruthenocene
Bridged Macrocages
The 44th Symposium on Main Group Element Chemistry,
Tokyo Inst. of Tech., 12.7-9, 2017 (poster)
10. Taro Tsuchiya, Yusuke Inagaki, Kentaro Yamaguchi,
Wataru Setaka
A Novel 1,2-Difluorophenylene Bridged Molecular Gyrotop asa Candidate for Dielectric Material
The 2nd International Symposium on Hydrogen Energy-based
Society, 2017.11.20-21, Tokyo Metropolitan University, Japan(poster)

11

Haruta Laboratory■Members■Outlines of the Research
1. Gas Phase Reactions by Metal Oxide-Supported Gold
Catalysts
Toru MURAYAMA, Takuya YOSHIDA, Yasunori INOUE,
Sinichi HATA, Mingyue LIN, Qianqian ZHU, Tamao ISHIDA,
Masatake HARUTA

Ayako TAKETOSHI
Assistant Professor /Dr. Eng.
Catalysis Chemistry,room:F-203 TEL: +81-42-677-2360
e-mail: taketoshi-ayako@tmu.ac.jp

Gold clusters were deposited on a Keggin-type polyoxometalate
by sol immobilization. Deposition of Au clusters smaller than 2
nm onto Cs4SiW12O40 was essential to show high catalyitc
activity for CO oxidation. The Au/Cs4SiW12O40 showed
extreamly high stability for at least one month at 0 °C with fullconversion. The catalytic activity drastically changed attemperatures higher than 40 °C, showing a unique behavior
called a U-shaped curve (Fig. 1). The reaction mechanism
changed in accordance with the temperature range. It was
revealed that the adsorption of water around gold promoted CO
oxidation at temperatures of less than 60 °C.

Masatake HARUTA
Professor /Dr. Eng.
Catalysis Chemistry, Nano-materials,
room:F-204 TEL: +81-42-677-2852
e-mail: haruta-masatake@center.tmu.ac.jp

Tamao ISHIDA
Project Professor /Dr. Eng.
Catalysis Chemistry,room:F-203 TEL: +81-42-677-2360
e-mail: tamao@tmu.ac.jp
Toru MURAYAMA
Project Professor /Dr. Eng.
Catalysis Chemistry,room:F-203 TEL: +81-42-677-2360
e-mail: murayama@tmu.ac.jp
Jun-ichi NISHIGAKI
Project Associate Professor /Dr. Sci.
Catalysis Chemistry,room:F-203 TEL: +81-42-677-2360
e-mail: jnishi@tmu.ac.jp
Takashi FUJITA
Project Assistant Professor /Dr. Sci.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360
e-mail: t-fujita@tmu.ac.jp

Figure 1. Effects of reaction temperature on CO oxidation over
Au/Cs4SiW12O40.
For efficient elimination of odors, selective oxidations
were carried out using various kinds of supported gold catalysts.
The selectivity depended on the kinds of support.
Catalysts that realize the NH3-selective catalytic reduction(NH3-SCR) under mild conditions are demanded in the NO
removal technologies. The V2O5 catalyst that we developed

Takuya YOSHIDA
Project Assistant Professor /Dr. Sci.
Catalysis Chemistry,
Daisuke ISHIKAWA
Project Assistant Professor /Dr. Eng.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360
e-mail: daisuke-ishikawa@tmu.ac.jp
Yasunori INOUE
Project Assistant Professor /Dr. Sci.
Catalysis Chemistry,
Sinichi HATA
Project Assistant Professor /Dr. Eng.
Catalysis Chemistry,
Mingyue LIN
Project Assistant Professor /Dr. Eng.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360
e-mail: mylin@tmu.ac.jp
Qianqian ZHUProject Assistant Professor /Dr. Eng.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360

Figure 2. Dependence of NO conversion on reaction
temperature in SCR of NO with NH3 using V2O5 and 23 wt%V2O5/TiO2.

Master’s course -2

12

addition, smaller Au(0) nanoparticles exhibited better
performance than larger ones. From these results, Au(0)nanoparticles can work as soft Lewis acid catalysts and theactivity was better than cationic Au when they are supported on
metal oxides.
Aliphatic esters are important compounds as flavors andfragrance. In industry, esters are produced by two steps,oxidation of aldehyde to carboxylic acid followed by acidcatalyzed esterification. From the point of view of green
chemistry, oxidative esterification by one step has been
attracting attention. We chose oxidative esterification of octanalwith ethanol as a model reaction to give ethyl octanoate. Various
kinds of supported gold catalysts have been screened in a batch
reactor (Fig. 4). After reaction for 5 h, ethyl octanoate wasobtained in high yields with high selectivities by Au/ZnO,
Au/Al2O3, and Au/SiO2. Next, the reaction was carried out in acontinuous flow reactor. The catalytic activity could bemaintained for at least 6 h.

showed extremely high denitrification rate at 200 ˚C or less by
the increase of acid sites due to the high specific surface area,
indicating that pure V2O5 with high specific surface area has
higher activity than conventional industrial catalysts (2-3wt%
V2O5/TiO2) in the low temperature range. These results are
expected to greatly contribute to the efficiencent improvementof the exhaust gas treatment system and is highly appreciated ina wide range of fields such as catalytic chemistry and processengineering.
2. Liquid Phase Reactions by Supported Metal Nanoparticle
Catalysts
Tamao ISHIDA, Ayako TAKETOSHI, Masatake HARUTA
We have found that oxidative sp2 C–H bond coupling forsynthesis of biaryls was catalyzed by supported gold
nanoparticles via electrophilic aromatic substitution reaction,
which takes place on the cationic gold atoms at the perimeterinterface with metal oxide supports. It has been also revealed bytheoretical chemistry that zero valent gold nanoparticles havesoft Lewis acidity. In this work, to evaluate the soft Lewis acidityof gold nanoparticles, we examined transfer vinylation ofcarboxylic acids with vinyl acetate which is traditionallycatalyzed by homogeneous Au(I) catalysts (Scheme 1).
OOH
0.5 mmolAcO
1 mL[Au] (1 mol%)air
100 oC,48 h

O
O

AcOH

Scheme 1. Transfer vinylation of benzoic acid with vinyl acetate.
Figure 4. Oxidative esterification of octanal with ethanol
catalyzed by gold nanoparticles.

We screened various kinds of metal oxide supported gold
catalysts (Au 1 wt%). Figure 3 shows the relationships between
acid-base properties of metal oxide supports and the productyield. As a result, gold particles on acidic and basic supports
showed inferior catalytic activity to those on amphoteric ones,
and Au/ZrO2 gave the highest yield. A decrease in Au loading to
0.3 wt% improved the yield due to a decrease in gold particle
size. The use of mixed-metal oxide, CeO2-ZrO2, further
improved the catalytic activity of gold to give vinyl benzoate up
to 92%.

3. Synergistic Effects of Gold Nanoparticle Catalysts with
Biofunctional Materials
Jun-ichi NISHIGAKI, Takashi FUJITA, Masatake HARUTA
3-1. Enzyme/Gold Hybrid Catalysts
We developed the catalytic reactions showing
synergistic/complementary effects by combining biological andartificial Au nanoparticle catalysts together. Nicotinamide
adenine dinucleotide (NADH as a reduced form and NAD+ as anoxidized one) works as a coenzyme that is comsumed inenzymatic reactions. Generally, stoichiometric amout of
NADH/NAD+ is required, so that a lot of amount of waste wasproduced after the reactions. If the catalytic recycling of
NADH/NAD+ is realized, the use of coenzymes can besignificantly decreased, contributing green chemistry. We
studied the catalytic reduction of NAD+ to NADH by supported
Au catalysts using H2. Small Au clusters (<2 nm) deposited on
basic supports (Au/CeO2 and Au/hydrotalcite (HT))
hydrogenated NAD+ under 1.0 MPa H2 to form NADH (Fig. 5).
The hydrogenation activity of Au catalysts was lower than thatof PtAu alloy catalysts, but NADH selectivity was higher. It
suggests that H2 was heterolytically activated on the interface of
Au clusters and basic supports. Now we synthesize smaller Aucluster catalysts to improve the catalytic performance and screen
the support materials which do not inhibit dehydrogenase
activity in the aim of enzyme/coenzyme/Au hybrid catalytic
systems to achieve in-situ coenzyme regeneration.

Figure 3. Relationships between electronegativity of metaloxide supports and the yield of vinyl benzoate.
The active Au species was also evaluated using Au/CeO2ZrO2 having different Au(III)/Au(0) ratio. Au(0) on CeO2-ZrO2
showed superior activity to Au(III) as a major species. In

13amount of TNF-α was significantly decreased by adding
Au/TiO2. This result suggests that Au/TiO2 attenuates LPSinduced inflammation. The similar effet was also observed on
Au/ZrO2. Although the Au-mediated anti-inflammatory
mechanism remains unclear at this stage, this study revealed that
Au/TiO2 and Au/ZrO2 are promising candidates for antiinflammatory agents.
4. Catalytic Reaction System in Interfacial DNA Film
Integrated with Gold Nanoparticles and Enzymes
Daisuke ISHIKAWA, Masatake HARUTA
A lattice-shaped DNA nanostructure capable of selectively
introducing gold catalysts and enzymes was prepared by using
DNA origami method (Fig. 7a). In this nanostructure, it ispossible to fix catalysts modified with single-stranded DNA byusing the hybridization at a designed location. The optimal salt
concentration and annealing conditions for producing thisstructure have been determined from many electrophoresis
analyses (Fig. 7b).
Figure 5. Hydrogenation of NAD+ by gold catalysts.
3-2. Biomedical Application of Gold Catalysts
For biomedical application of Au nanoparticle catalysts, we
examined the cytotoxic and inflammatory response of
macrophagic cells exposed to Au/MOx. Mice peritoneal primary
macrophages were exposed to 1–100 µg/mL particles of Au/TiO2
and TiO2 for 48 h. Neither Au/TiO2 nor TiO2 showed showed
cytotoxicity to the macrophagic cells by MTT and lactic aciddehydrogenase (LDH) assays. With regard to the inflammatory
response, a significant increase in TNF-α secretion was observedby exposure to TiO2 but was much less pronounced for Au/TiO2.
To examine this effect of Au/TiO2 in detail, lipopolysaccharide(LPS)-induced pro-inflammatory response was measured (Fig.
6).

Figure 7. (a) Schematic illustration of the lattice-shaped DNA
nanostructure, (b) Determination of MgCl2 concentration for
prepation of the DNA nanostructure.

■Papers with Peer Review

1.

2.

3.

Figure 6. TNFα levels after LPS-induced inflammation andexposition of machrophagic ceslls to Au/TiO2 and TiO2. C:
control experiment.
When TiO2 was added to the macrophagic cells, theamount of the pre-existing TNF-α was almost consistent withthat of the LPS-induced control experiment. In contrast, the4.

14

A. Taketoshi, T. Ishida, H. Ohashi, T. Honma, M. Haruta,“Preparation of gold clusters on metal oxides bydeposition-precipitation with microwave drying and theircatalytic performance for CO and sulfide oxidation”, Chin.
J. Catal. 2017, 38, 1888–1898.
Q. Lin, C. Han, H. Su, L. Sun, T. Ishida, T. Honma, X. Sun,
Y. Zheng, C. Qi, "Remarkable enhancement of Fe-V-Ox
composite metal oxide to gold catalyst for CO oxidation in
the simulated amosphere of CO2 laser", RSC Adv. 2017, 7,38780–38783.
Z. Zhang, Y. Kumamoto, T. Hashiguchi, T. Mamba, H.
Murayama, E. Yamamoto, T. Ishida, T. Honma, M.
Tokunaga, “Wacker Oxidation of Terminal Alkenes overZrO2 Supported Pd Nanoparticles under Acid- and CoCatalyst-Free Conditions”, ChemSusChem 2017, 10,3482–3489.
H. Murayama, T. Hasegwa, Y. Yamamoto, M. Tone, M.
Kimura, T. Ishida, T. Honma, M. Okumura, A. Isogai, T.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

Fujii, M. Tokunaga, “Chloride-Free and Water-Soluble Au
Complexes for Preparation of Supported Small
Nanoparticles by Impregnation Method”, J. Catal. 2017,
353, 74–80.
H. Ando, D. Kawamoto, H. Ohashi, T. Honma, T. Ishida,
Y. Okaue, M. Tokunaga, T. Yokoyama, “Adsorption
Behavior of Au(III) Complex Ion on Nickel Carbonate andNickel Hydroxide”, Colloids Surf. A 2018, 537, 383–389.
T. Ishida, Z. Zhang, H. Murayama, M. Tokunaga, “OxideSupported Palladium and Gold Nanoparticles for Catalytic
C-H Transformations”, J. Synth. Org. Chem., Jpn. 2017,75, 1150–1161.
A. Yada, T. Murayama, J. Hirata, T. Nakashima, M.
Tamura, Y. Kon, W. Ueda, “W-Ti-O Mixed Metal Oxide
Catalyzed Dehydrative Cross-etherification of Alcohols”,
Chem. Lett. 2018, in press.
T. Yoshida, T. Murayama, N. Sakaguchi, M. Okumura, T.
Ishida, M. Haruta, “Carbon Monoxide Oxidation by
Polyoxometalate‐Supported
Gold
Nanoparticulate
Catalysts: Activity, Stability, and Temperature‐Dependent
Activation Properties”, Angew. Chem. Int. Ed. 2018,57,1523–1527.
K. Nakajima, J. Hirata, M. Kim, N. K. Gupta, T.
Murayama, A. Yoshida, N. Hiyoshi, A. Fukuoka, W. Ueda,“Facile Formation of Lactic Acid from a Triose Sugar in
Water over Niobium Oxide with a Deformed
Orthorhombic Phase”, ACS Catal. 2018, 8, 283–290.
T. Baidya, T. Murayama, P. Bera, O. Safonova, P. Steiger,
N. Katiyar, K. Biswas, M. Haruta, “Low-temperature CO
oxidation over combustion made Fe and Cr doped Co3O4
catalysts: Role of dopant’s nature toward achieving
superior catalytic activity and stability”, J. Phys. Chem. C
2017, 121, 15256–15265.
S. Ishikawa, Y. Goto, Y. Kawahara, S. Inukai, N. Hiyoshi,
N. F. Dummer, T. Murayama, A. Yoshida, M. Sadakane, W.
Ueda, “Synthesis of crystalline microporous Mo-V-Bi
oxide for selective (amm)oxidation of light alkanes”,
Chem. Mater. 2017, 29, 2939–2950.
T. Murayama, K. Nakajima, J. Hirata, K. Omata, E. J. M.
Hensen, W. Ueda, “Hydrothermal Synthesis of a Layeredtype W-Ti-O Mixed Metal Oxide and its Solid Acid
Activity”, Catal. Sci. Tech. 2017, 7, 243–250.
S. Ishikawa, D. Jones, S. Iqbal, R. Christian, D. J Morgan,
D. J. Willock, P. Miedziak, J. K. Bartley, J. Edwards, T.
Murayama, W. Ueda, G. Hutchings, “Identification of thecatalytically active component of Cu-Zr-O catalyst for thehydrogenation of levulinic acid to γ-valerolactone”’,Green Chem. 2017, 19, 225–236.
K. Nomiya, K. Endo, Y. Murata, S. Sato, S. Shimazaki, S.
Horie, E. Nagashima, Y. Yasuda, T. Yoshida, S. Matsunaga,
T. Matsubara, "Polyoxometalate-Assisted, One-Pot
SynthesisofaPentakis[(triphenylphosphane)gold]ammonium(2+)
Cation Containing Regular Trigonal-Bipyramidal
Geometries of Five Bonds to Nitrogen", Inorg. Chem.
2018, 57, 1504–1516.
M. Okuno, D. Ishikawa, W. Nakanishi, K. Ariga, T.
Ishibashi, “The Symmetric Raman Tensor Contributes to
Chiral Vibrational Sum Frequency Generation from
Binaphthyl Amphiphile Monolayers on Water – Study ofElectronic Resonance Amplitude and Phase Profiles”, J.

16.

17.

18.

19.

20.

21.

Phys. Chem. C, 2017, 121, 11241–11250.
T. Sagami, S. Umemoto, Y. O. Tahara, M. Miyata, Y.
Yonamine, D. Ishikawa, T. Mori, K. Ariga, H. Miyake, S.
Shinoda, “pH-Responsive Cotton Effects in the d-d
Transition Band of Self-Assembling Copper (II)Complexes with a Cholesteryl-Armed Ligand”, Bull.
Chem. Soc. Jpn., 2017, 90, 739–745.
T. Mori, D. Ishikawa, Y. Yonamine, Y. Fujii, J. P Hill, I.
Ichinose, K. Ariga, W. Nakanishi, “Mechanically Induced
Opening-Closing Movements of Binaphthyl Molecular
Pliers: Digital Phase Transition v.s. Continuous
Conformational Change”, ChemPhysChem, 2017, 18,1470–1477.
S. Hata, T. Omura, K. Oshima, Y. Du, Y. Shiraishi, N.
Toshima, "Novel Preparation of Poly(3,4-ethylene
dioxythiophene)-Poly(styrenesulfonate)-Protected Noble
Metal Nanoparticles as Organic-Inorganic Materials", Bull.
Soc. Photogr. Imag. Jpn. 2017, 27, 13-18.
M. Sadakiyo, S. Hata, X. Cui, M. Yamauchi,"Electrochemical Production of Glycolic Acid from Oxalic
Acid
Using
a
Polymer
Electrolyte AlcoholElectrosynthesis Cell Containing a Porous TiO2 Catalyst",
Sci. Rep. 2017, 3, 17032.
Y. Shiraishi, S. Hata, Y. Okawauchi, K. Oshima, H. Anno,
N. Toshima, "Improved Thermoelectric Behavior ofPoly(3,4-ethylene
dioxythiophene)Poly(styrenesulfonate)using
Poly(N-vinyl-2pyrrolidone)-coated GeO2 Nanoparticles", Chem. Lett.
2017, 46, 933–936.
T. Fukushima, S. Kitano, S. Hata, M. Yamauchi, “Carbon
neutral energy cycles using alcohols”, Sci. Tech. Adv.
Mater. 2018, 19, 142–152.

■Books1.

T. Ishida, M. Haruta, "Supported Gold Nanoparticles
Leading to Green Chemistry", in Nanotechnology in
Catalysis: Applications in the Chemical Industry, Energy
Research, and Environment Protection, B. F. Sels, M. vande Voorde, Eds., Wiley-VCH, 2017, pp. 21–36.

■Invited Lectures
1.

2.

3.

4.

T. Fujita, M. Haruta, J. Boczkowski, “Gold catalysis: a
new anti-inflammaging therapeutic option”, JSPSINSERM Joint Symposium, Paris, France, 2017.7.3.
T. Ishida, "Palladium and Gold-Nanoparticle-Catalyzed
Oxidative C-H Functionalization", 8th World Congress on
Oxidation Catalysis (2017) (8WCOC), Krakow, Poland,
2017.9.5.
T. Murayama, H. Gi, K. Shinzato, M. Sadakane, H.
Miyaoka, T. Ichikawa, “Hydrogen desorption andabsorption in MgH2 assisted by catalytic effect of Nb2O5”,
The 2nd International Symposium on Hydrogen Energy‒
based Society, Tokyo Metropolitan University, 2017.11.21.
A. Taketoshi, “Oxidative Esterification of Octanal
Catalyzed by Gold Nanoparticles in Batch and Continuous
Flow Reactors”, TMU and PetroMat Joint Mini
Symposium on Catalysis and Advanced Materials 2018,
Tokyo Metropolitan University, 2018.1.31.

The other four invite lectures in Japan are written in Japaneseversion.

15

＊International (Poster)
1. T. Ishida, R. Sodenaga, T. Honma, M. Haruta, "Transfer
Vinylation Catalyzed by Supported Gold Catalysts", The
2nd International Symposium on Hydrogen Energy‒based
Society, Tokyo Metropolitan University, 2017.11.21■Academic Meeting＊International (oral)
1.
T. Murayama, K. Nakajima, N. K. Gupta, A. Fukuoka, M.
Haruta, “Gold nanoparticulate catalysts deposited on
niobium oxide and their catalytic activity for gas and liquid
phase oxidation”, 8th International Symposium on AcidBase Catalysis (ABC-8), Rio de Janeiro, Brazil, 2017.5.9.
2.
H. Gi, K. Shinzato, M. Sadakane, T. Murayama, H.
Miyaoka, T. Ichikawa, “Catalytic effect of various Nb2O5
on hydrogen desorption and absorption in MgH2”, The 1st
International Symposium on Fuels and Energy, Hiroshima,
Hiroshima, 2017.7.11.
3.
T. Murayama, K. Nakajima, N. K. Gupta, A. Fukuoka, M.
Haruta, “Low temperature gas/liquid phase oxidation bynanoparticulate gold catalysts deposited on niobiumoxide”, 13th European Congress on Catalysis(EUROPACAT 2017), Florence, Italy, 2017.8.28.
4.
T. Ishida, "Supported Gold Nanoparticle-Catalyzed
Coupling Reactions", Dalian Institute of Chemical
Physics-Tokyo Metropolitan University (DICP-TMU)
Joint Symposium on Gold Catalysis Research, Dalian,
China, 2017.9.29.
5.
T. Murayama, “Gold nanoparticulate catalysts deposited
on solid acid and their application for oxidation reactions”,
Dalian Institute of Chemical Physics-Tokyo Metropolitan
University (DICP-TMU) Joint Symposium on Gold
Catalysis Research, Dalian, China, 2017.9.29.
6.
J. Nishigaki, “Interconversion of NADH and NAD+ bygold cluster catalysts: regeneration of active coenzymes indehydrogenase catalytic process”, Dalian Institute ofChemical Physics-Tokyo Metropolitan University (DICPTMU) Joint Symposium on Gold Catalysis Research,
Dalian, China, 2017.9.29.
7.
T. Fujita, K. Shibamoto, M. Haruta, “Effects of calcination
temperature and atmosphere on Au/ZnO catalyst for CO
oxidation”, Dalian Institute of Chemical Physics-Tokyo
Metropolitan University (DICP-TMU) Joint Symposium
on Gold Catalysis Research, Dalian, China, 2017.9.29.
8.
A. Taketoshi, T. Ishida, M. Haruta, “Preparation of Gold
Clusters on Metal Oxides by Deposition-Precipitaion with
Microwave Drying”, Dalian Institute of Chemical PhysicsTokyo Metropolitan University (DICP-TMU) Joint
Symposium on Gold Catalysis Research, Dalian, China,
2017.9.29.
9.
R. Sodenaga, T. Ishida, M. Haruta, "Supported goldcatalyzed transfer vinylation of carboxylic acid", DalianInstitute of Chemical Physics-Tokyo Metropolitan
University (DICP-TMU) Joint Symposium on Gold
Catalysis Research, Dalian, China, 2017.9.29.
10. T. Murayama, “Nanoparticulate gold catalyst deposited onpolyoxometalate”, Workshop Cardiff & TMU, Cardiff
University, Cardiff, UK, 2018.2.5.
11. A. Taketoshi, “Oxidative Esterification of Aliphatic
Aldehydes Catalyzed by Gold Nanoparticles in Bach andContinuous Flow Reactors”, Workshop Cardiff & TMU,
Cardiff University, Cardiff, UK, 2018.2.5.
12. T. Ishida, “Supported Gold Nanoparticle Catalysts for CH Bond Transformation”, Workshop Cardiff & TMU,
Cardiff University, Cardiff, UK, 2018.2.5.

＊Domestic (oral)
See the annual report in Japanese (13 articles)＊Domestic (poster)See the annual report in Japanese (8 articles)■Awards

1.

T. Ishida, The 5th Seki Memorial Award, “Development ofOrganic Reactions by Supported Metal Cluster catalysts”,
Seki Memorial Foundation for Science, 2017.11.8.

■Others
1. Ultra-efficient removal of carbon monoxide using gold
nanoparticles on a molecular support ~New method andmechanism for state-of-the-art gas purification~, TOKYOMETROPOLITAN UNIVERSITY, EurelAlert!, PUBLIC
RELEASE: 9-FEB-2018.

16

Reports from Research Groups
Kanamura Laboratory■Members

EnergyChemistry,

Cell voltage / V

Koichi KAJIHARA
Associate Professor /Ph.D.
Inorganic Chemistry, Functional Material Chemistry,
Inorganic Materials/Physical Properties
room:9-246 TEL: +81-42-677-2827
e-mail: kkaji@tmu.ac.jp
Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-243 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp

Charge1
Charge2

Charge3

Voltage / V

Charge4
Charge5Compositecathode

3.6

60 °C

3.2

3

Charge6
Charge7
Charge8

0.6

60

0.4

40

0.2

20
0

100

200

300

-2

0
400

Charge920 µA cm–2

3.4

80

3. Research on optical and electrical properties of inorganicoxides and related materials
Koichi KAJIHARA
Fundamental properties of inorganic oxides, in particular, their
optical and electrical properties, were studied to fully utilize thefunctionalities of oxides. In this FY we focused on the studies onsolid electrolytes. We developed a facile method to obtain glassceramics of lithium boracite Li4B7O12Cl. In addition, we found
for the first time that the boron sites of this compound can be
replaced by other metal ions and discovered a new compound
Li4B4M3O12Cl(M = Al, Ga), exhibiting the highest Li+ ion
conductivity (~10−5 S cm−1 at room temperature) among known
lithium boracites (Fig. 4). The compound with M = Al was foundto be stable to contact with Li metal and is applicable to all-solidstate rechargeable lithium batteries. We also succeeded the hightemperature measurements of dc conductivity and transference
ceramic
numberof
Mg2+-ion-conducting
Mg0.5−x(Zr1−xNbx)2(PO4)3 (x = 0.15) using Mg electrodes invacuum, and demonstrated the dc conduction of Mg2+ ions in thiscompound directly (Fig. 5).

1. Research on Rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
Research and development on next generation rechargeable
batteries with high energy density and excellent safety were
promoted in order to realize a sustainable society based on highutilization of energy. We successfully improved theelectrochemcial performance of all solid state rechargeable
batteries using oxide-based solide electrolytes by using
composite electrode including ionic liquid and solid electrolyte
powder (Fig. 1). A practical solid electrolyte system with highflexibility composing of inorganic and organic electrolytematerials (Fig. 2) was also prepared.

3.8

0.8

Current density / mA cm
Fig. 3 Fuel cell operation at intermediate temperatures without
humidification.

■Outlines of the Research

4

100

0

Doctor’s course -7
Master’s course -15
Bachelor 4 -9

4.2

1Power density / mW cm -2

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

2. Research on Fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of a new fuel cell system that works atintermediate temperatures over 100 °C under non-humidified
conditions was promoted. In this fuel cell, a heat energy
produced from fuel cell is recovered by reforming system,
leading to high energy conversion efficiency. It is found that the
mixture of phosphoric acid / ionic liquid works as highly protonconductive stable electrolyte at intermediate temperatures. The
fuel cell operated at 180 ° C without humidification (Fig. 3) byusing this mixed electrolyte.

Charge10
Discharge1

1st -3rd

Discharge2
Discharge3
Discharge4

0

50
100
150
Capacity / mAh g–1

200

Discharge5
Discharge6

Fig. 1 Charge-discharge curves of the all solid state battery witha composite cathode prepared.

Fig. 4 Crystal structure of the newly discovered lithium-ionconducting compound Li4B4M3O12Cl (M = Al, Ga) andphotograph of a glass-ceramic sample of M = Al after contact
with Li metal.

Fig.2 A flexible solid electrolyte membrane composed ofinorganic and organic electrolyte materials.

17

Reports from Research Groups
12.

boron sites, Bull. Chem. Soc. Jpn. 90, 1279-1286 (2017)
Linards Skuja, Koichi Kajihara, Krisjanis Smits, Kalvis
Alps, Andrejs Silins, Janis Teteris, Luminescence
properties of chlorine molecules in glassy SiO2 and opticalfibre waveguides, Proc. Est. Acad. Sci 66, 455-461 (2017)■BooksSee the annual report in Japanese (3 articles)

Fig. 5 Arrhenisus plot of ac conductivity of
Mg0.5−x(Zr1−xNbx)2(PO4)3 (x = 0.15) pellets measured withblocking Pt and non-blocking Mg electodes (left) and dc
polarization profile of the pellet measured with Mg electrodes at
350°C (right).

■Invited Lectures
1.

Kiyoshi Kanamura, Interfacial Control of All Solid State
Battery with Li Metal Anode, LLZAl Electrolyte and
LiMO2 Cathode, PACRIM12, May, 2017, Waikoloa,
Hawaii, USA
2. Kiyoshi Kanamura, Masaki Haibara, Naohiro Kobori, andHirokazu Munakata, Interfacial Behavior of Li Metal
Anode in Nonaqueous Electrolytes Under Controlled
Current Distribution, 2017 International Workshop on
Electrified Interfaces for Energy Conversions, May, 2017,
Shonan Village Center, Kanagawa, Japan
3. Koichi Kajihara, Tatsuya Mori, Kiyoshi Kanamura,
Yoshitake Toda, Hidenori Hiramatsu, and Hideo Hosono,
Synthesis, structure, and properties of indium-based
ultraviolet-transparent electroconductive oxyfluoride InOF,
STAC10, Aug., 2017, Mielparque Yokohama, Kanagawa,Japan
4. Kanamura Kiyoshi, Kozuka Kyoko, Shoji Mao, Kimura
Takeshi, Munakata Hirokazu, Preparation of All solid State
Battery by Aero Sol Deposition Method, INESS2017, Aug.,
2017, Astana, Kazakhstan
5. Munakata
Hirokazu,
KikuchiShojiro,Ionic
Liquid/Phosphoric Acid Mixed Electrolyte for Nonhumidified Intermediate Temperature Fuel Cells,
INESS2017, Aug., 2017, Astana, Kazakhstan
6. Kiyoshi KANAMURA, Kyoko KOZUKA, Takeshi
KIMURA, Mao SHOUJI, Hirokazu MUNAKATA, Allsolid state battery with Li metal anode and oxide cathodeprepared by aero-sol deposition process, IUMRSICAM2017, Aug., 2017, Kyoto University, Kyoto, Japan
7. Kiyoshi Kanamura, Dendrite Suppression of Li Metal in
Various, ACEPS9, Aug., 2017, HICO, Gyeongju, Korea
8. Kiyoshi Kanamura, Takeshi Kimura, Kyoko Kozuka, Mao
Shoji, Hirokazu Munakata, Interface Formation of Allsolid-state Rechargeable Lithium Batteries, 1st World
Conference on Lithium Garnets, Competitors and Beyondfor Advanced Batteries, Sep., 2017, Hotel Ocean Spray,
Pondicherry, India
9. Kiyoshi Kanamura, Fabrication of All-Solid-State Battery
with Aero Sol Deposition Process for Cathode Layer, 2017
MRS Fall Meeting & Exhibit, Nov., 2017, Boston, USA
10. Hirokazu Munakata, Jungo Wakasugi, Kyoko Kozuka,
Takeshi Kimura, Mao Shoji, Kiyoshi Kanamura, Electrode
Fabrication for All-solid-state Rechargeable Lithium
Batteries using Li6.25Al0.25La3Zr2O12 Solid Electrolyte,
ICACC2018, Jan., 2018, Daytona Beach, Fla. USA■Papers with Peer Review

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

Yuta Maeyoshi, Shohei Miyamoto, Hirokazu Munakata,
Kiyoshi Kanamura, Enhanced cycle stability of LiCoPO4
by using three-dimensionally ordered macroporous
polyimide separator, J. Power Sources 350, 103–108(2017)Ryo MATSUOKA, Shigeo AOYAGI, Naoshi
MATSUMOTO, Masaaki MATSUDAIRA, Yasufumi
TAKAHASHI, Akichika KUMATANI, Hiroki IDA,
Hirokazu MUNAKATA, Katsuhiko IIDA, Hitoshi SHIKU,
Kiyoshi KANAMURA, Tomokazu MATSUE, Advanced
Scanning Electrochemical Microscope System for HighResolution imaging and Electrochemical Applications,Electrochemistry, 85, 316-326 (2017).
Sunghyun Lim, Ji-Hyun Kim, Yuto Yamada, Hirokazu
Munakata, Young-Seak Lee, Sung-Soo Kim, Kiyoshi
Kanamura, Improvement of rate capability by graphite
foam anode for Li secondary batteries, J. Power Sources
355, 164-170 (2017).
EnhancedElectrochemical
Performanceof
LiMn0.75Fe0.25PO4 Nanoplates from Multiple Interface
Modification by Using Fluorine-Doped Carbon Coating,
ACS Sustainable Chem. Eng., 5, 4637–4644 (2017).
Kei Nishikawa, Nobuyuki Zettsu, Katsuya Teshima,
Kiyoshi
Kanamura,
Intrinsic
electrochemical
characteristics of one LiNi0.5Mn1.5O4 spinel particle, J.
Electroanal. Chem., 799, 468-472 (2017).
Jungo Wakasugi, Hirokazu Munakata, Kiyoshi Kanamura,
Improvement of sintering of Li6.25Al0.25La3Zr2O12 by using
pre-heat treatment, Solid State Ionics, 309, 9–14 (2017).
Yanqing Wang, Zengqi Zhang, Masaki Haibara, Deye Sun,
Xiaodi Ma, Yongcheng Jin, Hirokazu Munakata, Kiyoshi
Kanamura, Reduced Polysulfide Shuttle Effect by Using
Polyimide Separators with Ionic Liquid-based Electrolytes
in Lithium-Sulfur Battery, Electrochim. Acta, 255, 109117 (2017).
Yuta Maeyoshi, Shohei Miyamoto, Hirokazu Munakata,
Kiyoshi Kanamura, Effect of conductive carbon additives
on electrochemical performance of LiCoPO4, J. Power
Sources, 376, 18-25 (2018).
Naoto Tezuka, Yuta Okawa, Koichi Kajihara, Kiyoshi.
Kanamura, Synthesis and characterization of lithium-ionconductive glassceramics of lithium chloroboracite
Li4+xB7O12+x/2Cl (x = 0–1), J. Ceram. Soc. Jpn. 125, 348352 (2017)
Koichi Kajihara, Hayato Nagano, Takaoki Tsujita,
H.irokazu Munakata, Kiyoshi Kanamura, Hightemperature conductivity measurements of magnesiumion-conducting solid oxide Mg0.5−x(Zr1−xNbx)2(PO4)3 (x =0.15) using Mg metal electrode, J. Electrochem. Soc. 164,
A2183-A2185 (2017)
Koichi Kajihara, Naoto Tezuka, Mao Shoji, Jungo
Wakasugi, Hirokazu Munakata, Kiyoshi Kanamura,
Li4B4M3O12Cl (M = Al, Ga): an electrochemically stable,lithium-ion-conducting cubic boracite with substituted■Academic Meeting＊International
1. Linards Skuja, Koichi Kajihara, Krisjanis Smits, Andrejs
Silins, Janis Teteris, Luminescence properties of chlorine
molecules in glassy SiO2 and optical fiber waveguides,
International Conference 'Functioanal Materials andNanotechnologies 2017 (FM&NT-2017), Apr., 2017, Tartu,
Estonia
2. Hasna Puthen Peediyakkal, Shojiro Kikuchi, Yu Jie,
Hirokazu Munakata, Kiyoshi Kanamura, Electrochemical
Oxygen Reduction on Nitrogen Doped Graphene in Ionic
Liquid at Intermediate Temperatures, 2017 International
Workshop on Electrified Interfaces for Energy Conversions,
May, 2017, Shonan Village Center, Kanagawa, Japan18

Reports from Research Groups
3.

4.
5.

6.

7.

8.

9.

10.

11.

12.

13.

Fumihiro SAGANE, Kenta OGI, Akinori KONNO,
Kiyoshi KANAMURA, Effect of the cyclic ethers on thereversible Mg plating/stripping reaction for Mg batteries,
IUMRS-ICAM2017, Aug., 2017, Kyoto University, Kyoto
Kei
NISHIKAWA,
Kiyoshi
KANAMURA,
Electrodeposition of Li metal from various electrolytes,
IUMRS-ICAM2017, Aug., 2017, Kyoto University, Kyoto
Hirokazu Munakata, Jungo Wakasugi, Kiyoshi Kanamura,
Investigation of sintering process of aluminum-doped
lithium lanthanum zirconate for dense pellet fabrication, 1stWorld Conference on Lithium Garnets, Competitors andBeyond for Advanced Batteries, Sep., 2017, Hotel Ocean
Spray, Pondicherry, India
Mao Shoji, Hirokazu Munakata, Kiyoshi Kanamura,Interface formation between LiCoO2 and Li7La3Zr2O12
using solvate ionic liquids for all-solid-state batteries, 1stWorld Conference on Lithium Garnets, Competitors andBeyond for Advanced Batteries, Sep., 2017, Hotel Ocean
Spray, Pondicherry, India
Takeshi Kimura, Mao Shoji, Hirokazu Munakata, Kiyoshi
Kanamura, Electrochemical properties of Solid/Liquid
Composite-type Electrolyte for Next-Generation Lithium
Batteries, 1st World Conference on Lithium Garnets,
Competitors and Beyond for Advanced Batteries, Sep.,
2017, Hotel Ocean Spray, Pondicherry, India
T. Mandai, K. Kanamura, A Key Concept of Utilization ofBoth Magnesium Chloride and Imide Salts for High
Temperature Rechargebale Mg Battery Electrolytes, 232nd
ECS meeting, Oct., 2017, National Harbor, USA
H. Puthen Peediyakkal, S. Kikuchi, J. Yu, H. Munakata, K.
Kanamura, The Electrochemical Activity of Nitrogen
Doped Graphene Towards Oxygen Reduction Reaction in
Ionic Liquid at Intermediate Temperature, 232nd ECS
meeting, Oct., 2017, National Harbor, USA
H. Munakata, J. Wakasugi, K. Kanamura, Investigation of
Thermal Compatibility of Various Cathode Materials with
Li6.25Al0.25La3Zr2O12 Solid Electrolyte for All-Solid-State
Rechargeable Lithium Batteries, 232nd ECS meeting, Oct.,2017, National Harbor, USA
H. Yamashita, T. Ogami, K. Kanamura, Enhanced
Electrochemical Performance of Li2Mn0.25Co0.75SiO4/C
Cathode Materials for Li-Ion Batteries through Reduced
Graphene Oxide Addition, 232nd ECS meeting, Oct., 2017,
National Harbor, USA
K. Nishikawa, K. Kanamura, Electrodeposition of Li Metal
Onto a Micro-Electrode in Various Electrolytes, 232nd ECS
meeting, Oct., 2017, National Harbor, USA
J. Yu, S. Kikuchi, H. P. Peediyakkal, H. Munakata, K.
Kanamura, Diethylmethylammonium Trifluoromethanesulfonate /Phosphoric Acid Mixture As Electrolyte for Non-Humidified
Intermediate Temperature Fuel Cells, 232nd ECS meeting,Oct., 2017, National Harbor, USA＊Domestic
See the annual report in Japanese (45 articles)■Patents

See the annual report in Japanese (1 patent)■Awards

1.

BCSJ Award (vol. 90, no. 12), Koichi Kajihara, Naoto
Tezuka, Mao Shoji, Jungo Wakasugi, Hirokazu Munakata,
Kiyoshi Kanamura, Li4B4M3O12Cl (M = Al, Ga): anelectrochemically stable, lithium-ion-conducting cubic
boracite with substituted boron sites, Bull. Chem. Soc. Jpn.
90, 1279-1286 (2017)19

Reports from Research Groups
Takagi Laboratory■Members
Shinsuke TAKAGIAssociate Professor /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

Fig. 1. The effective sunlight harvesting system toward artificial
photosynthesis. Dyes with complementary photo-absorption are placedon the clay surface densely without aggregation.

Chemistry,

2. Research on Novel Methodology to Control the Adsorption
Structure of Dyes on the Clay Surface
Shinsuke TAKAGI, Tetsuya SHIMADA
Saponite-type clays that have different cation exchange
capacities were successfully synthesized by hydrothermal
synthesis. The structure and properties were analyzed by X-ray
diffraction, X-ray fluorescence, 27Al NMR, FT-IR,
thermogravimetric and differential thermal analysis, atomic
force microscopy, and cation exchange capacity measurement.
The intercharge distances on the synthetic saponite (SS)surfaces were calculated to be 0.8-1.9 nm on the basis of ahexagonal array. The complex formation behavior between SS
and cationic porphyrins was examined. It turns out that the
average intermolecular distance between porphyrin moleculeson the SS surface can be controlled, depending on the charge
density of the SS. The adsorption behavior of porphyrin on the
SS surface can be rationally understood by the previously
reported “size-matching rule”. This methodology using
host-guest interaction can realize a unique adsorption structure
control of the porphyrin molecule on the SS surface, where thegap distance between guest porphyrin molecules is rather large.
These findings will be highly valuable to constructphotochemical reaction systems such as energy transfer in thecomplexes.

Tetsuya SHIMADA
Research Associate /Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Master’s course -15
Bachelor 4 -7

■Outlines of the Research

Our group challenges to control photochemical reactions
such as electron and energy transfer, by controlling theorientation and alignment of dyes on the inorganic surfaces.
Recently, organic/inorganic hybrids composed of porphyrins
and layered materials have been the subject of intensive
investigations to explore their novel properties andfunctionalities. We found out that a precise matching of
distances between the negatively charged sites on the clay
mineral layers and that between the positively charged sites inthe dye molecule is one of the most important factors todetermine the structure of the clay–dye complex. We havetermed this the “Size-Matching Rule” Our goal is finding out a
new methodology to control molecular assembly structure andrealizing functionalized photochemical reaction systems suchas 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 forconstruction of 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.

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. Surface – Fixation Induced Emission on the nanosheets
Shinsuke TAKAGI, Tetsuya SHIMADA
We investigated the fluorescence enhancement behavior of
AIE (Aggregation Induced Emission) – active dyes on the clay
nanosheet. Judging from their adsorption observation on theclay in water, the factor for the fluorescence enhancement isturned 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.

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

20Reports from Research Groups
4. Research on Novel Hybrid Complex of Semiconductor
Nano-Sheet and Dye
Shinsuke TAKAGI, Tetsuya SHIMADA
A semiconductor nano-sheet was focused as our new
research target in addition to the "insulator" clay nano-sheet.
We expected we effectively extend our distinctive research
about clay-dye hybridization methodology in order to create
new materials with good electron transfer property for artificial
photosynthesis system. We synthesized a novel TiO2 nano-sheet(TNS) and characterized it in detail. We observed adsorption
behavior of porphyrin dyes on the TNS and photochemicalinteraction between the dyes and the TNS.

9.

10.

11.

12.

13.

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

■Papers with Peer Review
1.

2.

3.

4.

5.

6.

7.

8.

Energy Transfer among Three Dye Components in a
Nanosheet-Dye Complex: An Approach To Evaluating
the Performance of a Light-Harvesting System, Y.
Ohtani, S. Kawaguchi, T. Shimada, S. Takagi, J. Phys.
Chem. C, 121, 2052-2058 (2017).
“Size-Matching Effect” in Cationic Porphyrin-Titania
Nanosheet Complex, A. Sonotani, T. Shimada, S. Takagi,
Chem. Lett., 46, 499-501 (2017).
Trapping of excess energy in a nano-layered
microenvironment to promote chemical reactions, V.
Ramakrishnan, Y. Nabetani, D. Yamamoto, T. Shimada,
H. Tachibana, H. Inoue, Phys. Chem. Chem. Phys., 19,4734-4740 (2017).
Photoinduced electron transfer in layer-by-layer thinsolid films containing cobalt oxide nanosheets,
porphyrin, and methylviologen, R. Sasai, Y. Kato, W.
Soontornchaiyakul, H. Usami, A. Masumori, W.
Norimatsu, T. Fujimura, S. Takagi, Phys. Chem. Chem.
Phys., 19, 5611-5616 (2017).
Unique Fluorescence Behavior of Dyes on the Clay
Minerals Surface: Surface Fixation Induced Emission(S-FIE), D. Tokieda, T. Tsukamoto, Y. Ishida, H.
Ichihara, T. Shimada, S. Takagi, J. Photoch. Photobio. A,
339, 67–79 (2017).
Light Energy Accumulation from Pyrene Derivative toTris(bipyridine)ruthenium on Clay Surface, D.
Morimoto, H. Yoshida, K. Sato, K. Saito, M. Yagi, S.
Takagi, T. Yui, Langmuir, 33, 3680–3684 (2017).
Highly Selective Photochemical Epoxidation of
Cyclohexene Sensitized by Ru(II) Porphyrin-ClayHybrid Catalyst, D. Tatsumi, T. Tsukamoto, R. Honna, S.
Hoshino, T. Shimada, S. Takagi, Chem. Lett., 46,
1311-1314 (2017).
Photoluminescence by Intercalation of a Fluorescent
β-Diketone Dye into a Layered Silicate, M. Hirose, F.
Ito, T. Shimada, S. Takagi, R. Sasai, T. Okada,Langmuir, 33, 13515–13521 (2017).

Adosorption And Photochemical Behavior Of
Mono-Cationic Porphyrin Onto Synthetic Saponite, S.
Wakayama, S. Takagi, T. Shimada, Clay Science, 20, 1-3(2017).
Characterization of Dispersed Titania Nanosheet under
Aqueous Conditions and its Complex Formation
Behavior with Cationic Porphyrin, K. Sano, A. Sonotani,
D. Tatsumi, Y. Ohtani, T. Shimada, S. Takagi, J.
Photoch. Photobio. A, 353, 597-601 (2018).
Active Species Transfer-Type Artificial Light
Harvesting System in the Nanosheet – Dye Complexes:
Utilization of Longer Wavelength Region of Sunlight, S.
Suzuki, D. Tatsumi, T. Tsukamoto, R. Honna, T.
Shimada, H. Inoue, S. Takagi, Tetrahedron Lett., inpress.
Elucidation of the Adsorption Distribution of Cationic
Porphyrin on the Inorganic Surface by Energy Transfer
as a Molecular Ruler, A. Nakayama, J. Mizuno, Y.
Ohtani, T. Shimada, S. Takagi, J. Phys. Chem. C, inpress.
Fluorescence Enhancement Behavior of Hemicyanine
Derivatives on the Clay Nanosheets: Aggregation
Induced Emission (AIE) vs. Surface - Fixation Induced
Emission (S-FIE), N. Kudo, T. Tsukamoto, D. Tokieda,
T. Shimada, S. Takagi, Chem. Lett. in press.

■Books1.

Inorganic Nanosheets and Nanosheet-Based Materials(Chapter 1. &14. ), S. Takagi, Springer (2017).

+2 articles in Japanese (See the annual report in Japanese)■Invited Lectures

1.

2.

3.
4.

5.

PHOTOCHEMICAL EPOXIDATION WITH LIGHT
HARVESTINGFUNCTIONALITYON
THE
INORGANIC SURFACES, S. Takagi, 2017 International
Conference on Artificial Photosynthesis (ICARP2017).
Environment-responsive materials composed by dyes andlayered compounds, S. Takagi, The 1st International
Workshop on Chromogenic Materials and Devices.
Dream of artificial photosynthesis, S. Takagi, Third FoSClub Meeting.
Unique absorption and emission behavior of layeredmaterials – dyes complexes in special session (Color
Materials
Science:
Coloration
Principles
andStimuli-Responsivity), S. Takagi, The 98th CSJ Annual
Meeting.
Unique reaction field provided by two-dimenssional
materials
in
specialsession(Next-generation
photofunctional materials innovated by dimensional
reaction fields), S. Takagi, The 98th CSJ Annual Meeting.

■Academic Meeting＊International
1.
Control of Molecular Assembly Structure on
Semiconductor Photocatalyst for Artificial Photosynthesis,
K. Sano, A. Sonotani, Y. Ohtani, T. Shimada, S. Takagi,
The 2nd International Symposium on Hydrogen Energy‒
based Society, Tokyo (Japan), November, 2017.

21

Reports from Research Groups＊Domestic
See the annual report in Japanese (20 articles)■Patents
1.

Patent No. 6183838, S. Takagi, S. Takagi, T. Umemoto,August, 2017.

■Awards

1.

2.

3.

4.

Keito SANO, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Presentation Award, September, 2017.
Minori MONMA, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Poster Award, September, 2017.
Jyunpei HARA, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Poster Award, September, 2017.
Keito SANO, The solid and surface photochemistry
conference 2017, Excellent oral presentation award,
2017.

22

Reports from Research Groups
Yamaguchi Laboratory■Members

Motowo YAMAGUCHI
Professor / Dr. Eng
Applied Coordination Chemistry,
Photofunctional Metal Complex
room:9-542 TEL: +81-42-677-2849
e-mail: yama@tmu.ac.jp
Kiyoshi SATO
Associate Professor /Dr. Eng.
Heterocyclic Chemistry, Molecular
Aromatic Chemistryroom:9-542 TEL: +81-42-677-2848
e-mail: sato-kiyoshi@tmu.ac.jp

lingand with a solvent molecule in the heterodinuclear complex
was slower than that of the deprotonated complex.
Oxidation

Recognition,c) Pyrazine-bridged macrocyclic tetranuclear complexes andtheir inclusion behavior: Utilizing the mononuclear ruthenium
complex with a tridentate ligand containing a pyrazine moiety
as a bridging moiety as the unit, we have found that themacrocyclic tetranuclear complex, molecular square, wereselectively obtained by self-assembly. It was found that a
rod-like anion, such as a thiocyanide ion or an azide ion, or aspherical ion, such as a halide ion, was included in the cavity ofthe macrocyclic tetranuclear ruthenium complex, and theinclusion behavior has been examined by 1H NMR and DOSY
spectra. The structures of host-guest complex with a halide ion
have been examined by DFT calculation. It was found that thehost-guest complex with a chloride or a bromide ion has threeminima, two in the rim and one in the center of the cavity,
while that with an iodide ion has only two in the rim and nonein the center since the ion was too large to be included in thecavity.

Catalyst,

Novel

Master’s course -4
Bachelor 4 -4■Outlines of the Research
1. Development of Photofunctional Ruthenium Complexes
Motowo YAMAGUCHIa) Switching function of ligand photodissociation: A
mixed-ligand type ruthenium complex with terpyridine
derivative having imidazolyl groups which was reversibly
protonated and deprotonated by acid and base has beensynthesized and the control of its ligand photodissociation has
been examined. The reversible protonation and deprotonation
was affirmed, then the ligand photodissociation has been
examined in acetone. It was found that the rate ofphoto-induced dissociation of the complex was considerably
inhibited by a factor of a hundred in the presence of base. The
high regulation of the rate of the reaction was successfully
attained by acid and base. Thus the imidazolyl groups wasfound to be the useful switch being controllable by the additionof acid and base, and its capability has been improved verymuch in the control of the rate of ligand dissociation of thecomplex. Further studies for its application are in progress.

Fig.2 Enegry optimized structure of pyrazine-bridged Ru4
molecular square
2. Development of Novel Ionic Aggregation-Induced
Emission (AIE) Flurophores
Kiyoshi SATO
Color tunable and stimuli responsible solid-state organic
fluorophores attract great attention because of their various
applications in bio-imaging dyes, solid-state sensors, andsecurity inks. However, most of typical organic fluorophores
showing strong emission in dilute solutions generally exhibit aweak or non-fluorescence in films or in the solid states due toaggregation-caused quenching (ACQ) effect. By contrast, Tangand co-workers reported an opposite phenomenon termed
aggregation-induced emission (AIE), which shows weak or
non-emission in solutions but strong emission by aggregation.
Although a number of AIEgens based on polyaryl-heterocycles
have been reported, there are few examples of AIE dyes
adopting an ionic heterocyclic core. However, these ionic AIEdyes still have a room for improvement. For instance, thefluorogen of bis(2,4,6-triphenylpyridinio)benzene (BTPPB)
yields a photo-bicyclized product during measurements of thefluorescence, the resulting planer polycyclic aromatic cationemits strong fluorescence in solution while forms non-emissive
π-stacked aggregates in the solid state. In addition, the AIE
activity of BTPPB is even lower than that of typical AIEgens.
In this work, we therefore designed a series of new ionic AIE

Fig.1 Control of the ligand photodissociation by external
stimulib) Synthesis of heterodinuclear ruthenium-neodymium
complex and its photochemical behavior: New heterodinuclear
ruthenium-neodymium complex has been synthesized by using
the ruthenium complex having a bridging ligand,bisbenzimidazole, by adding a solution of neodymium complex
in acetone. The rate of photoexchange reaction of a MeCN

23

Reports from Research Groups
dyes based on 1,2,4,6-tetraphenylpyridinium cation. The
heteroatom-bridged dimers (2-O, 2-S, and 2-NH) show a good
photostability, a high AIE activity, and a color tunable emission
in the aggregation state.
Initially, in order to verify the intramolecular charge transfer
effect on the photostability, the photocyclization of threepara-OMe substituted 1,2,4,6-tetraphenylpyridinium cations
were investigated. In the case of 1-MeOPh, no absorption
spectral change was observed after 2h photo-irradiation. The
ICT effect also affected to the fluorescence properties.
Moreover, 1-MeOPh exhibits higher AIE activity than2,6-MeOPh and 4-MeOPh derivaties. On the basis of the results
above, a series of bridged tetraphenylpyridinium dimers were
designed and prepared. The solid-state Φf values of the dimers
are higher than those of the corresponding monomers. In
addition, the heteroatom-bridged dimers, 2-O, 2-S and 2-NH,
exhibited good AIE characteristics and their emission
wavelengths of the aggregates varied with theelectron-donating strength of the heteroatoms.

Therefore, in this study, in order to elucidate the reactivity andthe regioselectivity, the photoreaction of polyarylpyridinium
cations was investigated.
The photoreaction of 1,2,3,5,6-pentaphenylpyridinium cation
afforded a bis-cyclized photoproduct. The reaction selectively
occurs at the 1,2,6-phenyl moiety and no further reaction orother cyclization at different site was observed. To confirm thelow reactivity between 2,3- (or 5,6-) phenyl rings, thephotoreaction of 1-methyl-2,3,4,5,6-pentaphenylpyridinium
and 1-methyl-2,3,5,6-tetraphenylpyridinium cations were
investigated. The progress of the reaction between 2,3- (or 5,6-)
phenyl rings was very slow. Based on the above findings, thephotoreaction of a preliminarily cyclized precursor to thehexabenzocoronene analog is now in progress.

■Papers with Peer Review

1.

Dual-mode Cross-coupling on Aromatic Imino
Compounds by Dihydridoruthenium Catalysts, D.
Hirasawa, Y. Watanabe, T. Yamahara, K. Tanaka, K. Sato,T. Yamagishi, Molecular Catalysis, in press (2018)■Academic Meeting＊International
1. Motowo YAMAGUCHI, Pyrazine-bridged Macrocyclic
Tetranuclear Ruthenium Complex: Synthesis, Inclusion
Behavior, and Electrochemical Properties, The 24th
International SPACC Symposium, Nov., 2017, Auckland,
New Zealand.
2. Wataru
MURATA,
Kiyoshi
SATO,
MotowoYAMAGUCHI, Exploring Efficient Metal Complexes as a
Catalyst for Hydrogenation and Dehydrogenation, The
2nd International Symposium on Hydrogen Energy‒based
Society, Nov., 2017, Hachioji, Japan.
3. Ken SEIMIYA, Kiyoshi SATO, Motowo YAMAGUCHI,
Application of Bis-Pyridinium Derivatives for a
Multi-Electron Anolyte of Aqueous Organic Redox Flow
Batteries, The 2nd International Symposium on Hydrogen
Energy‒based Society, Nov., 2017, Hachioji, Japan.

Fig.3 Fluorescence photograph of a heteroatom bridged
tetraphenylpyridinium dimer
3. Synthesis and Properties of Polycyclic Azonia Aromatic
Compounds by Multiple Photocyclization
Kiyoshi SATO
Fused heterocyclic cations having a graphitic-type quaternary
nitrogen atom at a bridgehead position of the sp2-carbon
frameworks are expected to exhibit an efficient catalytic
activity for water oxidation and their potential use as opticalsensors, and electronic devices. The photobiscyclization of
1,2,4,6-tetraarylpyridinium cation is a facile method for thesynthesis of the polycyclic heteroaromatic cations. However, insome cases, the photochemical cyclodehydrogenation ofsubstituted 1,2,4,6-tetraphenylpyridiniums stopped at themono-cyclization stage or completely interrupted due to theelectronic influence and/or steric hindrance of the substituents.
On the other hand, photobiscyclization of hexaarylpyridinium
took place between the 3,4,5-phenyl groups, the reaction site isdifferent from the case of 1,2,4,6-tetraphenylpyridinium. In
addition, the photoreaction stopped even though three phenylgroups remained.

hν
R

R
N+

＊Domestic
4. Motowo YAMAGUCHI, Kento AOSHIMA, Aya
HAMAZAKI, and Kiyoshi SATO, Syntheses, Inclusion
Behavior,
andElectrochemical
Properties
ofPyrazine-bridged Macrocyclic Tetranuclear Ruthenium
Complex, 67th Conference on Coordination Chemistry ofJapan, Sept., 2017, Sapporo. (in English)
5. Sakurako TAMAI, Kiyoshi SATO, and Motowo
YAMAGUCHI,
Synthesis
andPropertyof
Ruthenium-neodymium Dinuclear Complex, 67th
Conference on Coordination Chemistry of Japan, Sept.,
2017, Sapporo. (in Japanese)
6. Kengo
NOZAKI,
SachioKIMURA,
MotowoYAMAGUCHI, and Kiyoshi SATO, Aggregation-induced
Emission Property of Aryl-substituted Pyridinium andImidazolium Based on Rational Design，28th Symposiumon Physical Organic Chemistry, Sept. 2017, Fukuoka. (inJapanese)
7. Moe TORII, Yusuke IKEDA, Motowo YAMAGUCHI,
andKiyoshi
SATO,
SynthesisofDiazoniahexabenzoperylene by Multiple Photocyclization,
28th Symposium on Physical Organic Chemistry, Sept.
2017, Fukuoka. (in Japanese)

N+

R=H
R = PhhνN+N+

Fig.4 Photobiscyclization of 1,2,4,6-tetraphenylpyridinium andhexaphenylphenylpyridinium cations

24

Uchiyama Laboratory■Members

capilly gas chromatography and capillary electrophoresis.
Currently, the technique is applied to on-line sample preconcentration for capillary electrophoresis and to liquid-liquid
extraction.

Katsumi UCHIYAMA
Professor /Dr. Pharmacol.
Analytical Chemistry, Micro Chemistry, Micro-TAS, Laser
spectrometry
room: 9-339 TEL: +81-42-677-1111 Ext.4877
e-mail: uchiyama-katsumi@tmu.ac.jp
Hizuru NAKAJIMA
Associate Prof. / Dr.Eng.
Analytical Chemistry, Micro-TAS, Chromatography,
Electrophoresis, Chemical sensor, Bio sensor
room: 9-343 TEL: +81-42-677-1111 Ext.4882
e-mail: nakajima-hizuru @tmu.ac.jp
Shungo KATO
Associate Prof. / Dr.Eng.
Atmospheric Chemistry, Analytical Chemistry, Geochemistryroom: 9-338 TEL: +81-42-677-1111 Ext.4875
e-mail: shungo @tmu.ac.jp

2. Development of Ultra Small Droplet ELISA Using Inkjet
Microchip
Katsumi UCHIYAMA and Hu-lie ZENG
Enzyme linked immunoSorbent assay (ELISA), which isbased upon the antigen-antibody reaction, is one of the sensitive
determination methods for protein. ELISA is usually carried out
with micro titer plate with 96 holes and this enables
simultaneous determinations for various samples on the plate.
However, in order to complete the whole assay process, it takes
much time and sometimes complex procedure is necessary. In
order to solve the problem, we have developed ultra small
reaction chamber with small droplet formed by ink-jet
technology. The system realized acceralation of ELISA assay
time and drastic reduction of reagents and sample consumption.

Hidetaka NORITOMIAssistant Prof. / Dr.Eng.
Bioprocess, Enzyme Technology, Nanomaterial
room: 9-148 TEL: +81-42-677-1111 Ext.4838
e-mail: noritomi @tmu.ac.jp
Hu-lie ZENG
Assistant Prof. / phD
Analytical Chemistry, Micro-TAS
room: 9-344 TEL: +81-42-677-1111 Ext.4883
e-mail: zeng-hulie @tmu.ac.jp
Meng SUN
Specially Appointed Associate Prof. / phD
Analytical Chemistryroom: 9-344 TEL: +81-42-677-1111 Ext.4883
sunmeng@tmu.ac.jp
Sueo KAGAWA
Tech. Assistantroom: 9-290 TEL: +81-42-677-1111 Ext.4872
e-mail: kagawa @tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistantroom: 9-291 TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp

3. Development of Micro Chemical Pen
Katsumi UCHIYAMA
We have developed a new micro chemical pen, which enabled
micro chemical modification of the surface of materials. The
pen feeded reaction reagent and catalyst onto the material
surface that was placed in a liquid and formed micro raction
region (sub micrometer to micro meter). Chemical pattern wasformed by scanning the pen with x,y stage. This tool will beapplied to the arrangement tool for molecular machine and its
micro expression of the function, highly functionalization of
micro machines and micro total analysis system.

Doctor’s course -2
Master’s course -7
Bachelor 4 -9

■Outlines of the Research

1. Development of Ultra Small Sample Injection Method Using
Inkjet Microchip
Katsumi UCHIYAMA and Hu-lie ZENG
Ink-jet technology, which enables handling of ultra smallliquid samples, has been applied not only to printer but also
various fields such as chemistry and material sciences. We
have developed ultra small sample introduction method for25

200(mm
EL
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LPF
9CH&PD
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50(mm
50(mm
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9CH

6. Development of Chemiluminescence Analysis System Using
Organic Photodiodes as Photo Detector
Hizuru NAKAJIMA
Chemiluminescence method enables high sensitive detectionof trace components in environmental and biological samples
since the method does not require a light sorce and is not affectedby background noise derived from the light sorce. However, it isdifficult to apply the chemiluminescence method for on-site
analysis since a photomultiplier tube typically used as photodetector in the method is large-size and very expensive. In thisstudy, organic photodiodes (OLEDs) were fabricated on a
microfluidic device and then a novel chemiluminescenceanalysis system was developed using the OLEDs-integrated
microfluidic device. The system was successfully used in thedetermination of hydrogen peroxide based on the enhanced
chemiluminescence using luminol.

4. Development of Micro Total Analysis System Using a
Compact Disk-type Microfluidic Device
Hizuru NAKAJIMA
We have developed a flow-based ELISA system using a
microfluidic device. However, many pumps and valves are
required for multiple immunoassays, which affect total size ofthe analytical system. In this study, we developed a solution
sending method based on the centrifugal force generated byrotation of a compact disk-type microfluidic device. A novelsurface plasmon resonance sensor, a fluorescence detection
system and an electrochemical detection system were developed
using the compact disk-type microfluidic device. Since pumps
and valves are unnecessary, these systems would be useful foron-site analysis, such as environmental monitoring, food safety
testing and point-of-care testing.

Data logger

Reagent②

Dark boxPC①
Syringe pump
SampleOPD

I/V conversion amplifier

Injector
Power supply

Light receiving
section②

H2O2①

Reagent①•

0.1 M Tris-HCl (pH 8.5)

②

•
•
•
•

1.2 mM luminol containing
1.0 mM p-iodophenol
0.1 mg/mL HRP
0.05 % Tween20

Sample•0-16.6 mM H2O2 (500 μL)

Flow rate : 100 μL/min

7. Development of Portable ELISA System for Infection Disease
Diagnosis
Hizuru NAKAJIMA
Tropical area-specific infection diseases such as dengue feverand chikungunya fever are menaced to society in the world since
the viruses, which cause these infection diseases, are easily
spread on a global scale by globalization of the economy. In
order to minimize the damage of the infection diseases, a rapid
diagnostication and a non-proliferation for the viruses are very
important. However, these countermeasures for the danger is not
sufficient in developing countries because of the economic andtechnical problems. In this study, we developed a simple,
portable and inexpensive ELISA system that can be used for
rapid antibody test in the field. The portable ELISA system was
successfully used in the antibody tests for measles and rubellaviruses.

5. Development of Fluorescence Analysis System Using
Organic Light Emitting Diodes as Light Source
Hizuru NAKAJIMA
The microfluidic lab-on-a-chip has provided a platform to
conduct chemical and biochemical analysis in a miniaturized
format. A common detection method for lab-on-a-chip is laser
induced fluorescence. However, the method is not suitable foron-site analysis because of the size, weight and cost of theperipheral devices such as lasers and microscopes. We havesucceeded in incorporating a light-emitting diode (LED) and an
optical fiber into a polymeric microfluidic device in order tominiaturize the total size of the detection system. Recently,
organic light emitting diodes (OLEDs) have been very
successful for lightweight full-color flat panel displays. The
OLEDs have a flat surface, which makes it easy to integrate withmicrofluidic devices and flexible to fabricate into the required
size and shape by photolithography techniques. In this study, wedeveloped a novel portable fluorescence detection system using
OLEDs as light source. The system was successfully used in themeasurement of IgA in human saliva.

26

Shungo KATO
Atmospheric carbon monoxide, ozone, and various volatileorganic compounds were continuously observed at remotesites: cape Hedo in Okinawa, Moshiri in Hokkaido, Suzu in
Ishikawa.

8. Development of surface plasmon resonance sensor using an
optical fiber prepared by electroless displacement gold
plating method
Hizuru NAKAJIMA
Optical fiber-type surface plasmon resonance (SPR) sensor
has some attractive advantages such as small volume of analytes,
miniaturization of senser system and potential capacity forremote sensing. However, it is time-consuming and very costly
to form ideal thickness of gold thin film for SPR (ca.50 nm) onto
the circular cylinder shaped fiber core, precisely. In this study, asimple and low-cost method for fabricating an optical fiber for
SPR sensor was proposed. The method was based on theelectroless nickel plating and the subsequent displacement gold
plating on the core of the optical fiber. The sensitivity andresolution of the SPR sensor using the fabricated optical fiber
was comparable to that of the commercially available SPR
sensors. The sensor was successfully used in the measurement of
IgA in human saliva.

12. Measurements of atmospheric pollutants at mountain sites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide were observed atsummit of Mt. Fuji during summer. There was no influence fromlocal pollution source and typical air at remote site during
summer was observed. Plume from volcano was observed at Mt.
Fuji. For future winter time measurement without commercial
electric power, test measurements of low power gase sensor wasdemonstrated.
13. Atmospheric trace gas measurements using small gas sensor
Shungo KATO
Atmospheric trace gases was measeured by small gas sensors
at urban area and clean remote site at the top of Mt. Fuji. Also,
portable system working by battely was constructed.
14. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen concentration in suburban was observed.

13. Application of biochar to stress resistance of proteins
Hidetaka NORITOMI
To reduce greenhouse gas emissions, biochar was preparedfrom forestry residues, which are carbon neutral, and was used
as a protein carrier. We found that biochar imparts high heatstress resistance and organic solvent stress resistance toproteins. This result would be expected to the applications tobiosensors, bioreactors, biofuel cells, and so on.
9. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
uburban site (Minamiosawa, Tsukuba). Emission sources,
contribution to ozone formation of each VOC were estimated.

■Papers with Peer Review

1. Sifeng Mao, Yong Zhang, Haifang Li, Hulie Zeng, Jin-Ming
Lin, Katsumi Uchiyama
Writing of nanowires via high viscosity-induced nanodiffusive layer
Journal of Materials Chemistry C, 2017,5, pp.11666-11671
2. Yong Zhang, Sifeng Mao, Yuma Suzuki, Yumi Tanaka,
Masato Kawaguchi, Weifei Zhang, Hulie Zeng, Hizuru
Nakajima, Ming Yang, Katsumi Uchiyama
Elaborately programmed nanowires fabricated using atapered push–pull nozzle system
Chemical Communications, 2018,54, pp.719-722
3. Sifeng Mao, Wanling Zhang, Qiushi Huang, Mashooq Khan,
Haifang Li, Katsumi Uchiyama, Jin-Ming Lin
In Situ Scatheless Cell Detachment Reveals Correlation
between Adhesion Strength and Viability at Single-Cell
Resolution
Angew. Chem. Int. Ed, 2018, 57, pp.236 –240
4. Hulie Zeng, Sifeng Mao, Yong Zhang, Hizuru Nakajima,
Katsumi Uchiyama
Reversibly electro-controllable polymer brush for electroswitchable friction
J. Mater. Chem. C, 2017 5, pp5877-5881.
5. Hulie Zeng, Yong Zhang, Hizuru Nakajima,
Katsumi Uchiyama
Reversibly electro-switchable poly-allyloxy hydroxypropyl

10. Studies atmospheric pollutants at sub-urban forest area
Shungo KATO
Various trace gas species were observed at suburban forest
area (FM-Tama). Vertical distribution of trace gases wereobserved on the flux tower at forest area. Influence of biogenic
VOCs to ozone was discussed.

11. Atmospheric trace species measurements at remote sites
27sulfonate branched brushes and its applications
Sensor. Actuat. B, 2017, 251, pp334-338.
6. Yoshihiro Nakashima1, Hiroshi Tsurumaru, Ramasamy,
Sathiyamurthi, Yosuke Sakamoto, Shungo Kato, Yasuhiro
Sadanaga, Tomoki Nakayama, Yuzo Miyazaki, Tomoki
Mochiduki, Ryuichi Wada, Kazuhide Matsuda1, Yoshizumi
Kajii
Ambient measurements and survey of the sources of gaseous
glyoxal at suburban site in Tokyo during summer season
J. Jpn. Soc. Atmos. Environ., 2017, Vol.52, No.6, pp.167-176
7. Tomoki Nakayama, Yuuki Kuruma, Yutaka Matsumi, Yu
Morino, Kei Sato, Hiroshi Tsurumaru, Sathiyamurthi
Ramasamy, Yosuke Sakamoto, Shungo Kato, Yuzo
Miyazaki, Tomoki Mochizuki, Kimitaka Kawamura,
Yasuhiro Sadanaga, Yoshihiro Nakashima, Kazuhide
Matsuda, Yoshizumi Kajii
Missing Ozone-Induced Potential Aerosol Formation at a
Suburban Deciduous Forest
Atmospheric Environment, 2017, 171, pp.91-97
8. Chang-Feng Ou-Yang, Chih-Chung Chang, Jia-Lin Wang,
Kojiro Shimada, Shiro Hatakeyama, Shungo Kato, Jia-Yang
Chiu, Guey-Rong Sheu, Neng-Huei Lin
Characteristics of Summertime Volatile Organic Compounds
in the Lower Free Troposphere: Background Measurements
at Mt. Fuji
Aerosol and Air Quality Research, 2017, 17(12), pp.30373051
9. Hidetaka Noritomi, Jumpei Nishigami, Nobuyuki Endo,
Satoru Kato, Katsumi Uchiyama
Influence of water activity on protease adsorbed on biochar
in organic solvents
Journal of Materials Science Research, 2017, 6(4), pp. 96102

Okochi, Masashi Kamogawa, Naoki Kaneyasu, Yoko
Katayama, Kazuya Sasaki, Shungo Kato, Yukiya Minami,
Hiroshi Kobayashi
Ten years research at Mount Fuji research station2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
5. K. Shimada, C. F. Ou-Yang, S. Kato, N. H. Lin1, C. K. Chan,
Y. P. Kim, and S. Hatakeyama
Aerosol chemistry in summer at the top of Mt. Fuji
2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
6. Ryota Kataoka, Kazuhiko Miura, Masahiro Momoi, Yoko
Iwamoto, Masanori Yabuki, Katsuhiro Nagano, Shungo Kato,
Hiroshi Kobayashi, Hiroshi Hayami, Hiroshi Okochi
Properties of new particle formation at the summit of Mt. Fuji,
Japan - Measured results during summer from 2006 to 2016 ?
2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
7. Yosuke Miyauchi, Hiroshi Okochi, Kojiro Shimada, Naoya
Katsumi, Yukiya Minami, Hiroshi Kobayashi, Kazuhiko
Miura, Shungo Kato, Masaki Takeuchi, Kei Toda, Shinichi
Yonemochi
Observation of acidic gases and aerosols in the upper
atmospheric boundary layer and in the free troposphere on Mt.
Fuji (2)2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
8. Tatsuya Yamaji, Hiroshi Okochi, Satoshi Ogawa, Naoya
Katsumi, Kojiro Shimada, Hiroshi Kobayashi, Yukiya
Minami, Kazuhiko Miura, Shungo Kato, Shin-ichi Yonemochi,
Natsumi Umezawa, Kiyoshi Nojiri, and Kei Toda
Observation of gaseous mercury at the top and the foot of Mt.
Fuji
2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
9. Ryuichi Wada, Yasuhiro Sadanaga, Shungo Kato, Naoya
Katsumi, Hiroshi Okochi, Yoko Iwamoto, Kazuhiko, Miura,
Hiroshi Kobayashi, Hitoshi Kamogawa, Jun Matsumoto,Seiichiro Yonemura
NOy measurements at the top of Mt. Fuji
2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
10. Shinji Muramoto, Indra Chandra, Yayoi Inomata, Hidenori
Higashi, Yoshio Otani, Takafumi Seto, Kazuhiko Miura, Yoko
Iwamoto, Shungo Kato
Measurement of particle size distribution of nanoparticles atsummit of Mt. Fuji
2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
11. Megumi Nakamura, Hiroshi Okochi, Kojiro Shimada, Naoya
Katsumi, Yukiya Minami, Hiroshi Kobayashi, Kazuhiko
Miura, Shungo Kato
Observation of cloud water chemistry in the free troposphereand the atmospheric boundary layer on Mt. Fuji (4)2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
12. ○Hidetaka Noritomi, Jumpei Nishigami, Nobuyuki Endo,
Satoru Kato, Katsumi Uchiyama
Effect of water activity on enzymes adsorbed on biomass
charcoal in organic media
Third International Conference on Science, Engineering &■Books■Invited Lectures

1. Katsumi Uchiyama
Analytical and Chemical Application of Ink-jet
IUPAC International Congress on Analytical Sciences 2017
(ICAS2017), Hainan InternationalConvention & Exhibition
Center, 6p-CA-K2■Academic Meeting＊International
1. Katsumi Uchiyama
The use of an inkjet injection technique for quantitative online electrophoretically mediated micro
Advances in Pharmaceutical Analysis 2017(APA 2017),
Wuhan University, China, K14
2. R. Kataoka, M. Momoi, K. Miura, Y. Iwamoto, M. Yabuki,
S. KatoFactors controlling daytime and nighttime new particle
formation at the summit of Mt. Fuji, Japan
Asian Aerosol Conference (AAC) 2017, Jeju
3. Shungo Kato, Hiroshi Okochi, Kazuhiko Miura
CO and O3 observation at the summit of Mt. Fuji during
summer2017 Symposium on Atmospheric Chemistry and Physics at
Mountain Sites, Gotemba
4. Yukiko Dokiya, Shiro Hatakeyama, Kazuhiko Miura, Hiroshi
28

Environment (SEE-USQ 2017), University of Southern
Queensland, Brisbane, Australia, 3600
13. Miyu Nakajima, Atsushi Shoji, Kenji Morita, Kazuhiro
Morioka, Akio Yanagida, Akihide Hemmi, Hulie Zeng,
Shungo Kato, Katsumi Uchiyama, Hizuru Nakajima
Development of surface plasmon resonance sensor using
an optical fiber prepared by electroless displacement gold
plating method
PITTCON2018, Orlando, Florida , USA, 660-21P＊Domestic
See the annual report in Japanese (27articles)■Awards

1. Moeko Osashima (Master's course 1years)
Royal Society of Chemistry Analyst Poster Prize“Development of fluorescence detection system for on-site
analysis using pipette tips”
Proc. of the 66th annual meeting of the Japan Society for
Analytical Chemistry (Tokyo University of Science ) (inJapanese)
2. Hulie Zeng, Leading Scientist, Graduate School of Urban
Environmental Sciences,Tokyo Metropolitan University29

Reports from Research Groups
Kubo Laboratory■Members
Yuji Kubo
Professor /Dr. Eng.
Organic Chemistry, Supramolecular Chemistry, Functional Dye
room: 9-539 TEL: +81-42-677-3134
e-mail: yujik@tmu.ac.jp
J. Yan Mulyana
Associate Professor / Ph.D.
Coordination Chemistry, Photochemistryroom: 9-149 TEL: +81-42-677-2823
e-mail: ymulyana@tmu.ac.jp
Ryuhei Nishiyabu
Assistant Professor / Dr. Eng.
Supramolecular Chemistry, Organic Chemistry, Matetials
Chemistryroom: 9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: ryuhei@tmu.ac.jp

3. Synthesis of Dyes Applicable to Dye-Sensitized Solar Cells
Name: Yuji Kubo
Due to our interest in the development of functional dyes that
can absorb longer wavelength of radiations, synthesis andcharacterization of π-extended dibenzo-boron-dipyrromethenes(dibenzo-BODIPYs) have been investigated. For the approach,the related sensitizers applicable to dye-sensitized solar cells
are worthwhile to be investigated. In this study,
dibenzo-BODIPYs with a phenothiazinylcyanoacrylic acidgroup and rhodamine groups have been newly prepared,
respectively.

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

■Outlines of the Research
1. Synthesis of Tetraphenylethylene-Containing Boronate andtheir Self-Assembly for Chiral Sensing
Name: Yuji Kubo
There has been growing interest in π-conjugated moleculeswith aggregation-induced emission (AIE) capability, whichhave prompted chemists to develop new luminescent systems
in materials science. To develop hierarchical supramolecules
based on boronate esterification, dehydration of di(boronicacid)-appended tetraphenylethylene with tartaric acid wasinvestigated for chiral sensing.

4. Synthesis of Selenophene-containing Dyes
Name: Yuji Kubo
Selenium is relatively more polarizable and softer than sulfur,
due to its size. Although the low oxidation potential leads toelectrondonating
propertyofselenium-containing
π-conjugation to endow it with promising OFET materials, theproposal of emissive compounds with selenium are limited
because of the heavy atom effect. On another front, there has
been increasing demand for the development of dyes withstableexcitedtripletstates.
In
thisstudy,
selenophene-substituted BODIPY (Se-BDP) has been newly
synthesized
5. Construction of Triplet-Triplet Annihilation-Based
Upconversion Molecular Systems
Name: Yuji Kubo
Triplet-triplet
annihilation-based
photonupconversion(TTA-UC) have attracted increasing attentions as promising
methods for energy conversion from low-energy excitation tohigher energy light because of various applications involving
solar cells, photocatalysts, and so on. However, TTA-UC is ahighly oxygen sensitive process, resulting in a low efficiency inthe presence of oxygen. In this study, a Co complex was used
to overcome such difficulty, which is known as an oxygen
scavenger. Subsequently, we found that the addition of the Co
complex into the solution of Pt(II) porphyrin (PtOEP) as asensitizer and 9,10-diphenylanthracene (DPA) as an annihilator
led to significant quenching of UC emission, whereas
phosphorescence emission due to the sensitizer almost
remained.

2. Visible Light-induced Water Splitting with Photosensitizing
Dye
Name: Yuji Kubo and J. Yan Mulyana
There is an urgent need for creating new energy materials
capable of producing hydrogen fuel from water as analternative to the use of fossil fuels. Our research is concernedwith creating bio-inspired energy materials, namely photoelectrochemical (PEC) cells, which are capable of harvesting
light energy to drive the water splitting process. The
construction of the devices involves the synthesis of organicand inorganic materials, which can be assembled withappropriate semiconductors such as titanium oxide (TiO2) andindium tin oxide (ITO) nanoparticles.

6. Synthesis of a 1-hydroxy-2,3,1-benzodiazaborine-containing
π-conjugated system
Name: Yuji Kubo and Ryuhei Nishiyabu
A
1-hydroxy-2,3,1-benzodiazaborine
conjugatedwith
1,8-naphthalimide was synthesized. Its fluorescence wasdramatically affected by the nature of the solvent. In particular,
the use of DMSO, which has a relatively high donor number,
led to a remarkable decrease in the fluorescence intensity,
possibly due to intermolecular hydrogen-bonding interactions.
30

Reports from Research Groups
The presence of the hydroxyl group on boron led to asolvent-driven colorimetric response towards anions; highselectivity for fluoride ion over other anions in DMSO, andresponded to acetate ion and fluoride ion in THF.

10.1039/C7CC00490G
7. K. Sakakibara, Y. Takahashi, R. Nishiyabu and Y. Kubo, A
Zn2+-coordinated boronate dipyrrin as a chemodosimeter
toward hydrogen peroxide, J. Mater. Chem. C, 2017, 5,3684−3691. DOI: 10.1039/C7TC00405B (2017 Journal of
Materials Chemistry C HOT papers)
8. Y. Satta, R. Nishiyabu, T. D. James and Y. Kubo, A
1-hydroxy-2,3,1-benzodiazaborine-containing π-conjugatedsystem: synthesis, optical properties and solvent-dependent
response toward anions, Tetrahedron, 2017, 73, 2053−2061.
DOI: 10.1016/j.tet.2017.02.050
9. Y. Kubo and R. Nishiyabu, White-light emissive materials
based on dynamic polymerization in supramolecularchemistry,
Polymer,
2017,
128,257−275.
DOI:10.1016/j.polymer.2016.12.082.

7. A zinc-coordinated boronate dipyrrin as a chemodosimeter
toward hydrogen peroxide
Name: Yuji Kubo and Ryuhei Nishiyabu
To develop a chemodosimeter for the visual detection ofhydrogenperoxide,adipyrrindye
with
4-pinacolborylbenzyloxy groups was synthesized. An ethanol
solution of the dye was reddish-violet in color. The addition ofhydrogen peroxide into the solution induced a remarkable color
change from reddish-violet to blue. . For practical applications,the related drop-cast paper strips were fabricated to visuallydetect hydrogen peroxide vapor.
8. Development of Chemical Modifiers for Surface
Functionalization of Polyvinyl Alcohol.
Name: Yuji Kubo and Ryuhei Nishiyabu
Chemical modifiers with boronic acid groups as anchoringgroups have been synthesized for the development ofmaterial-based chemosensors and 3D cell culture matrix
through surface functionalization of PVA sponges.

■Invited Lectures
1. Hierarchical supramolecules using boronic acid building
blocks, Yuji Kubo, The 4th International Seminar of
Chemistry, Bundung (Indonesia), September 29th, 2018
(Plenary lecture).
See the annual report in Japanese for other invited lectures (twopresentations).

9. Development of near-infrared absorbing photoelectric
conversion devices.
Yuji Kubo
There has been a growing interest in near-infrared(NIR)-absorbing dyes with absorption or emission bands
beyond 700 nm due to their potential applications in organic
electronics. In this study, naphtho[1,3,2]oxazaborinine-type
dibenzo-BODIPYs was newly synthesized and incorporated
optoelectric devices. The resultant devices would be applicable
to near-infrared absorbing photodetectors.

■Academic Meeting＊International
1. A near-infrared organic photosensitizer for use in dye
sensitized photoelectrochemical water splitting ， Okta
Suryani, Yuta Higashino, J. Yan Mulyana, Yuji Kubo，
Chemistry conference for young scientists，Blankenberge，Belgium，2018，Feb 21st
＊Domestic
See the annual report in Japanese for other presentations (13presentations).
1. A near-infrared organic photosensitizer for use in dye
sensitized photoelectrochemical water splitting ， Okta
Suryani, Yuta Higashino, J. Yan Mulyana, Yuji Kubo，1C03，
Annual meeting on photochemistry 2017 ， Tohoku
University，2017，Sep 4th
2. A near-infrared organic photosensitizer for use in dye
sensitized photoelectrochemical water splitting ， Okta
Suryani, Yuta Higashino, J. Yan Mulyana, Yuji Kubo，2P-54，
International symposium on novel energy nanomaterials,
catalysts and surfaces for future earth，The University ofelectro-communications，2017，Oct 29th
3. A new and robust ruthenium photosensitizer for
light-induced hydrogen production from water indye-sensitized photoelectrochemical cells (DSPECs)，Indra
Purnama, Yuji Kubo, Jacob Yan Mulyana ， 2P-55 ，International symposium on novel energy nanomaterials,
catalysts and surfaces for future earth，The University ofelectro-communications，2017，Oct 29th
4. A near-infrared organic photosensitizer for use in dye
sensitized photoelectrochemical water splitting ， Okta
Suryani, Yuta Higashino, J. Yan Mulyana, Yuji Kubo，P-13，
The 2nd International symposium on hydrogen energy-basedsociety，Tokyo Metropolitan University，2017，Nov 21st
5. A new and robust ruthenium photosensitizer for
light-induced hydrogen production from water indye-sensitized photoelectrochemical cells (DSPECs)，Indra
Purnama, Yuji Kubo, Jacob Yan Mulyana，P-3，The 2nd■Papers with Peer Review

1. Y. Kubo, S. Tobinaga, Y. Ueno, T. Aotake, Hi. Yakushiji, andT. Yamamoto, Near-infrared-absorbing Photodetectors Basedon Naphtho[1,3,2]oxazaborinine-type Dibenzo-BODIPY
Dyes, Chem. Lett., 2018, 47, 300−303. DOI:
dorg/10.1246/cl.171061
2. I. Purnama Y. Kubo, J. Y. Mulyana, A robust ruthenium
complex with nonyl-substituted bpy ligand for
dye-sensitized photoelectrochemical cell application, Inorg.
Chim.
Acta,
2018,
471,
467−474.
DOI:
10.1016/j.ica.2017.11.052
3. M. Kawai, A. Hoshi, R. Nishiyabu and Y. Kubo, Fluorescentchirality recognition by simple boronate ensembles withaggregation-induced emission capability, Chem. Commun.,2017, 53, 10144−10147. DOI: 10.1039/C7CC05784A
4. S. Erten-Ela, Y. Ueno, T. Asaba and Y. Kubo, Synthesis of adibenzo-BODIPY-incorporating phenothiazine dye as apanchromatic sensitizer for dye-sensitized solar cells, New. J.
Chem.,
2017,
41,10367−10375.
DOI:
10.1039/C7NJ01735A
5. O. Suryani, Y. Higashino, J. Y. Mulyana, M. Kaneko, T.
Hoshi, K. Shigaki and Y. Kubo, Near-infrared organic
photosensitizer
for
use
in
dye-sensitized
photoelectrochemical water splitting, Chem. Commun., 2017,53, 6784−6787. DOI: 10.1039/C7CC02730C
6. R. Nishiyabu, S. Iizuka, S. Minegishi, H. Kitagishi, and Y.
Kubo, Surface modification of polyvinyl alcohol spongewith functionalized boronic acid to develop porous materials
for multicolor emission, chemical sensing and 3D cell
culture, Chem. Commun., 2017, 53, 3563−3566. DOI:

31

Reports from Research Groups
International symposium on hydrogen energy-based society，Tokyo Metropolitan University，2017，Nov 21st
6. Synthesis of a quinoline amide dye with a boronic
acid-grafting group and its application to chemosensors,
Uji;Pramoto, Yuji Kubo, 1F5-36, The 98th CSJ Annual
meeting Nihon University，2018，March 20th,
7. Photocatalytichydrogenproductionusingadibenzo-BODIPY-incorporated
phenothiazineaspanchromatic photosensitizer，Okta Suryani, Yumi Maeda, J.
Yan Mulyana, Yuji Kubo，3I1-07，The 98th CSJ Annual
meeting Nihon University，2018，Mar 22nd
8. Dynamics of water reduction by dye-sensitized
photoelectrochemicalcells
incoporating
ruthenium
photosensitizers ， Indra Purnama, Yuji Kubo, Jacob Yan
Mulyanaoral ， 2B5-43 ， The 98th CSJ Annual
meeting，Nihon University，2018，Mar 22nd

32

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

constructing polyfunctionalized arenes. Hence, the developmentof a novel catalytic system with a wide substrate scope as wellas substantial environmental compatibility is highly important.
In this year, we found that supported PdAu alloy catalysts
showed high activity for [2+2+2] cycloaddition of alkynes.
Furthermore, detailed structural analyses of the alloy catalysts
revealed that the coexistence of Pd species and Au species is
indispensable for the efficient cycloaddition over Pd–Au NPs.

chemistry,

Lidan Deng
Assistant Professor /Dr. Eng.
Catalysis Science
room:9-538 TEL: +81-42-677-2851 (Ext. 4958)
e-mail: deng-dan@tmu.ac.jp

Au

Pd

Doctor’s course -1
Master’s course -15
Bachelor 4 -7

PdAu alloy

3. Green transformation of organic molecules by transitionmetal catalysts
Hiroki Miura, Tetsuya Shishido■Outlines of the Research

1. Metal-oxide based catalysts effective for converstion of
exhaust gas from vehicles
Tetsuya Shishido, Hiroki Miura

Selective C-C bond formation by transition-metal catalysts isimportant method for synthesizing complex organic molecules
often found in midicines and functional organic materials. In thisyear, we investigated ruthenium-catalyzed addition of aromatic
acids to aldehydes to give isobenzofuranone derivatives. Under
optimized conditions, a series of isobenzofuranones wereobtained in good to high yields. Furthermore, we also found that
supported Ru catalysts were effective for the title reaction, andthe supported catalytsts could be reused for several times without
significant loss of activity.

The reduction of the amount of PGM or the development of
replaceable materials have been investigated extensively.
However, this is still a challenging subject, especially the
reduction of NOx (NO and NO2) into N2 without PGM.
We studied catalytic performance of supported Rh catalysts,
which possess a high surface area and thermal stability. The
catalytic activity was evaluated using test reactions of NO, CO,and C3H6 under various simulated exhausts with different air-tofuel ratios. As a result, Rh/NbOPO4 showed higher catalytic
activity than conventional Rh/Al2O3 catalyst. Especially,
Rh/NbOPO4 exhibited superior NO reduction activity under O2excess condition (lean condition).

■Papers with Peer Review

1.

2.

3.
2. Development of supported alloy nanoparticle catalysts
effective for [2+2+2] cycloaddition of alkynes
Tetsuya Shishido, Hiroki Miura
Transition metal-catalyzed [2+2+2] cycloaddition of substituted
alkynes, which involves the formation of three C-C bonds, is themost elegant, versatile and atom-economical method for

4.

33

Hydrosilylation of Allenes over Palladium–Gold Alloy
Catalysts: Enhancing Activity and Switching Selectivity
by the Incorporation of Palladium into Gold Nanoparticles
Miura, H.; Sasaki, S.; Ogawa, R.; Shishido, T. Eur. J. Org.
Chem. 2018, DOI:10.1002/ejoc.201800224
Dynamic Behavior of Rh Species of Rh/Al2O3 Model
Catalyst During Three-Way Catalytic Reaction – An
Operando XAS Study Asakura, H.; Hosokawa, S.; Ina, T.;
Kato, K.; Nitta, K.; Uera, K.; Uruga, T.; Miura, H.;
Shishido, T.; Ohyama, J.; Satsuma, A.; Sato, K.;
Yamamoto, A.; Hinokuma, S.; Yoshida, H.; Machida, M.;
Yamazoe, S.; Tsukuda, T.; Teramura, K.; Tanaka, T. J. Am.
Chem. Soc. 2018, 140, 176-184.
Selective Hydrogenolysis of Tetrahydrofurfuryl Alcohol
over Pt/WO3/ZrO2 Catalysts : Effect of WO3 loading
amount on activity Feng, S.; Nagao, A.; Aihara, T.; Miura,
H.; Shishido, T. Catal. Today 2018, 303, 207-212.
Concerted Functions of Surface Acid-Base Pairs andSupported Copper Catalysts for Dehydrogenative
Synthesis of Esters from Primary Alcohols Miura, H.;
Nakahara, K.; Kitajima, T.; Shishido, T. ACS Omega 2017,
2, 6167-6173.

5.

6.

7.

8.

9.

Effect of WO3 loading on the activity of Pt/WO3/Al2O3
catalysts in selective hydrogenolysis of glycerol to 1,3propanediol Aihara, T.; Kobayashi, H.; Feng, S.; Miura,
H.; Shishido, T. Chem. Lett. 2017, 46, 1497-1500.
Highly active and stable Pt-Sn/SBA-15 catalyst preparedby direct reduction for ethylbenzene dehydrogenation:
Effects of Sn addition Deng, L.; Arakawa, T.; Ohkubo, T.;
Miura, H.; Shishido, T.; Hosokawa, S.; Teramura, K.;
Tanaka, T. Ind. Eng. Chem. Res. 2017, 56, 7160-7172.
Strong metal-support interaction between Pt and SiO2
following high-temperature reduction: a catalytic interface
for propane dehydrogenation Deng, L.; Miura, H.;
Shishido, T.; Hosokawa, S.; Teramura, K.; Tanaka, T.
Chem. Commun. 2017, 53, 6937-6940.
Supported Palladium–Gold Alloy Catalysts for Efficientand Selective Hydrosilylation under Mild Conditions with
Isolated Single Palladium Atoms in Alloy Nanoparticles as
the Main Active Site Miura, H.; Endo, K.; Ogawa, R.;
Shishido, T. ACS Catal. 2017, 7, 1543–1553.
Ruthenium-catalyzed Addition of Aromatic Amides toInternal Alkynes and Subsequent Intramolecular
Cyclization for the Atom-Economical Synthesis of
Isoindolinones Miura, H.; Terajima, S.; Tsutsui, K.;
Shishido, T. J. Org. Chem. 2017, 82, 1231–1289.

2.

3.

4.

5.

6.

7.

■Invited Lectures

1.

2.

3.

4.

5.

6.

7.

8.

37th annual meeting of Hydrogen Energy Systems Societyof Japan, “Approach to realization of low-carbon society
based on hydrogen energy in TMU” (invited lecture) 」
2018/3/1 Nihon University
1st Open symposium of Hybrid catalysts in innovative area,“Molecular transformation by supported alloy
nanoparticle catalysts” 2018/1/30 Nagoya University.
17th Lecture ship of hokkaido division of japan petroleum
institute “Approach to realization of low-carbon society
based on hydrogen energy” (invited lecture) 2018/1/26
Kitami institute of technology
Zasshikai
seminar1709th,「 Synthesis
andcharacterization of nano-sized alloy catalyst (Invitedlecture) 」 2017/12/19 （ The University of Tokyo, 3F
Lecture Room, Chemistry Main Bldg.）
7th CSJ chemistry festa 2017, “Function of niobium andtantalum oxide as solid acid catalyst and photo catalyst”(invited lecture) 2017/10/19 Tower Hall Funabori
120th CatSJ Meeting “Approach to realization of lowcarbon society based on hydrogen energy”, 2H10 (invitedlecture) 2017/9/13 Ehime University
The 4th colloquium of Center for Functional Nano
Oxide ”Catalysis of niobium oxide; acid-base catalysis andphotocatalysis” (invited lecture)」 2017/5/26 （Hiroshima
Unicversity）“Hydrosilylation of Unsaturated Organic Molecules overSupported PdAu Alloy Catalysts”, H. Miura, K. Endo, R.
Ogawa, S. Sasaki, T. Shishido, 16th Japan-Taiwan Joint
Symposium on Catalysis January, 29-31, 2018 Kyoto,
Japan

Hydrogenolysis of glycerol to C3 diols over Pt/WO3/Al2O3
and Pd/L-Nb2O5, T Aihara, H Kobayashi, S Feng, H Miura,
T Shishido, 16th Korea-Japan Symposium on Catalysis(16KJSC, Sapporo) May 15-17, 2017, Hokkaido, Japan
Hydrosilylation of Alkynes and α,β-Unsaturated Ketones
by Supported PdAu Catalysts, H. Miura, K. Endo, R.
Ogawa, S. Sasaki, T. Shishido, EUROPACAT 2017
August, 26-30, 2017 Florence, Japan
Promotion effect of a tiny amount of platinum on theactivity of Ni/TiO2 catalyst for the selective hydrogenation,
K. Noguchi, H. Miura, T. Shishido, EUROPACAT 2017
August, 26-30, 2017 Florence, Japan
Steam reforming of dimethyl ether over Cu/ZnO/Al2O3
coupled with H-ZSM-5: Effect of SiO2/Al2O3 ratio on theactivity, E. Kawai, H. Miura, T. Shishido, The 2nd
International Symposium on Hydrogen Energy‒based
Society November 20-21, 2017 Tokyo, Japan
Selective catalytic reduction of NO with CO and C3H6 over
Rh/NbOPO4, S. Imai, H. Miura, T. Shishido, The 8thJapan-China Workshop on Environmental Catalysis
December 5-6, 2017, Tsukuba, JapanThe effect of WO3 loding on the activity of Pt/WO3/ZrO2
catalysts for hydrogenolysis of tetrahydrofurfuryl alcohol,
Feng, Shixiang・Nagao, Aiko・Miura, Hiroki・Shishido,
Tetsuya, 4th International Congress on Catalysis for
Biorefineries ,11-15, December, 2017, Lyon, France＊Domestic
See the annual report in Japanese (36 articles)■Awards

1. Poster Award ‘‘Development of supported Pd catalysts
effective for hydrogen evolution from ammonia borane”
Mitsuhiro Tominaga, Kengo Nakajima, Hiroki Miura,
Tetsuya Shishido ， 119th CatSJ Meeting (21-22 March
2017, Tokyo Metropolitan University).
2. Poster Award ‘‘Dehydrogenative coupling of alcohols by
Cu/ZrO2” Karin Nakahara, Kengo Nakajima, Hiroki Miura,
Tetsuya Shishido ， 119th CatSJ Meeting (21-22 March
2017, Tokyo Metropolitan University).
3. Poster Award ‘‘Study on selectivity control inhydrogenolysis of glycerol over supported metal catalysts”
Takeshi Aihara, Hiroki Miura, Tetsuya Shishido， 119th
CatSJ Meeting (21-22 March 2017, Tokyo Metropolitan
University).
4. Poster Award ‘‘Preparation of sulfo-functionalized siloxane
gel catalysts with high hydrophobic surface and theircatalysis for ester hydrolysis” Shutaro Kameyama, Hiroki
Miura, Tetsuya Shishido ， 15th Catalyst workshop in
Takaoka, August 1, 2017, Takaoka.
5. Poster Award ‘‘Dehydration of glycerol over WO3/Al2O3
catalysts” Katsuya, Asazuma, Hiroki Miura, Tetsuya
Shishido， 11th Shokubai Dojo in Kochi, September 25, 2017,
Kochi.
6. Excellent Poster Award ‘‘Selective hydrogenolysis ofglycerol over Pt/WO3/Al2O3 catalysts” Takeshi Aihara,
Hiroki Miura, Tetsuya Shishido， 7th CSJ chemistry festa
2017, Funabori. 17-19 October 2017, Tower Hall Funabori
7. Excellent Poster Award ‘‘Dehydrogenation of ammonia
borane over supported AuPd alloy catalyst.” Mitsuhiro
Tominaga, Kengo Nakajima, Hiroki Miura, Tetsuya Shishido，■Academic Meeting＊International
1.
Steam Reforming of Dimethyl Ether over Solid Acid
Catalyst Coupled with Cu-based Catalyst, E. Kawai, Y.
Kubo, H. Miura, T. Shishido, 16th Korea-Japan
Symposium on Catalysis May 15-17, 2017 Hokkaido,
Japan
34

7th CSJ chemistry festa, Funabori. 17-19 October 2017,
Tower Hall Funabori
8. Excellent Poster Award ‘‘Interconversion between
ammonium bicarbonate and ammonium formate oversupported Pd alloy catalyst” Kengo Nakajima, Hiroki Miura,
Tetsuya Shishido， 37th annual meeting of Hydrogen Energy
Systems Society of Japan, (4-5 December 2017, Funabori(Tokyo)35

Applied Chemistry Colloquium

369th

2017/4/21
Kazuhiko Nakabayashi (Division of Developmental Genomics, National
Research Institute for Child Health and Development)“Epigenomics: History and Perspectives in Biology and Medicine”

370th

2017/5/8
Jorge Boczkowski (INSERM, Paris Est Créteil University, France)“Effects of manufactured Nanoparticles on inflammation”

371st

2017/7/21
Hiroki Sakaguchi (Tottori University)“Development of Silicon-based Negative Electrodes for Next Generation
Lithium-ion Battery”

372nd

2017/12/8
Masaru Yoshitake (Fuel Cell Development Information Center)“Current trends and future prospects toward hydrogen and fuel-cell
utilized society”

373th

2017/12/15
Takao Aoyagi (Department of Materials and Applied Chemistry, Nihon
University)“Design and Synthesis of Smart Polymer for Biomaterials”

364th

2018/1/16
Dr. Kenichiro Koshika (National Traffic Safety and Environment
Laboratory)“Research for FCVs and EVs in National Traffic Safety andEnvironment Lab.”365th

2018/1/30
Prof. Dr. Zeev Gross（Schulich Faculty of Chemistry, Technion – Israel
Institute of Technology）“Energy Relevant Processes Catalyzed by Corrole Metal Complexes”

36Annual Report 2017

Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Division of Applied Chemistry
April 1, 2017