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

Annual Report 2018

IndexReports from Research Groups
Kawakami Laboratory

▪▪▪▪▪

1

Masuda Laboratory

▪▪▪▪▪

7

Asayama Laboratory

▪▪▪▪▪

9

Kubo Laboratory

▪▪▪▪▪

11

Setaka Laboratory

▪▪▪▪▪

14

Kanamura Laboratory

▪▪▪▪▪

16

Kajiwara Laboratory

▪▪▪▪▪

19

Takagi Laboratory

▪▪▪▪▪

21

Uchiyama Laboratory

▪▪▪▪▪

25

Shishido Laboratory

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30

Shudo Laboratory

▪▪▪▪▪

34

▪▪▪▪▪

35

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

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

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

2. Study of Polymer Electrolyte Membrane
Hiroyoshi KAWAKAMI, Manabu TANAKA
Polymer electrolyte fuel cells have attracted much attention
as clean and sustainable energy systems. We have reported
composite polymer electrolyte membranes based on phytic acid(Phy)-doped polybenzimidazole nanofibers (PBINF) showed
outstanding fuel cell performances under low relative humidity
conditions.
In this year, we fabricated polymer composite membranes
containing proton conductive nanofibers that were modified
with acid and/or zwitterion molecules. (Figure 2). The novel
polymer composite membranes showed higher proton
conductivity than the conventional composite membranes,
especially under low humidity conditions, which are assumed
as future fuel cell operation conditions.

Manabu TANAKA
Assistant Professor / Dr. Eng.
Polymer Chemistry, Polymer Energy Materials, Fuel Cells,
Secondary Batteries, Nanofibers, Polymer Membranes
Rm. 9-639, +81-42-677-1111 Ext. 4586
tanaka-manabu@tmu.ac.jp
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 -9
Research student 1■Outlines of the Research
1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO,
Manabu TANAKA

Figure 2. Schematic illustration of the novel polymer
electrolytecompositemembranes
based
on
the
surface-modified nanofibers.

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.

3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA, Manjit Singh
GREWAL
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

In this year, we focused on the mixing effect ofspherical
nanoparticles
and
pearl
necklace
nanoparticles. As a result, CO2 permeability was
successfully improved by mixing the particles withdifferent shapes. We also began expanding the surface
modification area and developing new composite
membranes.
1Reports from Research Groups
therapy. The new EpC carriers show regulation abilities of
DNA methylation and epithelial to mesenchymal transition(EMT) in cancer cells. We also prepared a novel liposome
carrier capable of induction of mitophagy of damaged
mitochondria to suppress cellular senescence. These EpC
carriers will provide new therapeutic methods for acquired
diseases caused by epigenomic alterations.

unique characteristics. Ultrafine nanofibers with their diameters
less than 50 nm were also obtained.
In this year, we mainly focused on the fabrication ofpolymer nanofibers bearing lithium ion conductive polymer
brushes on their surface for the secondary battery applications(Figure 3). The novel lithium ion conductive nanofiber
composite membranes showed high lithium ion conductivity
and good charge-discharge properties.

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

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

4. Supramolecular system for multi-electron redox catalyst
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA

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

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 dinuclear supramolecularsystem, metalloporphyrin and metallosalen complexes
encapsulated in cucurbit[10]uril. The supramolecular systemshould act as a unique multi-electron catalysis. Efficient
combination of the two metal centers for the electrocatalytic
reduction of environmentally important CO2 and N2 gases areunder investigation.

Superoxide dismutase (SOD) or catalase (CAT) are wellknown to efficiently eliminate superoxide radicals or hydrogen
peroxide as the most important antioxidants.
We
demonstrated that a water-soluble cationic Mn-porphyrin with
SOD activity or catalase activity exhibited anticancer activity
as well as antioxidative activity.
In this year, we have prepared a novel cationic manganese
N-confused porphyrin (MnNCP) as a coreductant-free catalyst
for the ONOO- disproportionation. The pyridinium-appended
tetracationic MnNCP showed a higher ONOO- eliminating
activity than that of Mn corrole under physiological conditions
without coreductants. Furthermore, the intracellular toxicity of
the MnNCP was the same level as control experiment.
Therefore, MnNCP would be expected for an efficient artificial
antioxidant having biocompatibility.

Two-electron redox catalyst

Cucurbit[10]uril

Metallo-bisbipyridine

Metallo-porphyrins

M=Cu, Co, Fe etc

M=Mn, Fe, Co etc

R

Multifunctional＆ multifunctional redox catalyst
CO2 reduction

H2 production
2H+

CO, HCOOH,
CH3OH etc

H2

CO2

O2

Oxygen reduction

N
N

R

Mn

R

H2O

C
N

N

Figure 4. Multi-electron redox reactions by supramolecular
bimetallic complex.
5. Study of Epigenetics Engineering
Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTAR

R = -CH2Py+

Figure 6. Cationic-N-confused Mn-porphyrin (MnNCP) withperoxynitrite eliminating activity.

The development and maintenance of an organism isorchestrated by a set of chemical reactions that switch parts ofthe genome off and on at strategic times and locations.
Epigenetics is the study of these reactions and the factors that
influence them.
In this year, we have prepared novel epigenetics control(EpC) carriers for expanding the application field of epigenetic

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

2

Reports from Research Groups
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.

Magnetic Fields toward Anisotropic Materials, IOP Conf.
Ser.: Mater. Sci. Eng. 424 012076 (2018).
7. S. Asayama, K. Nagashima, Y. Negishi, H. Kawakami,“Byproduct-Free Intact Modification of Insulin by
Cholesterol End-Modified Poly(ethylene glycol) for in Vivo
Protein Delivery”, Bioconjugate Chemistry, 29, 67-73(2018).
8. F. Ito, H. Yamada, K. Kanamura, H. Kawakami, “Preparationof Biodegradable Polymer Nanospheres Containing
Manganese Porphyrin (Mn-Porphyrin)”, Journal of
Inorganic and Organometallic Polymers and Materials, inpress.
■Books
1. Hiroyoshi Kawakami，Development and application of CO2,
H2 separation membrane, CMC (2018). (in Japanese)
2. Hiroyoshi Kawakami，CO2 separation by using nanospace,
Kobunshi, 67, 4,183-186 (2018). (in Japanese)
3. Hiroyoshi Kawakami, Kiyoshi Sato, Riku Kubota, Annual
Survey of Catalytic Science and Technologies （2019） (inJapanese)
4. Manabu Tanaka, Hiroyoshi Kawakami, Fuel cell applicationof ion conductive nanofibers, JETI, 66(8), 65-68 (2018). (inJapanese)
5. Atsushi Mori, Masafumi Yamato, Kohki Takahashi,
Structural anisotropy in silica gels prepared in magnetic
field from viewpoint of alignment transition, 2017 Annual
report of high field laboratory for superconducting materials
in institute for materials research at Tohoku university，
p.p.156-159 (2018) (in Japanese)
6. Masafumi Yamato, Kohki Takahashi,, Study in interaction
between organic molecules and clay using magneticalignment, 2017 Annual report of high field laboratory forsuperconducting materials in institute for materials researchat Tohoku university，p.p. 158-159 (2018) (in Japanese)
7. Masafumi Yamato，Principle of magnetic process and its
application to orientation control of anisotropic filler,J. Jpn.
Coating Tech. Assoc., 53,154-161 (2018). (in Japanese)

Figure 8. Relationship between adsorption
amount of NIPAm and retardation at 10 T of
Nipam/clay dispersion (upper) and schematic
diagram of adsorption of NIPAm on clay(bottom).

In this year, we focused on research of anisotropic
organic / inorganic hybrid gels. In order to clarify
adsorption of monomer on clay, adsorption amount
was estimated by quantitative NMR method, andadsorption isotherm was obtained. Furthermore, wedeveloped an equipment that can quantify retardation
value in a magnetic field and studied in the adsorptionof the monomer on the clay by using magnetic
orientation.
■Papers with Peer Review
1. M. S. Grewal, M. Tanaka, H. Kawakami, “Bifunctionalpoly(ethylene glycol) based crosslinked network polymers aselectrolytes for all-solid-state lithium ion batteries”, Polymer
International, in press.
2. T. Ibaraki, M. Tanaka, H. Kawakami, “Fast surface proton
conduction on acid-doped polymer nanofibers in polymer
electrolyte composite membranes”, Electrochimica Acta, 296,
1042-1048 (2019).
3. 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, 317, 244-255(2018).
4. H. Mikami, A. Osawa, M. Tanaka, H. Kawakami, “Gasseparation membrane composed of polyimide andsurface-modified
nanoparticles:
Influenceof
surface-modification structures on gas permeation
properties”, Journal of Photopolymer Science andTechnology, 31, 593-598 (2018).
5. R. Kubota, T. Takabe, K. Arima, K., H. Taniguchi, S.
Asayama, H. Kawakami, “New class of artificial enzyme
composed of Mn-porphyrin, imidazole, and cucurbit[10]uril
toward use as a therapeutic antioxidant”, Journal of
Materials Chemistry B, 6, 7050-7059 (2018).
6. T. Ando, D. Katayama, N. Hirota, O. Koike, R. Tatsumi, M.
Yamato, Structure Formation of Magnetic Particles under■Invited Lectures
1. Hiroyoshi Kawakami, CO2 Separation Polymer Membranes
Containing
Nanoparticles
with
Gas
Permeable
Nano-Space,International Conference and Expo on
Separation Science and Technology 2018 (Dubai, UAE)
(April 2018) Invited Lecture
2. Hiroyoshi Kawakami, Development of Nanofiber Composite
Ultra-thin Polymer Electrolyte Membrane for Fuel Cells(IGEM 2018) (Kuala Lumpur, Malaysia) (October 2018)
Requested Lecture
3. Hiroyoshi Kawakami, CO2 Management by Polymer
Membranes Containing Nanoparticles with Gas Permeable
Nano-space, The 12th SPSJ International Polymer
Conference (IPC2018) (Hiroshima, Japan) (December 2018)
Invited Lecture
4. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2018 Basic seminar of polymer science for young
engineers, Oct. 2018, Hiratsuka, Japan (in Japanese).
5. Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and Fuel
Cell Evaluation of Polymer Electrolyte Membranes
Composed of Proton Conductive Nanofiber Framework,
The 25th Fuel Cell Symposium (Tokyo), B-13（May 2018）
6. Manabu Tanaka, Ion Conductive Polymer Nanofibers:

3

Reports from Research Groups(Nagoya International Conference Center), 2Pf062, May
2018 (in Japanese)
12.Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, andHiroyoshi Kawakami, Preparation of polymer membranes
containing
surface-modified
pearl-necklace
shapednanoparticles to achieve high CO2 permeability, The 67th
SPSJ Annual Meeting (Nagoya International ConferenceCenter), 2F14, May 2018 (in Japanese)
13.Takuya Muramoto, Hiroto Mikami, Manabu Tanaka,
Masafumi Yamato, and Hiroyoshi Kawakami, Gas
permeation properties of composite membranes containing
surface-modified silica nanoparticles, The 67th SPSJ Annual
Meeting (Nagoya International Conference Center), 2Pa096,
May 2018 (in Japanese)
14.Hiroto Mikami, Azusa Osawa, Manabu Tanaka, Hiroyoshi
Kawakami, Gas Separation Membrane Composed of
Polyimide and Surface-modified Nanoparticles: Influence ofSurface-modification Structures on Gas Permeation
Properties, The 35th International Conference of
Photopolymer Science and Technology, Makuhari Messe,
Japan, B1-02 (May, 2017 ) (in Japanese)
15.Manabu Tanaka, Hiroyoshi Kawakami, Proton Conductive
Polymer Nanofiber Framework: Fabrication and Application
to Polymer Electrolyte Fuel Cells, The Fiber Society’s
Spring 2018 Conference (Tower Hall Funabori), (June2018).
16.Kaito Takenaka, Inafune Yuta, Nakazawa Shun, Manabu
Tanaka, Hiroyoshi Kawakami, Fabrication and evaluation of
the polymer electrolyte composite membranes composed oflithium ion conductive surface modificated nanofibers forsecondary battery application, The Annual Meeting of The
Society of Fiber and Technology (Tower Hall Funabori),
2F06, June 2018 (in Japanese)
17.Kaito Takenaka, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication of novel lithium ion conductive PVA nanofiberand nanofiber composite electrolyte membranes forsecondary battery application, The Annual Meeting of The
Society of Fiber and Technology (Tower Hall Funabori),
2P220, June 2018 (in Japanese)
18.Kazuma Komine, Masafumi Yamato, and Hiroyoshi
Kawakami, Structure analysis of crosslinking point of
nanocomposite gel by using thermal analysis, The Annual
Meeting of The Society of Fiber and Technology (Tower
Hall Funabori), 2C02, June 2018 (in Japanese)
19.Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, andHiroyoshi Kawakami, Preparation and gas permeability
measurement of polymeric membranes containing
surface-modified pearl-necklace shaped nanoparticles, The
Annual Meeting of the Society of Fiber Science andTechnology (Tower Hall Funabori) , 2P223, June 2018 (inJapanese)
20.Takuya Muramoto, Hiroto Mikami, Manabu Tanaka,
Masafumi Yamato, and Hiroyoshi Kawakami, Preparationand gas permeability measurement of PIM-1 composite
membranes containing surface-modified silica nanoparticles,
The Annual Meeting of the Society of Fiber Science andTechnology (Tower Hall Funabori), 2F05, June 2018 (inJapanese)
21.Manabu Tanaka, Hiroyoshi Kawakami, Development and
Fuel Cell Application of Polymer Electrolyte Membranes
Based on Proton Conductive Polymer Nanofiber Framework,

Fabrication, Characterization, and Application, The
Chemical Society of Japan, Asian International Symposium(Konan University) (March 2019)■Academic Meeting
1. M. Yamato, E. Ito, M. Tanaka, H. Kawakami，Study on CO2
dynamics in composite membrane containing silica
nanoparticle by using 13C NMR, 40th Annual Meeting on
The Membrane Society of Japan, Waseda University, May
2018 (in Japanese)
2. Manabu Tanaka、Risa Sakaguchi、Takahiro Ogura、Hiroki
Harad, Hiroyoshi Kawakami, Fabrication and evaluation ofnovel nanofiber composite membranes to improve proton
conductivity at low humidity, 40th Annual Meeting on The
Membrane Society of Japan, Waseda University, 2C-02 May2018 (in Japanese)
3. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, andHiroyoshi Kawakami, Preparation and evaluation of PIM-1
compositemembranes
containing
surface-modified
pearl-necklace shaped nanoparticles having highly gas
permeable properties, 40th Annual Meeting of The
Membrane Society of Japan (Waseda University), P-21S,
May 2018 (in Japanese)
4. Kazuma Komine, Masafumi Yamato, and Hiroyoshi
Kawakami, Enthalpy change associated with phasetransition of nanocomposite gel with different water mole
fraction, 40th Annual Meeting of The Membrane Society ofJapan (Waseda University), P-46S, May 2018 (in Japanese)
5. Kaito Takenaka, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation of composite membrane consists of novel PVA
nanofiber with lithium ion conductivity and evaluation, 40th
Annual Meeting of The Membrane Society of Japan(Waseda University), P-36S, May 2018 (in Japanese)
6. Riku Kubota, Taiga Takabe, and Hiroyoshi Kawakami,
Water-soluble supramolecular system for hydrogenproduction, The 67th SPSJ Annual Meeting, (Nagoya
Congress Center), May 2018 (in Japanese)
7. Masafumi Yamato, K. Komine, H. Kawakami, Study instructure of physical cross-linking point of nanocomposite
gel by using transition enthalpy, 67th SPSJ annual meeting,May 2018, Nagoya, Japan (in Japanease).
8. Masafumi YAMATO, Eiko ITO, Manabu TANAKA,
Hiroyoshi KAWAKAMI , 13C NMR measurement of CO2 inpolymer separation membrane, 67th SPSJ annual meeting,May 2018, Nagoya, Japan (in Japanease).
9. Manabu Tanaka, Shun Nakazawa, Yuta Inafune, Kaito
Takenaka, Hiroyoshi Kawakami, Fabrication of lithium ion
conductive polymer nanofiber framework composite
electrolyte membranes for future secondary battery
applications, The 67th SPSJ Annual Meeting (Nagoya
International Conference Center), 2Pe063, May 2018 (inJapanese)
10.Manjit Singh Grewal, Manabu Tanaka, and Hiroyoshi
Kawakami, Bifunctional PEG-based Cross-linked Network
Polymer Electrolytes for Lithium Ion Batteries, The 67th
SPSJ Annual Meeting, (Nagoya Congress Center), May
2018
11.Manabu Tanaka, Risa Sakaguchi, Hiroyoshi Kawakami,
Fabrication of polymer nanofibers containing sulfonic andphosphoric acid groups and fuel cell characterizations of thecomposite membranes, The 67th SPSJ Annual Meeting4Reports from Research Groupsof clay-dispersed N-isopropyl acrylamide aqueous solution,
79th JSAP Autumn Meeting, Sep. 2018, Nagoya, Japan (inJapanease).
34.Takahiro Ogura, Manabu Tanaka, and Hiroyoshi Kawakami,
Fabrication and fuel cell applications of novel nanofiber
composite electrolyte membranes with connected effecive
proton conductive pathways, 56th symposium on Polymer
and Water Japan(Tokyo University of Marine Science andTechnology), P11 (November, 2017) (in Japanese)
35.Kazuma Komine, Masafumi Yamato, and Hiroyoshi
Kawakami, DSC study of the amount of hydration water inpoly (NIPAm) based nanocomposite gels with different
water contents, 56th Symposium on Polymer andWater(Tokyo University of Marine Science and Technology),
P12, November 2018 (in Japanese)
36.Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, New Insights into Cross-linked Network
Polymer Electrolytes for Future Secondary Battery
Applications, The 59th Battery Symposium in Japan, Japan(Osaka International Convention Center), 3B18 (November
2018)
37.Shun Nakazawa, Yuta Inafune, Mitsuki Ochiai, Yu Matsuda,
Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami,
Fabrication and All-Solid-State Battery Application of Solid
Polymer Electrolytes Using Lithium Ion Conductive
Nanofiber Framework, The 59th Battery Symposium inJapan, Japan (Osaka International Convention Center), 3B18
(November 2018) (in Japanese)
38.Hiroto Mikami, Takuya Muramoto, Eiko Ito, Manabu
Tanaka, Masafumi Yamato, Hiroyoshi kawakami,
Fabrication and characterizations of intrinsic microporous
polymer gas separation membrane for improving gas
permeability, 26th symposium of polyimide and Aromatic
polymer, Toho University, Japan,P07 (November, 2018 ) (inJapanese)
39.Riku Kubota, Hiroyoshi Kawakami, New Class ofBimetallic Supramolecules Based on Cucurbit[10]uril andMetalloporphyrins Toward Energy Conversion Materials,
The 12th SPSJ International Polymer Conference (IPC2018),
International Conference Center Hiroshima, November
2018.
40.Ayano Imai, Takuya Muramoto, Manabu Tanaka, Masafumi
Yamato, Hiroyoshi Kawakami, CO2 separation of mixed
matrix membrane containing surface-modified silica
nanoparticles, The 12th SPSJ International Polymer
Conference (Hiroshima, Japan), 7P-T4-120b (December,
2018)
41.Minami KAWAI, Riku KUBOTA, Shoichiro ASAYAMA,
Kiyoshi SATO, Hiroyoshi KAWAKAMI, Bioinspired
water-soluble Mn-porphyrin complexes as a catalase mimic
for anti-oxidative activety, The 12th SPSJ International
Polymer Conference (IPC2018), International ConferenceCenter Hiroshima, Hiroshima, JAPAN, 6P-T8-097c,(December, 2018)
42.Motoki Nishizawa, Risa Sakaguchi, Takahiro Ogura,
Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and fuelcell application of proton conductive nanofibers containing
sulfonic and acid group, The 12th SPSJ International
Polymer Conference (IPC2018), (International ConferenceCenter Hiroshima), 7P-T4-115a (Descember 2019)
43.Masafumi Yamato, Takahiro Miyazaki, Hiroyoshi

The 16th International Symposium on Polymer Electrolytes(ISPE-16), Japan (Yokohama Symposia), (June 2018)22.Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, PEG-based solid-state cross-linked polymer
electrolytes for future lithium ion battery application, The
16th International Symposium on Polymer Electrolytes(ISPE-16), Japan (Yokohama Symposia), (June 2018)
23.Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami,
Development of lithium single-ion conducting polymer
electrolytes based on polymer nanofibers, The 16th
International Symposium on Polymer Electrolytes(ISPE-16), Japan (Yokohama Symposia), P1-38 (June 2018)
24.Yuta Inafune, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and Evaluation of Lithium Ion Conductive
Nanofiber Composite Electrolyte Membranes, The 16th
International Symposium on Polymer Electrolytes(ISPE-16), Japan (Yokohama Symposia), (June 2018)
25.Tomokazu Aoyama, Riku Kubota, Hiroyoshi Kawakami,
Preparation and catalytic function of novel water-solublesupramolecular system aimed at hydrogen production, 68th
Conference of Japan Society of Coordination Chemistry.
（Sendai International Center） 1PA-64, July 2018.
26.Wataru MURATA, Hiroyoshi KAWAKAMI, Kiyoshi SATO,
Exploring efficient metal complexes as a catalyst forhydrogenation and dehydrogenation, The 68th conference ofJapan Society of Coordination Chemistry, Sendai
International Center, 1PF-009 (July, 2017) (in Japanese)
27.Kosuke Chikuma, Kohei Arima, Dai Tabata, Ryousuke
ShinoharaRiku Kubota, Shoichiro Asayama, Hiroyoshi
Kwakami, Induction of cell differentiation by epigenetics
control carrier for treatment of diabetes, 47th Medical
macromolecular symposium, P29, July 2018, Tokyo,
Japan(in Japanese)
28.Wataru MURATA, Hiroyoshi KAWAKAMI, Kiyoshi SATO,
Design and Synthesis of Ruthenium Complexes with N‐
Heterocyclic Carbene Ligands as Catalysts for Reversible
Hydrogenation and Dehydrogenation, The 3rd International
Symposium on Hydrogen Energy‒based Society, TMU(Aug 2017)29.Masafumi Yamato, Kazumasa Komine, Takahiro Miyazaki
Hiroyoshi
Kawakami,
Magneticalignmentofnano-composite gel containing montmorillonite and its
anisotropy, 67th annual meeting on Macromolecules, Sep.
2018, Sapporo, Japan (in Japanease).
30.Masafumi YAMATO, Eiko ITO, Takuya Muramoto,
Manabu TANAKA, Hiroyoshi KAWAKAMI, 13C NMR
measurement of CO2 in polymer membrane, 67th
Symposium on Macromolecules, Sep. 2018, Sapporo, Japan
31.Manabu Tanaka, Takahiro Ogura, Hiroki Harada, Motoki
Nishizawa, Hiroyoshi Kawakami, Construction of
three-dimensional proton conductive network structures andtheir application to fuel cell electrolytes, 67th Symposiumon Macromolecules (Hokkaido University) 1O11
(September 2018) (in Japanese)
32.Manabu Tanaka, Kaito Takenaka, Shun Nakazawa, Manjit
Singh Grewal, Hiroyoshi Kawakami, Advancement in
performance of solid polymer electrolyte for secondary
batteries by utilizing nanofiber framework ,67th Symposiumon Macromolecules (Hokkaido University) 3Pb086(September 2018) (in Japanese)
33.Masafumi Yamato, Kohki Takahashi, Magneto birefringence5

Reports from Research Groups
Kawakami, Measurement of magneto-birefringence of clay
dispersion containing NIPAM, 12th Annual Meeting of theMagneto-Science Society of Japan, Nov. 2018, Sendai,
Japan (in Japanease).
44.Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi
Kawakami,* In-situ* magneto-birefringence of clay
dispersion modifying NIPAm, Applied Physics Society the
Magneto-Science
SocietyofJapan2017,
Tokyo
Metropolitan University Akihabara satellite campus, P-15
(December, 2018) (in Japanese)
45.Takuya Muramoto, Manabu Tanaka, Masafumi Yamato,
Hiroyoshi Kawakami, Effect of surface-modified silica
nanoparticles on gas permeability of mixed matrix
membranes, 28th Annual Meeting of MRS-J (Kitakyusyu
International Conference Center), F8-P19-003, Dec. 2018
46.Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi
Kawakami,
HirotaNoriyuki,*In-situ*
magneto-birefringence of clay dispersion modifying NIPAm,
The 66th JSAP Spring Meeting, 10p-M113-4 (March, 2019)(in Japanese)■Patents

1. P2018-31082A, Surface-modified nanofibers, electrolyte
membranes, and fabrication method of electrolyte
membranes, membrane electrode assembly, and polymer
electrolyte fuel cells, Hiroyoshi Kawakami, Manabu Tanaka,
Takahiro Makinouchi
2. P2018-32484A, Fabrication method of battery materials andelectrolyte membrane, and battery materials, Hiroyoshi
Kawakami, Manabu Tanaka, Tsukasa Watanabe
3. P2018-34152A, Multi-electron redox catalyst, Hiroyoshi
Kawakami, Riku Kubota, Hideaki Taniguchi, Taiga Takabe
4. P2018-123315A, Surface modification reagent, Shoichiro
Asayama, Hiroyoshi Kawakami, Kana Nagashima, Yuua
Sone

■Awards
1. Student poster award, 2018 Annual Meeting on The Societyof Fiber Science and Technology, Japan, Takuya Muramoto,
Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami,
Preparation and gas permeability measurement of polymeric
membranes containing surface-modified pearl-necklace
shaped nanoparticles,
2. Poster award (Inorganic Chemistry Frontier (IFC) Award),
The 68th Japan Society of Coordination Chemistry
Tomokazu Aoyama, Riku Kubota,
Conference, 23.
Hiroyoshi Kawakami, Preparation and catalytic function ofnovel water-soluble supramolecular system aimed athydrogen production.
3. Poster award (IPC2018 Poster Award: Polymers Award sponsored by MDPI), The 12th SPSJ International Polymer
Conference (IPC2018), Motoki Nishizawa, Risa Sakaguchi,
Takahiro Ogura, Manabu Tanaka, Hiroyoshi Kawakami,
Fabrication and fuel cell application of proton conductive
nanofibers containing sulfonic and acid group.
4. Poster award (Award for Encouragement of Research), The
28th Annual Meeting of MRS-J, Takuya Muramoto,
Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami,,
Effect of surface-modified silica nanoparticles on gas
permeability of mixed matrix membranes

6

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, 36, 031802 (2018).
3. Takashi Yanagishita, Taito Inoue, Toshiaki Kondo, andHideki Masuda
Preparation of Monodisperse LiCoO2 Hollow Particles by
Membrane Emulsification Using Anodic Porous Alumina
Chem. Lett., 47, 551 (2018).
4. Toshiaki Kondo, Sun Hasegawa, Takashi Yanagishita,
Naoshi Kimura, Takashi Toyonaga, and Hideki Masuda
Control of Thermal Radiation in Metal Hole Array
Structures Formed by Anisotoropic Anodic Etching of Al
Optics Express, 26, 27865 (2018).

SEM image of anodic porous alumina

5. Toshiaki Kondo, Hayato Miyazaki, Takashi Yanagishita, andHideki Masuda
Anodic Porous Alumina with Elliptical Apertures
Electrochem. Commun., 96, 61 (2018).

(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
7Reports from Research Groups
2. Takashi Yanagishita, Toshiaki Kondo, and Hideki Masuda,
Preparation of Ordered Porous Alumina Through-Hole
Membranes by Two-Layer Anodization
The 8th Aluminum Surface Science & Technology
Symposium, 2018/5，Denmark

6. Takashi Yanagishita, Hiromi Inada, Toshiaki Kondo, Nhat
Truong Nguyen, Patric Schmuki, and Hideki Masuda
Efficient Preparation Process for TiO2 Through-Hole
Membranes with Ordered Hole Arrangements
J. Electrochem. Soc., 165, E763 (2018).

Toshiaki Kondo, Shota Hirano, Sanami Nagao, Toko Tmamura,
Takashi Yanagishita, and Hideki Masuda,
Fabrication of Ideally Ordered Anodic Porous TiO2 and Its
Application to Photonic Crystal
2018 MRS Fall Meeting, 2018/11, US

7. Takashi Yanagishita, Kaito Murakoshi, Toshiaki Kondo, andHideki Masuda
Preparation of Superhydrophobic Surfaces with Micro/Nano
Alumina Molds
RSC Adv., 8, 36697 (2018).

＊Domestic
See the annual report in Japanese (24 articles)

8. Takashi Yanagishita, Yuki Okubo, Toshiaki Kondo, andHideki Masuda
Selective Throug-Hololing of Anodic Porous Alumina
Membranes with Large Area
RSC Adv., 8, 38455 (2018).

■Patents

See the annual report in Japanese (3 articles)■Awards

See the annual report in Japanese (1 articles)

9. Takashi Yanagishita, Hiroaki Awata, Kenichi Kobayashi,
Toshiaki Kondo, and Hideki Mausda
Preparation of PolymerNanofibers with Controlled
Diameters by Continuous Spinning Using Ordered Anodic
Porous Alumina as SpinneretChem. Lett., 48, 86 (2019).

■Reviews and Books
See the annual report in Japanese (7 articles)■Invited Lectures＊International
1. Hideki Masuda, Toshiaki Kondo ,and Takashi Yanagishita
Fabrication of Ordered Semiconductor Nanostructures forEnergy Conversion Based on Anodization Processes
233rd ECS Meeting，2018/ 5, US
2. Toshiaki Kondo , Takashi Yanagishita, and Hideki Masuda
Highly Ordered Anodic Porous Alumina for Functioanl
Nanodevices
Plasmonic Devices Obtained Using Anodic Porous Alumina，
ICEAN2018, 2018/10，Austratia
3. Toshiaki Kondo , Takashi Yanagishita, and Hideki Masuda
Anisotropic Anodic Etching of Al and its Application to
Thermal Radiation Control Device
International workshop on nanoopics & nanophotonics,
2019/3，Yokohama＊Domestic
See the annual report in Japanese (6 articles)■Academic Meeting＊International
1. Takashi Yanagishita, Masahiko Imaizumi, and Toshiaki
Kondo, and Hideki Masuda
Preparation of Ordered Porous Alumina Spheres by
Anodization of Small Al Particles
22nd Topical Meeting of the International Societry ofElectrochemistry, 2018/4, Tokyo

8

Asayama Laboratory■Members

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

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

Insulinsecretion

InsulinPancreas

Liver

H
C CH2

Master’s course -1
Bachelor 4 -3
Research student -1

NProtein■Outlines of the Research

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

+

Delivery toUnexplored
Space

O
H2N

N

N

1-x-y

Zn2+

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

Mono-Ion Complex【MIC】
C(CH2)nN

In this year, Zn2+ have been chelated by carboxymethyl poly(1vinylimidazole), CM-PVIm, for intracellular Zn2+ delivery.
The resulting Zn2+/CM-PVIm complex exhibited maximum 1.28
mol% Zn2+ chelation per CM-PVIm monomer unit. The
cellular uptake of Zn2+ in HepG2, liver model cell, treated with
the Zn2+/CM-PVIm was higher than that with Zn2+ alone.
These results suggest that CM-PVIm is high potential carrier fortherapeutic Zn2+ delivery.

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

+

N

H
C CH2

y

Figure 2. Remote control of hypoglycemic hormone in blood.

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

+

H
C CH2

x

+
N
N
(CH2)nCH3

N+

Survival insulin
to whole body

Zn 2+

PEG

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

CH2CH2O

n

H3C
CH3
H3C

H
CH2CH2CH2N C O
OBy-product by
conventional
covalent
PEGylation

Surface modification
with biocompatibility

DiseaseCH3

H3C

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

InsulinIn this year, biodegradable ester bond has been introduced forcleavage of PEG from the mono-ion complex (MIC) at various
charge ratios to optimize in vivo delivery system for sustainablegene expression. The resulting MIC enhanced gene expression
after 2 weeks post-transfection in vivo, suggesting that cellular
uptake and endosomal escape proceeded by temporal hydrolysis
of ester bond to produce endosomal-pH-sensitive carboxylgroups on the side of the MIC.

7

8

9
10
11
Elution volume / mL

12

Figure 3. Development of novel bio-function by Chol-PEG.
In this year, Functional dialysis membranes have beensynthesized for establishing sustainable biomaterials.
Manganese porphyrins (Mn-porphyrins) were adsorbed onto theregenerated cellulose dialysis membrane coated with PVIm
derivatives for mimicking enzyme active-center.
The
absorbance (240 nm) from hydrogen peroxide decreased during
dialysis, suggesting the surface of the resulting membrane
worked as catalase mimic.

2. Bioactive Substance (Zn2+, protein) Delivery System
Shoichiro ASAYAMA
To give DDS carrier the ability for definitive treatment, we havedesigned pH-sensitive polyvinylimidazole (PVIm) derivateives
as intelligent materials to change their structure and function in

9

■Papers with Peer Review

1. Riku Kubota, Taiga Takabe, Kohe Arima, Hideaki Taniguchi,
Shoichiro Asayama, Hiroyoshi Kawakami, New class of
artificial enzyme composed of Mn-porphyrin, imidazole, andcucurbit[10]uril toward use as a therapeutic antioxidant, Journalof Materials Chemistry B: Materials for Biology and Medicine,
6, 7050-7059 (2018).
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).

■Books

1. Shoichiro Asayama, Hiroyoshi Kawakami, Design of pHsensitive carboxymethyl polyvinylimidazole for gene delivery
and artificial enzyme, Stimuli-Responsive Polymers Handbook,
pp.483-488 (2018).
■Academic Meeting＊International
1. Shoichiro Asayama, Sakura Taneichi, Hiroyoshi Kawakami,
Yoichi Negishi, Biocompatible highly condensed plasmid DNA
by mono-iIon complexes for in vivo diffusive gene delivery,
American Society of Gene & Cell Therapy 21st Annual Meeting,P-925 (Chicago, USA) (May, 2018).
2. Yuya Sone, Hiroyoshi Kawakami, Shoichiro Asayama, Highdensity modification of poly(propylene) surface with cholesterol
end-modified poly(ethylene glycol) for biocompatibility, 1st
G’L’owing Polymer Symposium in KANTO, P36 (December,
2018).
＊Domestic
See the annual report in Japanese (8 articles)■Patents
1. Patent No. 6358661, Shoichiro Asayama, Atsushi Nohara,
Hiroyoshi Kawakami, Yoichi Negishi (June, 2018).

■Awards

1. Outstanding Performance Award for Graduate Students on
47th Biomedical Polymer Symposium
Yuya Sone, Hiroyoshi Kawakami, Shoichiro Asayama,
Fabrication of PEG brush with high density by noncovalent
PEGylation using cholesterol end-modified poly(ethylene
glycol).

10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, Photochemistry
Room: 9-149 TEL: +81-42-677-2823
e-mail: ymulyana@tmu.ac.jp

Figure 2. Triplet–triplet annihilation upconversion photosensitized by selenium-containing BODIPY.

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

3. Synthesis of NIR Light Absorbing Dye for Photodetectors
Name: Yuji Kubo
The steep demand for developing photodetectors with NIR
absorption led us to prepare monolayer devices composed ofindiumtinoxide,
NIR
dibenzo-BODIPY
withnaphtho[1,3,2]oxazaborinine (1), and Al. When the dye
1-loaded device was irradiated with 800 nm light, a large
on-to-off current ratio was produced and the excellent
photostability of the devices indicate that this system has great
promise as a NIR photodetector in image sensing applications.

Doctor’s course -3
Master’s course -11
Bachelor 4 -8

■Outlines of the Research
1. Synthesis of Dye-sensitized Photocatalysts for Hydrogen
Production by Water Splitting
Name: Yuji Kubo
A visible-to-near-infrared (visible-to-NIR) light-driven
photocatalyst was prepared by loading a boron-dipyrromethene(BODIPY)-phenothiazine conjugate dye as a photosensitizer on
hierarchical porous TiO2 semiconductor. The loaded dye
showed panchromatic sensitization of the porous TiO2 and thesystem exhibited hydrogen generation with a light-to-fuelefficiency of 6.96%. This study provides important information
for the development of metal-free organic photosensitizers witha wide spectral response up to the NIR region forphotocatalytic water-splitting hydrogen production.

Figure 3. A monolayer device based on NIR dibenzo-BODIPYwith naphtho[1,3,2]oxazaborinine (1) as a NIR photodetector.
4. Emissive nanoparticles of tetraphenylethylene-containing
boronate macrocycles
Name: Yuji Kubo, Ryuhei Nishiyabu
It was found that boronate esterification of di(boronicacid)-appended tetraphenylethylene with structurally flexible
ditrimethylolpropane in methanol gave boronate dots with blue
emission under UV irradiation. Several spectroscopic and
X-ray diffraction analysis indicated the selective formation of[2+2] boronate macrocycles through boronate self-sorting
behavior. Our interest to explore the functionality allowed us tofind that the emissive boronate dots composed of the [2+2]boronate macrocycles sensed nitroaromatics in water to cause asignificant emission quenching.

Figure 1. Dye-sensitized photocatalytic hydrogen production bywater splitting.
2. Synthesis of Selenium-containing Dyes as Photosensitizers
for Triplet–triplet Annihilation Upconversion
Name: Yuji Kubo
Selenium-containing BODIPY dyes were synthesized as
photosensitizers for triplet–triplet annihilation upconversion(TTA-UC). Bis(phenylselanyl)-BODIPY absorbed visible lightand exhibited fluorescence with a low fluorescence quantum
yield. The low value was ascribed to heavy atom effects. When
a TTA-UC system comprising this dye and the triplet acceptor
perylene was set up, a purplish white emission was observedwith a significant anti-Stokes shift of 77 nm and a high UC
quantum yield of 17% in CH2Cl2. Notably, the intramolecularcharge transfer of this dye enabled us to tune the emission colorof the TTA-UC system.

Figure 4. Emissive nanoparticles of tetraphenylethylenecontaining boronate macrocycles.

11

Reports from Research Groups
5. Synthesis of ruthenium polypyridyl dyes for photoelectrochemical devices
Mulyana J. Yan and Yuji Kubo
The subtle variation in the alkyl substituents of the ruthenium
photosensitizers
controls
thephoto-electrochemical
performance of the dye-only DSPECs (do-DSPECs) and thosewith sacrificial agent (sa-DSPECs). The detailed investigationin the two DSPEC types reveals that the dyes’ electron injection
capacity is not the only energetic factor that govern the device
performance, but other factors such as dyes’ reorganizationenergy and dyes’ hydrophobicity on TiO2 surface proved toalso contribute crucially to the hydrogen production capacity of
the DSPEC devices.

4.

5

6.

7.

8.

BODIPY dyes as photosensitizers for triplet-triplet
annihilation upconversion, J. Mater. Chem. C, 2018, 6,
6208-6215. DOI: 10.1039/C8TC00944A
Indra Purnama, Salmahaminati,, Minori Abe, MasahikoHada, Yuji Kubo and Jacob Yan Mulyana, Factors
influencing the photoelectrochemical device performancesensitized by ruthenium polypyridyl dyes, Dalton Trans.,
2019, 48, 688-695. DOI: 10.1039/c8dt03502d
Mariia Pushina, Petr Koutnik, Ryuhei Nishiyabu, Tsuyoshi
Minami, Pavel Savechenkov and Pavel Anzenbacher, Jr.,
Chem. Eur. J., 2018, 19, 4879-4884. DOI: 10.1002/chem.201705387
Ryuhei Nishiyabu, Miku Tomura, Tomo Okade, and Yuji
Kubo, Boronic acids as molecular inks for surfacefunctionalization of polyvinyl alcohol substrates, New J.
Chem., 2018, 42, 7392-7398. DOI: 10.1039/C8NJ00992A
Yuji Kubo, Shun Tobinaga, Yoshihide Ueno, Tatsuya
Aotake, Hidenori Yakushiji, and Tatsuya 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.1710612.
Indra Purnama, Yuji Kubo, and Jacob Yan Mulyana, A
robust ruthenium complex with nonyl-substituted bpy
ligand for dye-sensitized photoelectrochemical cellapplication, Inorg. Chim. Acta, 2018, 471, 467-474. DOI:
10.1016/j.ica.2017.11.052■Invited Lectures
1. AIE-active boronate systems for chemosensing
applications, Yuji Kubo, 6th International Conference on
Molecular Sensors and Molecular Logic Gates(MSMLG2018), June 5, 2018.

Figure 5. Ruthenium polypyridyl dyes for photoelectrochemical devices.
6. Boronic acids as molecular inks for surface functionalizationof polyvinyl alcohol substrates
Name: Ryuhei Nishiyabu and Yuji Kubo
Boronic acids are proposed to be used as molecular inks. This
allows chemical modification of the surface of polyvinyl
alcohol (PVA) and PVA-related materials with boronic
acid-containing molecules through boronate esterification using
marker pen applicators. The resulting materials exhibit
functional properties, such as fluorescence, halochromism,
chemical sensing abilities, and water repellency.

■Academic Meeting＊International
1. A phenothiazine-appended dibenzo-BODIPY dye as apanchromatic sensitizer for dye-sensitized solar cells，
Yoshihide Ueno，Erten-Ela Sule，Yuji Kubo，The 3rdInternational Symposium on Hydrogen Energy‒based
Society，Tokyo Metropolitan University (Tokyo)，2018，
Aug，23rd.
2. A
panchromatic
photosensitizer
basedon
dibenzo-BODIPY-phenothiazine conjugate for light-drivenhydrogen production，Haruka Sato，Okta Suryani，Yuta
Higashino，Yuji Kubo，The 3rd International Symposiumon Hydrogen Energy‒based Society，Tokyo Metropolitan
University (Tokyo)，2018，Aug，23rd.
3. A near-infrared absorbing organic photosensitizer for use
in p-type dye-sensitized solar cells，Yuta Higashino，Erten-Ela Sule ， Yuji Kubo ， The 3rd International
Symposium on Hydrogen Energy‒based Society，Tokyo
Metropolitan University (Tokyo)，2018，Aug，23rd.

Figure 6. Chemical modification of the surface of polyvinyl
alcohol (PVA) with boronic acid-containing molecules using
marker pen applicators.

■Papers with Peer Review＊Domestic
1. Emissive self-assembly of tetraphenylethylene-containing
boronate macrocycles，Mitsuki Hoshi，Naoyoshi Kaneko，Ryuhei Nishiyabu，Yuji Kubo，2P-20，16th Symposium on
Host-Guest and Supramolecular Chemistry ， Tokyo
University of Science (Chiba)，2018，Jun，3rd.
2. Synthesis of a boronate ester-appended 1,8-naphthalimide
with a fluorescence responsivity to H2O2 ， Wakana
Mochida，Ryuhei Nishiyabu，Yuji Kubo，2P-10，16th
Symposium on Host-Guest and Supramolecular Chemistry，Tokyo University of Science (Chiba)，2018，Jun，4th.
3. A
panchromatic
photosensitizer
basedon
dibenzo-BODIPY-phenothiazine conjugate for application

1. Okta Suryani, Yuta Higashino, Haruka Sato, and Yuji
Kubo,
Visible-to-Near-Infrared
Light-Driven
Photocatalytic
Hydrogen
Production
Using
Dibenzo-BODIPY and Phenothiazine Conjugate as Organic
Photosensitizer, ACS Appl. Energy Mater., 2019, 2,
448-458. DOI: 10.1021/acsaem.8b01474
2. Mitsuki Hoshi, Naoyoshi Kaneko, Ryuhei Nishiyabu andYuji Kubo, Formation of emissive nanoparticles fromtetraphenylethylene-containing boronate macrocycles:
preparation, characterization and functionalization, J.
Mater. Chem. C, 2018, 6, 11052-11062. DOI:
10.1039/C8TC03748E
3. Mika Nakashima, Keita Iizuka, Masanobu Karasawa,Kazuyuki Ishii and Yuji Kubo, Selenium-containing
12

Reports from Research Groups
in dye-sensitized solar cell and photocatalytic hyderogenproduction，Haruka Dato，Okta Suryani，Yuta Higashino，
Yoshihide Ueno，Erten-Ela Sule，Yuji Kubo，2D04，Annual
Meeting on Photochemistry 2018 ， Kwansei Gakuin
University (Hyogo)，2018，Sep，6th.
4. Synthesis and Characterization of a near-infraredabsorbing sensitizer for p-type，Higashino Yuta，Erten-Ela
Sule ， Yuji Kubo ， 2P054 ， Annual Meeting on
Photochemistry 2018 ， Kwansei Gakuin University(Hyogo)，2018，Sep，6th.
5. Selenium-cantainig BODIPY dyes as photosensitizers fortriplet-triplet annihililation upconversion，Keita Iizuka，Mika Nakashima，Masanobu Karasawa，Kazuyuki Ishii，Yuji Kubo，C03，29th Symposium on Physical Organic
Chemistry，Tokyo Institute of Technology (Tokyo)，2018，
Sep，8th.
6. Synthesisofnaphtho[1,3,2]oxazaborinine-typed
near-infrared absorbing dyes for application tophoton-to-electron conversion devices，Yoshihide Ueno，
Shun Tobinaga，Yuji Kubo，Tatsuya Aotake，Hidenori
Yakushiji，Tatsuya Yamamoto，O-33，The 45th symposium
on main group element chemistry，Niigata Convention
Center (Niigata)，2018，Dec，19th.
7. Synthesis and characterization of a boronic acid-appended
dicyanodistyrylbenzene，Soya Kojima, Mitsuki Hoshi, Yuji
Kubo, 1H3-19，The 99th CSJ Annual meeting，Konan
University (Hyogo)，2019，Mar 16th.
8. A panchromatic photosensitizer for photocatalytichydrogen production，Haruka Sato, Yuta Higashino, Okta
Suryani, Yuji Kubo ， 1G2-54 ， The 99th CSJ Annual
meeting，Konan University (Hyogo)，2019，Mar 16th.
9. Synthesisofthieno[1,3,2]oxazaborinine-typed
aza-BODIPY dyes with near-infrared absorption band，
Takuma Shimada, Yuji Kubo, 1G2-53，The 99th CSJ
Annual meeting，Konan University (Hyogo)，2019，Mar
16th.
10. The room-temperature phosphorescent property ofmono-dispersed boronate particles，Mitsuki Hoshi, Ryuhei
Nishiyabu, Yuji Kubo, 3-20，The 99th CSJ Annual meeting，
Konan University (Hyogo)，2019，Mar 16th.
11. Synthesis of several arylseranyl-BODIPY dyes and thesubstitution effect on photon upconversion ， Ryohei
Hasegawa, Keita Iizuka, Yuji Kubo, 2B4-46，The 99th CSJ
Annual meeting，Konan University (Hyogo)，2019，Mar
17th.
See the annual report in Japanese for other presentation (2poster presentation)■ Review (in Japanese)
See the annual report in Japanese.

13

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

The dynamics of the rotor inside a crystalline state can beanalyzed by dielectric spectra and solid-state NMR
spectroscopy. Crystals without a solvent molecule show usual
dielectric relaxation spectra due to orientation polarization of
the dipolar rotor, while a crystal having ethanol as the
crystalline
solvent
molecule
showednovel
temperature-dependent dielectric relaxation switching by
crystalto-crystal phase transition, which is induced byhydrogen-bonding interactions between thiophene dioxide andethanol.

Yusuke Inagaki
Assistant Professor / Dr. Sci.
Main-group Chemistry, Functional Organic Chemistryroom: 9-545 TEL: +81-42-677-1111 (Ext.4957)
e-mail: yinagaki@tmu.ac.jp

The stable redox properties of ferrocene/ferrocenium have beenused to investigate ferrocene-based functional materials. Herein,
the steric effects of an exteriorcage on the redox properties ofinterior metallocenes have been investigated using cyclic
voltammetry measurements of ferrocene-diyl bridged
macrocages and their noncage isomers (Figure 3, paper #2).

Doctor’s course -0
Master’s course -5
Bachelor 4 -3

■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.

Figure 3. Cycloc voltamogram of ferrocenes (paper #2).
As the half-wave potential (E1/2) depends on ferrocenium
stabilization through solvation, positive shifts in the E1/2 wereobserved in the macrocages. As peak separation between
potentials of the anodic and cathodic peaks depends on the rateof electron transfer, marked broadening from the ideal value
was observed in the macrocages due to the insulating effect of
the outer cage. These steric effects of the cage on the redox
properties of ferrocenes could aid the molecular design ofmetallocene-based functional molecules.

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.

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
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 (Figure 4).

Figure 1. molecular gyrotop.
In this year, following papers were published.
Thiophene dioxide is one of the highly polared -electron
systems because of large dipole moment (3.9 D). Moleculargyrotop with a bridged thiophene dioxide was designed andsynthesized (paper #1).

Figure4. Cluch-decluch function in a novel molecular gear.

Figure 2. Dielectric spectra of molecular gyrotop with abridged thiophene dioxide (paper #1).

14

Reports from Research Groups■Papers with Peer Review

Fenabori, 2018.10.23-25 (Tokyo, Japan).(10/23
P2-044)(poster)

1. Dielectric Relaxation of Powdered Molecular Gyrotops
Having a Thiophene Dioxide-diyl as a Dipolar Rotor,
M. Tsurunaga, Y. Inagaki, H. Mommma, E. Kwon, K.
Yamaguchi, K. Yoza, and W. Setaka, Org. Lett., 20, 6934-6937(2018). DOI: 10.1021/acs.orglett.8b03087

3. Synthesis and Photophysical Properties of a caged
Thieno[3,2-b]thiophene
Daiki Hayashi, Yusuke Inagaki, Wataru Setaka
8th CSJ Chemistry Festa, 2018.10.23-25, Tower Hall ofFenabori, 2018.10.23-25 (Tokyo, Japan).(10/25
P7-056)(poster)

2. Ferrocene-diyl Bridged Macrocages: Steric Effects of theCage on the Redox Properties of Ferrocene Moiety
H. Takashima, Y. Inagaki, H. Momma, E. Kwon, K.
Yamaguchi, and W. Setaka, Organometallics, 37, 1501-1506(2018). doi:10.1021/acs.organomet.8b00154

4. Observation of Large Solid-solid Phase Transition Enthalpy
Change due to Switching of Molecular Motions
Wataru Setaka, Hideaki Takashima, Kentaro Yamaguchi
The 99th CSJ Annual Meeting, Konan University (Kobe)■Invited Lectures
1. Crystalline Molecular Gyrotops as Regularly Arranged
Dipolar Rotor
Wataru Setaka
The 3rd International Conference on Emerging Advanced
Nanomaterials (ICEAN 2018), 2018.10.30-11.2, the Newcastle
Exhibition and Convention Center (Newcastle, NSW,
Australia) (11/2 7E-IL-3)(invited)
2. Structural Chemistry of Moleculargyrotop
Wataru Setaka
Seminor at Kindai University (Higashiosaka, Osaka)■Awards
1. Wataru Setaka received the excellent professor award, Tokyo
Metropolitan University, 2019.1.
■Academic Meeting*International
1. Thiophenediyl-bridged Macrocages as Crystalline MolecularDipolar Rotors
W. Setaka and K. Yamaguchi
24th IUPAC Conference on Physical Organic Chemistry(ICPOC24),
Algrave
University,
2018.7.1-6,(Faro,
Portugal)(7/5, OP51) (oral)
2. Rotation of the π-System Rotor in Crystalline MolecularGyrotops
Y. Inagaki, K. Yamaguchi, and W. Setaka
24th IUPAC Conference on Physical Organic Chemistry(ICPOC24),
Algrave
University,
2018.7.1-6,(Faro,
Portugal)(7/3, P35) (poster)
3. A Thienylthiophenedioxide-bridged Macrocage as a
Fluorescent Dielectric Material
Daiki Hayashi, Yusuke Inagaki, Kentaro Yamaguchi, Wataru
SetakaThe 3rd International Symposium on Hydrogen Energy-based
Society, 2018.8.22-23, Tokyo Metropolitan University(Tokyo,
Japan) (8/23, P-4) (poster)*Domestic
1. Synthesis and Structures of 2,2'-Bipyridine-bridged
Molecular Gyrotops
Masaya Ito, Yusuke Inagaki, Kentaro Yamaguchi, Wataru
SetakaThe 29th Symposium on Physical Organic Chemistry (POC29),
Tokyo Institute of Technology, 2018.9.6-8 (Tokyo, Japan).(9/6
1C05)(oral)
2. Synthesis and Dynamics of Tin-linked Molecular Bevel
Gears
Satoshi Hososno, Yusuke Inagaki, Wataru Setaka
8th CSJ Chemistry Festa, 2018.10.23-25, Tower Hall of15

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

4.2
4Chemistry,

Voltage / V

EnergyHirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-246 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp

2200

3. Research on Fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
Toward the realization of a hydrogen society, the developmentof a new fuel cell system that works at intermediate temperatures
over 100 °C under non-humidified conditions was promoted
continuously in this FY based on the use of phosphoric acid /ionic liquid mixed electrolytes that have high proton
conductivity and thermal stability. In order to mature this fuelcell as a more practical system, the exhaust gases were analyzed
during the cell operation (Fig. 4).

3

-2

5

I / mA cm

50
100
150
Capacity / mAh g–1

Fig.3 A thin and flexible solid electrolyte sheet densigned forsolid-state battereis.

10

0
-5

0

Fig.2 Application of ionic liquids to the cathode for improving
the charge-discharge performance of the cell using a solid
electrolyte.

2+

1

－1st
－5th
－10th
－20th
－30th
－40th
－50th

3.4

3

■Outlines of the Research
1. Research on Rechargeable magnesium batteries
Kiyoshi KANAMURA
Rechargeable magnesium batteries are attracting much attention
as next generation batteries to replace current lithium ion
batteries due to its abundant resources on the earth. In this FY,
we mainly carried out the research on electrolyte solutions forrechargeable magnesium batteries, and successfully obtained
their design guideline based on electrochecmial andspectroscopic measurements.
E / V vs. Mg/Mg

3.6

3.2

Doctor’s course -5
Master’s course -12
Bachelor 4 -70

3.8

EtOMgCl-based
Et2NMgCl-based
EtSMgCl-based

-10
-3

-2

-1

0

+

1

E / V vs. Ag/Ag

Fig. 4 The operation of fuel cells applied with phosphoric acid /ionic liquid mixed electrolytes at intermediate temperatures
without humidification, and evaluation of exhaust gases.

Fig. 1 Electrochemcial deposition/dissolution behaviors anddeposition morphologies of magnesium in various electrolyte
solutions.

■Papers with Peer Review

1.

2. Research on Safe rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of rechargeable lithium batteries with highenergy density and excellent safety was carried out continuously
in this FY, mainly based on the researches of the electrodefabrication using ionic liquids (Fig. 2) and the flexible quasisolid electrolytes (Fig. 3).

2.

16

Keisuke Ando, Yuto Yamada, Kei Nishikawa, Tomoyuki
Matsuda, Daichi Imamura, Kiyoshi Kanamura,
Degradation Analysis of LiNi0.8Co0.15Al0.05O2 for CathodeMaterial of Lithium-Ion Battery Using Single-Particle
Measurement, ACS Appl. Energy Mater., 1, 4536–4544(2018).
Yuto YAMADA, Yusaku NODA, Hirokazu MUNAKATA,
Shuhei YOSHIDA, Daisuke SHIBATA, Kiyoshi

Reports from Research Groups

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

KANAMURA, Investigation of Carbon-coating Effect on
the Electrochemical Performance of LiCoPO4 Single
Particle, Electrochemistry, 86, 145-151 (2018).
Koichi KAJIHARA, Ryo TAKAHASHI, Hirohiko KATO,
Kiyoshi KANAMURA, Seed-free hydrothermal synthesisof all-silica deca-dodecasil 3R with essential reagents,
Journal of the Ceramic Society of Japan, 126, 221-229(2018).
Hiroki YAMASHITA, Takaaki OGAMI, Kiyoshi
KANAMURA, Hydrothermal synthesis and catalytic
activity of Pt–Rh/CeO2/Al2O3 three-way catalysts forautomotive exhaust gas, J. Ceram. Soc. Jpn. 126, 394-401(2018).
Hiroki YAMASHITA, Takaaki OGAMI, Kiyoshi
KANAMURA,
Enhanced
EnergyDensityof
Li2MnSiO4/C Cathode Materials for Lithium-ion Batteries
through Mn/Co Substitution, Electrochemistry, 86, 324–
332 (2018).
Akichika Kumatani, Yasufumi Takahashi, Chiho Miura,
Hiroki Ida, Hirotaka Inomata, Hitoshi Shiku, Hirokazu
Munakata, Kiyoshi Kanamura, Tomokazu Matsue,
Scanning electrochemical cell microscopy forvisualization and local electrochemical activities oflithium‐ion (de) intercalation process in lithium‐ion
batteries electrodes, Surf Interface Anal., 1–4 (2018).
Mayu Suda, Ryosui Nakagawa, Kiyoshi Kanamura,
Koichi Kajihara, Sol–gel-derived transparent silica–(Gd,Pr)PO4 glass-ceramic narrow-band UVB phosphors,
Dalton Trans., 47, 12085–12091 (2018).
Minato Egashira, Kaori Hiratsuka, Kouki Matsubara,
Yasuhiro Akita, Hirokazu Munakata, Kiyoshi Kanamura,Multi-dentate phenoxyimine magnesium chloride complex
for magnesium battery electrolyte, Materials Today Energy,
9, 279-284 (2018).
Fuminori Ito, Hidetaka Yamada, Kiyoshi Kanamura,
Hiroyoshi Kawakami, Preparation of Biodegradable
Polymer Nanospheres Containing Manganese Porphyrin(Mn-Porphyrin), Journal of Inorganic and Organometallic
Polymers and Materials, 28, 1-9 (2018).
Hasna PUTHEN PEEDIYAKKAL, Jie YU, Hirokazu
MUNAKATA, Kiyoshi KANAMURA, Highly Durable
Non-Platinum Catalyst for Protic Ionic Liquid Based
Intermediate Temperature PEFCs, Electrochemistry, 87,
35-46 (2019).
Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei
Onodera, Shinji Kohara, Structure, Microscopic Ordering,and Viscous Properties of Amorphous Poly(n‐alkylsilsesquioxane) Liquids and Solids Synthesized by
Cosolvent‐Free Hydrolytic Polycondensation of n‐Alkyltrimethoxysilanes, Physica Status Solidi A, 216,
1800475 (2019).
Motoko Nagasaki, Takuya Masuda, Kei Nishikawa,
Kiyoshi Kanamura, Surface State Change of Lithium
Metal Anode in Full Cell during Long Term Cycles,
Electrochemistry, 87, 1-5 (2019).
Masashi Hattori, Kentaro Yamamoto, Masaki Matsui, Koji
Nakanishi, Toshihiko Mandai, Ashu Choudhary, Yoshitaka
Tateyama, Keitaro Sodeyama, Tomoki Uchiyama, Yuki
Orikasa, Yusuke Tamenori, Tatsuya Takeguchi, Kiyoshi
Kanamura, Yoshiharu Uchimoto, Role of Coordination
Structure of Magnesium Ions on Charge and Discharge

14.

15.

16.

Behavior of Magnesium Alloy Electrode, The Journal of
Physical Chemistry C, 122, 25204-25210 (2018).
Li Chunyan, Kei Nishika, Jinhee Moon, Kiyoshi
Kanamura,
Electrodeposition
of
Zn
from
1‑allyl‑3‑methylimidazolium bromide containing ZnBr2,
Journal of Electroanalytical Chemistry, 832, 467-474(2019).
Shoji Mao, Cheng, Eric Jianfeng, Kimura, Takeshi,
Kanamura, Kiyoshi, Recent progress for all solid statebattery using sulfide and oxide solid electrolytes, J. Phys.
D: Applied Physics, 52 (2019).
Fumihiro Sagane, Kenta Ogi, Akinori Konno, Kiyoshi
Kanamura, The Effect of Cyclic Ethers on Mg
Plating/Stripping Reaction in Ionic Liquid Electrolytes, J.
Electrochem. Soc., 166, A5054-A5058 (2019).

■Books and reviews
See the annual report in Japanese (8 articles)■Invited Lectures

1.

2.

3.

4.

5.

6.

Kiyoshi Kanamura, All Solid State Batteries with QuasiSolid Electrolyte and Composite Cathode, CMCEE2018,
Jul. 2018, Suntec Convention & Exhibition Center,
Singapore
Hirokazu Munakata, Yoshiyuki Shibata, Kiyoshi Kanamura,
Development of a quasi-solid composite electrolyte for 3Dstructured batteries, The 6th International Conference on
advanced nanomaterials and energy storage systems(INESS-2018), Aug. 2018, Astana, Kazakhstan
Kiyoshi Kanamura, Electrochemical Characterization of
All-Solid-State Battery with Li7La3Zr2O12 Solid Electrolyte,
2018 MRS Fall Meeting & Exhibit, Nov. 2018, Boston,USA
Hirokazu Munakata, Electrochemical evaluation of active
materials for lithium-ion batteries by single particle
measurement, Oct. 2018, Karlsruher Institut fürTechnologie, Karlsruhe, Germany
M. Shoji, K. Hommo, Eric J. Cheng, H. Munakata, K.
Kanamura, Characterization of composite cathode withionic liquid for all solid state lithium batteries, Work shop
on Lithium Battery and Next Generation Batteries, Nov.
2018, Qingdao, China
Toshihiko Mandai, Kenya So, Yukihiro Nakabayashi,
Kiyoshi Kanamura, Modification of structure of supporting
salt for high voltage magnesium rechargeable batteries,
Work shop on Lithium Battery and Next Generation
Batteries, Nov. 2018, Qingdao, China

See the annual report in Japanese (the other 8 Japanese articles)■Academic Meeting＊International
1. Jie Yu, Shojiro Kikuchi, Hirokazu Munakata, Kiyoshi
Kanamura, Development of electrolyte membranes apply
on non-humidified intermediate temperature fuel cells,
EVS31 ＆ EVTeC2018, Sep. 2018, KOBE convention
center, Hyogo
2. Kiyoshi Kanamura, Masaki Matsuzawa, Discharge andCharge Characteristics of LiMnXFeyPO4 Cathode for
Rechargeable Lithium Metal Battery, The 12th JapanFrance Joint Seminar on Battery, Sep. 2018, Nagaragawa
Convention Center, Gifu
17

Reports from Research Groups
3.

Kei Nishikawa, Chunyan Li, Kiyoshi Kanamura,
Mechanism of First Charging of One Silicon Particle, The
12th Japan-France Joint Seminar on Battery, Sep. 2018,
Nagaragawa Convention Center, Gifu

＊Domestic
See the annual report in Japanese (21 articles)

18

Reports from Research Groups
Kajihara Laboratory■Member
Koichi KAJIHARA
Associate Professor /Ph.D.
Inorganic Chemistry, Functional Material Chemistry,
Inorganic Materials/Physical Properties
room:9-336 TEL: +81-42-677-2827
e-mail: kkaji@tmu.ac.jp

rhombohedral particles, whose adsorption properties and crystal
morphology are the best for the applications for adsorption andgas separation.

Master’s course -4
Bachelor 4 -2

■Outlines of the Research
1. Studies on photoluminescent silica glasses
Koichi KAJIHARA
Silica glass exhibits wide transparency window from nearinfrared to deep ultraviolet spectral ranges, high mechanicalstrength, chemical stability, and shape workability. These
properties are suitable for hosts of optically active centers. We
are studying rare-earth (RE)-doped silica glasses, and havedeveloped glass-ceramics containing REPO4 nanocrystals thatexhibit excellent rancparency. This year we focused on thedevelopment of glasses containing (Gd,Pr)PO4 nanocrystals,
which exhibit narrow-band UVB emission at 313 nm attributed
to the 6P7/2 → 8S7/2 transiton of Gd3+ ions. This emission is
attractive for the phototherapy of skin diseases such as psoriasis
and vitiligo. We obtained glasses with internal quantum
efficiency of the emission close unity under excitation at 220 nm.
The external quantum efficiency of the glasses exceeds 0.9
because of the high absorption coefficient of the excitation light.
These glasses are promising for narrow-band UVB phosphors.

Fig. 2 Synthesis and characterization of silica zeolite DDR.
3. Studies on polysilsesquoxanes
Koichi KAJIHARA
Silsesquioxanes (SQs) are silicon-based organic-inorganic
hybrids with general formula of RSiO3/2. We have developed thegreen synthetic routes of polymers of SQs (polysilsesquoxanes,
PSQs) and are investigating the properties and applications of
PSQs. This year we perfomed the structure analysis of liquid andsolid forms of poly(alkylsilsesquioxanes) by high-energy
synchrotron X-ray diffraction, and evidenced that they exhibit
microscopic ordering with a periodicity of ~10nm, the origin of
the periodicity is the surface modification of the silica-richpahses consisting of Si-O bonds with alkyl groups of fixed
lengths, the structural similarity of solid and liquid phases, andthe structural similarity of silica-rich phases and silica glass (aSiO2). The Q0 peaks originating from the periodic structures areintense and sharp (Fig. 3), indicating that the periodic structure
is distinct and the disorder is reatively small. Such liquids withorderd structurs are scarce and interesting. This microscopic
ordiering may be responsible for the very slow polycondensationand long pot life of the liquid.

Fig. 1 Development of highly-efficient narrow-band UVB
phosphor glasses.
2. Studies on silica zeolites
Koichi KAJIHARA
Abstract
Silica zeolites consist only of strong SiO bonds, and exhibit highchemical and thermal stabilites, which are suitable forapplications including separation technology. On the other hand,the synthesis of silica zeolites are often difficult, and they havebeen studied less than conventional multicomponent zeolites.
This year we explored ways to synthesize deca-dodecasil 3R(DDR), which can be utilized for the separation of CO2 from CH4
or N2, and water and alcohols. Seed-free synthesis of DDR fromessential reagents, i. e., silica source, water, and organic structure
directing agent, was studied, and it was found that this method
enables synthesis in 5 days in the shortest case. We also
determined the crystal faces of resultant DDR crystal particles(Fig. 2), and evindenced that synthesis at relatively low
temperature at 160°C is the most suitable in obtaining

Fig. 3 Structure analysis of liquid and solid forms ofpoly(alkylsilsesquioxanes) by high-energy X-ray diffraction.

■Papers with Peer Review
1. K. Kajihara, R. Takahashi, H. Kato, K. Kanamura, Seed-freehydrothermal synthesis of all-silica deca-dodecasil 3R withessential reagents, J. Ceram. Soc. Jpn. 126, 221-229 (2018)
2. M. Suda, R. Nakagawa, K. Kanamura, K. Kajihara, Sol-gelderived transparent silica–(Gd,Pr)PO4 glass- ceramic narrow19

Reports from Research Groups
band UVB phosphors, Dalton Trans. 47, 12085-12091 (2018)
3. K. Kajihara, R. Seto, K. Kanamura, Y. Onodera, S. Kohara,
Structure, microscopic ordering, and viscous properties ofamorphous poly(n-alkylsilsesquioxane) liquids and solids
synthesized by cosolvent-free hydrolytic polycondensation ofn-alkyltrimethoxysilanes, Phys. Status Solidi A 216, 1800475(2019)
4. L. Skuja, N. Ollier, K. Kajihara, K. Smits, Creation of glasscharacteristic point defects in crystalline SiO2 by 2.5MeV
electrons and by fast neutrons, J. Non-Cryst. Solids 505, 252259 (2019)■Reviews＊Domestic
See the annual report in Japanese (2 articles)■Invited Lectures＊Domestic
See the annual report in Japanese (1 lecture)■Academic Meeting＊International
1. K. Kajihara, A. Sakuragi, Y. Igarashi, Y. Fukuda, K.
Kanamura, Cosolvent-free synthesis of polysilsesquioxane
liquids and polysilsesquioxane-based organic-inorganic
hybrid glasses, SiO2 2018, Bari, Italy, 2018/6/13
2. K. Kajihara, N. Tezuka, M. Saito, Y. Kizuki, M. Shoji, H.
Munakata, K. Kanamura, New lithium-ion-conducting cubic
boracite Li4B4M3O12Cl (M = Al, Ga) and the application tosolid-state lithium secondary batteries, 3rd International
Symposium on Hydrogen Energy-Based Society, Tokyo,
Japan, 2018/8/23
3. K. Kajihara, S. Yamaguchi, M. Suda, K. Kanamura,
Cosolvent-free sol-gel synthesis of monolithic highlytransparent silica-REPO4 glass-ceramics with bright visible
and ultraviolet photoluminescence, ICG Annual Meeting
2018, Yokohama, Japan, 2018/9/25
4. R. Seto, K. Kajihara, K. Kanamura, Synthesis ofpoly(phenylsilsesquioxane) glasses with low melting
temperatures by cosolvent-free hydrolytic polycondensation
via aging,
ICG Annual Meeting 2018, Yokohama,Japan, 2018/9/25＊Domestic
See the annual report in Japanese (7 articles)■Patents＊Domestic
See the annual report in Japanese (1 article)■Awards
1. Front Cover & Editor’s Choice, J. Ceram. Soc. Jpn. vol. 126,
no. 4
K. Kajihara, R. Takahashi, H. Kato, K. Kanamura, Seed-freehydrothermal synthesis of all-silica deca-dodecasil 3R withessential reagents, J. Ceram. Soc. Jpn. 126, 221-229 (2018)
2. Inside Front Cover, Dalton Trans. vol. 47, no. 35
M. Suda, R. Nakagawa, K. Kanamura, K. Kajihara, Sol-gelderived transparent silica–(Gd,Pr)PO4 glass- ceramic narrowband UVB phosphors, Dalton Trans. 47, 12085-12091 (2018)20

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

Chemistry,

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

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

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

Tetsuya SHIMADA
Assistant Prof. / Ph.D.
Physical Chemistry, Spectroscopy
Room: 9-445 TEL: +81-42-677-1111 (Ext.4897)
e-mail: shimada-tetsuya@tmu.ac.jp
Hidetaka NORITOMIAssistant Prof. / Dr.Eng.
Enzyme Technology, Nanomaterial, Bioprocess
Room: 9-148 TEL: +81-42-677-1111 (Ext.4838)
e-mail: noritomi @tmu.ac.jp
Master’s course -13
Bachelor 4 -6

■Outlines of the Research

Our group challenges to control photochemical reactions suchas electron and energy transfer, by controlling the orientation andalignment of dyes on the inorganic surfaces.
Recently,organic/inorganic hybrids composed of porphyrins and layeredmaterials have been the subject of intensive investigations to
explore their novel properties and functionalities. We foundout that a precise matching of distances between the negatively
charged sites on the clay mineral layers and that between thepositively charged sites in the dye molecule is one of the mostimportant factors to determine the structure of the clay–dye
complex. We have termed this the “Size-Matching Rule” Our
goal is finding out a new methodology to control molecularassembly structure and realizing functionalized photochemical
reaction systems such as an artificial light harvesting system.

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

1. Research on Artificial light harvesting system
Shinsuke TAKAGI, Tetsuya SHIMADA
The quantitative excited energy transfer reaction between
cationic porphyrins on an anionic clay surface was successfully
achieved. The efficiency reached up to ca. 100% owing to the“Size- Matching Rule” that is our original technique. It was
revealed that the important factors for the efficient energy
transfer reaction are (i) suppression of the self-quenching
between adjacent dyes, and (ii) suppression of the segregatedadsorption structure of two kinds of dyes on the clay surface.
These findings indicate that the clay/porphyrin complexes arepromising and prospective candidates to be used for constructionof an efficient artificial light-harvesting system. 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. 3. Adsorption of protein on nanosheets and formation of
apoprotein..

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 the clay
in water, the factor for the fluorescence enhancement is turned
out not to be AIE, but is to be Surface - Fixation Induced
Emission (S - FIE) mechanism. While the effect of AIE
21

Reports from Research Groups
depended on the molecular structure of dye in water-dioxane, S- FIE worked even for the dye that has bulky substituent.

Table 1. Transfer vinylation of supported Au catalysts.

Fig. 4. Surface – Induced Emission on the nanosheets. Left: without
nanosheet, Right: with nanosheet..

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 researchtarget 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 withgood electron transfer property for artificial photosynthesis
system. We synthesized a novel TiO2 nano-sheet (TNS) andcharacterized it in detail. We observed adsorption behavior of
porphyrin dyes on the TNS and photochemical interaction
between the dyes and the TNS.

In addition, hydroxyapatite (HAP) supported Au catalysts
were examined for the activation of alkenes. Wang who is ourcollaborator in China has reported that Au/HAP showed inverse
strong metal-support interaction (SMSI) in which Au NPs are
partly covered by HAP under oxidative conditions, and Au atoms
at the perimeter interface became cationic under the inverse
SMSI (Fig. 6). Therefore, Au/HAPs with SMSI seem to be a
promising candidate as a soft Lewis acid catalysts. Au/HAPs
were prepared under oxidative and reductive conditions andwere abbreviated as Au/HAP_O2 and Au/HAP_H2, respectively.
Whereas the sizes of Au nanoparticles were almost similar (ca. 3nm), Au/HAP_O2 with SMSI exhibited superior activity to
Au/HAP_H2 without SMSI and Au/CeO2-ZrO2. This result
suggests that the electronic interaction between Au and HAP thinlayer of Au/HAP_O2 with SMSI enhaces the soft Lewis acidity,
resulting in high catalytic activity for transfer vinylation.

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

5. Research on Gold Nanoparticle-Catalyzed Organic Reactions
Tamao, ISHIDAGold nanoparticles have been reported to work as a soft Lewis
acid catalyst for such as hydroamination of alkynes, but thesubstrates are generally alkynes. In the case of alkenes as
substrates, the examples are limited to intramolecular reaction.
We have studied on the development of Au catalysts that are
applicable to the activation of alkenes using transvinylation ofcarboxylic acid as a model reaction. We have screaned several
kinds of metal oxide-supported Au catalysts and found thatamphoteric oxides such as ZrO2 and CeO2-ZrO2 were suitablesupports. In hthis year, we studied the effect of particle size andchemical states of Au for Au/CeO2-ZrO2 on the reaction in detail(Table 1). Au(III)-, Au nanoparticles-, and Au clustersdeposoited on CeO2-ZrO2 were prepared by varying thecalcination atmosphere and temperatures. The catalysts obtained
were characterized by X-ray absorption fine structure (XAFS)
and high-angle annular dark field scanning transmission electron
microscopy) measurements. Among three catalysts, Au clustersdeposited on CeO2-ZrO2 exhibited the highest catalytic activity.
This is probably due to an increase in cationic Au species at theperimeter intereface with a decrease in Au particle size.

Fig. 6. Schematic representation of SMSI effect for Au/HAP.

6. 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 tobioprocesses such as bioreactors, biosensors, and biofuel cells.

■Papers with Peer Review

1. Adsorption and Emission Enhancement Behavior of 4,4'Bipyridine on Dispersed Montmorillonite Nano-sheets
under Aqueous Conditions, R. Nakazato, T. Shimada, Y.
Ohtani, T. Ishida, S. Takagi, Tetrahedron Lett., 59, 24592462(2018).
2. Fluorescence Enhancement Behavior of Hemicyanine
Derivatives on the Clay Nanosheets: Aggregation Induced
Emission (AIE) vs. Surface - Fixation Induced Emission (SFIE), N. Kudo, T. Tsukamoto, D. Tokieda, T. Shimada, S.
Takagi, Chem. Lett., 47, 636-639(2018).
3. Efficient Electron Injection from Excited Porphyrin to22

Reports from Research Groups
Ishida, T. Shimada, 27th IUPAC International
Symposium on Photochemistry, Dublin (Ireland), July,
2018.
5. Adsorption and Emission Enhancement Behaviour of
Nonionic Molecules on Dispersed Clay Nano-Sheets under
Aqueous Conditions, R. Nakazato, T. Shimada, T. Ishida,
S. Takagi, 27th IUPAC International Symposium on
Photochemistry, Dublin (Ireland), July, 2018.
6. Photochemistry of Various Cationic Porphyrins on Titania
Nanosheet Surface, K. Sano, A. Sonotani, R. Ohnishi, T.
Shimada, T. Ishida, S. Takagi, 27th IUPAC International
Symposium on Photochemistry, Dublin (Ireland), July,
2018.
7. A control of negative charge arrangement on the clay
surface under the mild condition, K. Arakawa, T.
Shimada, T. Ishida, S. Takagi, The 3rd International
Symposium on Hydrogen Energy‒based Society, Tokyo(Japan), August, 2018.
8. Photochemical properties of porphyrin/titania-nanosheet
complex, Y. Hirade, K. Sano, T. Shimada, T. Ishida, S.
Takagi, The 3rd International Symposium on Hydrogen
Energy‒based Society, Tokyo (Japan), August, 2018.
9. Dye-sensitized hydrogen production reaction using
dye/Rh-doped titania nanosheet complex, R. Onishi, K.
Sano, T. Shimada, T. Ishida, S. Takagi, The 3rdInternational Symposium on Hydrogen Energy‒based
Society, Tokyo (Japan), August, 2018.
10. Preparation of transparent TiO2 dispersion for molecularcatalyst sensitized water splitting systems, K. Sano, R.
Sebastian, K. Fazalurahman, T. Shimada, T. Ishida, H.
Tachibana, H. Inoue, S. Takagi, The 3rd International
Symposium on Hydrogen Energy‒based Society, Tokyo(Japan), August, 2018.
11. Photochemical Behavior of Zwitterionic Photochromic
Dye on Clay Nanosheets, A. Nakayama, T. Shimada, T.
Ishida, S. Takagi, The 10th Asian Photochemistry
Conference, Taipei (Taiwan), December, 2018.
12. Stabilization of Transparent Aqueous Dispersion of TiO2
Nanoparticles Prepared by Novel Sol/Gel Method and its
Photocatalytic Activity, K. Sano, F. Kuttassery, S.
Remello, T. Shimada, T. Ishida, H. Tachibana, S. Takagi,
H. Inoue, The 10th Asian Photochemistry Conference,
Taipei (Taiwan), December, 2018.
13. Development and Characterization of Magnesium
Porphyrin/Clay Mineral Hybrid Film as Optical Relative
Humidity Indicator, T. Fujimura, T. Shimada, R. Sasai,
S. Takagi, International Congress on Pure and Applied
Chemistry Langkawi 2018, Langkawi (Malaysia),
October, 2018.
14. Anti-inlammatory effect of gold nanoparticles supported
on metal oxides, T. Fujita, T. Ishida, T. Murayama, M.
Haruta, S. Lanone, J. Boczkowski, GOLD2018, Paris(France), July, 2018.
15. Polyoxometalate-Supported Gold Nanoparticulate
Catalysts Prepared by Sol Immobilization Method andTheir Catalytic Activity, T. Murayama, T. Yoshida, M.
Lin, N. Sakaguchi, T. Ishida, M. Haruta, GOLD2018,
Paris (France), July, 2018.
16. Gold Nanoparticles as Soft Lewis Acid Catalysts forTransfer Vinylation, T. Ishida, R. Sodenaga, T. Honma,
M. Haruta, GOLD2018, Paris (France), July, 2018.

Titania Nanosheet, A. Sonotani, K. Sano, S. Wakayama, T.
Shimada, S. Takagi, Chem. Lett., 47, 803-805(2018).
4. How does the Tin(IV)-Insertion to Porphyrins Proceed in
Water at Ambient Temperature?: Re-Investigation by Time
Dependent 1H NMR and Detection of Intermediates, Y.
Ohsaki, A. Thomas, F. Kuttassery, S. Mathew, S. Remello,
Y. Nabetani, T. Shimada, S. Takagi, H. Tachibana, H. Inoue,
Inorg. Chim. Acta, 482, 914-924(2018).
5. Artificial Photosynthesis Model: Photochemical Reaction
System with Efficient Light-Harvesting Function on
Inorganic Nanosheets, T. Tsukamoto, T. Shimada, S. Takagi,
ACS Omega, 3, 18563–18571(2018).
6. Effect of solvent on catalysis of protease adsorbed on
biochar in organic media, H. Noritomi, J. Nishigami, N.
Endo, S. Kato, S. Takagi, J. Mater. Sci., 7, 46-52(2018).
7. Selective adsorption of 1,3-dimethyltrisulfane (DMTS)
responsible for aged odour in Japanese sake using supported
gold nanoparticles, H. Murayama, Y. Yamamoto, M. Tone,
T. Hasegawa, M. Kimura, T. Ishida, A. Isogai, T. Fujii, M.
Okumura, M. Tokunaga, Sci. Rep., 8, 16064(2018).
8. Supported gold cluster catalysts prepared by solid grinding
using a non-volatile organogold complex for lowtemperature CO oxidation and the effect of potassium on
gold particle size, L. Dien, T. Ishida, A. Taketoshi, D.
Truong, H. Chinh, T. Honma, T. Murayama, M. Haruta, Appl.
Catal. B: Environ., 241, 539-547(2019).
9. Direct transformation of terminal alkenes with H2O into
primary alcohols over metal oxide-supported Pd catalysts, Z.
Zhang, T. Mamba, E. Yamamoto, H. Murayama, T. Ishida,
T. Honma, T. Fujitani, M. Tokunaga, Appl. Catal. B:
Environ., 246, 100-110(2019).
10. Role of the Acid Site for Selective Catalytic Oxidation of
NH3 over Au/Nb2O5, M. Lin, B. An, N. Niimi, Y. Jikihara, T.
Nakayama, T. Honma, T. Takei, T. Shishido, T. Ishida, M.
Haruta, ACS Catal., 9, 1753–1756(2019).
+1 articles in Japanese (See the annual report in Japanese)■BooksSee the annual report in Japanese (2 articles)■Academic Meeting＊International
1. Preparation and Catalytic Porperties of Supported Gold
Nanoparticles and Clusters, T. Ishida, Singapore-Japan
Bilateral Meeting on Functional Materials Chemistry,
Nanyang (Singapore), April, 2018 (Invited).
2. Heterogeneous Gold Nanoparticles as Soft Lewis Acid
Catalysts for Transfer Vinylation of Carboxylic Acids, T.
Ishida, Intenational Symposium on Catalysis and Fine
Chemicals (C&FC) 2018, Bangkok (Thailand),
December, 2018 (Invited).
3. Photochemical Reaction System Sensitized by
Metalloporphyrin with Efficient Light Harvesting Function
on Inorganic Nanosheets, S. Takagi, D. Tatsumi, T.
Tsukamoto, T. Ishida, H. Inoue, T. Shimada, The 10th
Asian Photochemistry Conference, Taipei (Taiwan),
December, 2018 (Invited).
4. Fluorescence Enhancement Behavior of Hemicyanine
Derivatives on The Inorganic Nanosheet: Aggregation
Induced Emission (AIE) vs. Surface - Fixation Induced
Emission (S-FIE), S. Takagi, N. Kudo, T. Tsukamoto, T.
23

Reports from Research GroupsEndo, S. Kato, S. Takagi, The Fourth International
Conference on Science, Engineering & Environment(SEE2018), Nagoya (Japan), November, 2018.
＊Domestic
See the annual report in Japanese (39 articles)

17. Efficient Elimination of Ammonia over Niobium Oxide
Supported Gold Catalyst at Room Temperature, M. Lin,
B. An, N. Niimi, Y. Jikihara, T. Nakayama, T. Ishida, M.
Haruta, T. Murayama, GOLD2018, Paris (France),
July, 2018.
18. Oxidative Esterification of Aliphatic Aldehydes by Gold
Nanoparticle Catalysts in a Continuous Flow Reactor, A.
Taketoshi, T. Ishida, T. Murayama, M. Haruta,
GOLD2018, Paris (France), July, 2018.
19. Redox Reaction of NAD+/NADH by Au Cluster Catalysts
Related to the Coenzyme Regeneration for
Dehydrogenases, J. Nishigaki, T. Ishida, M. Haruta,
GOLD2018, Paris (France), July, 2018.
20. Selective Catalytic Oxidation of Trimethylamine overSupport Gold Catalysts at Low Temperature, B. An, M.
Lin, N. Niimi, Y. Jikihara, T. Nakayama, T. Ishida, M.
Haruta, T. Murayama, GOLD2018, Paris (France),
July, 2018.
21. Gold Nanoparticle-Catalyzed Transfer Vinylation of
Carboxylic Acids: Effects of Supports and Gold Particle
Size, R. Sodenaga, T. Ishida, T. Honma, M. Haruta,
GOLD2018, Paris (France), July, 2018.
22. Preparation of supported gold nanoparticles andapplication to adsorbents of sulphur compounds, H.
Murayama, T. Hasegawa, Y. Yamamoto, M. Tone, M.
Kimura, T. Ishida, T. Honma, GOLD2018, Paris(France), July, 2018.
23. DFT study for adsorptive decomposition of 1,3dimethyltrisulfane (DMTS) over gold nano clusters: theelimination of aged odour in Japanese sake, M.
Okumura, H. Murayama, Y. Yamamoto, M. Tone, T.
Hasegawa, M. Kimura, T. Ishida, M. Tokunaga,GOLD2018, Paris (France), July, 2018.
24. Selective adsorption of 1,3-dimethyltrisulfane (DMTS)
responsible for aged odor of Japanese sake with supported
gold nanoparticles, M. Tokunaga, H. Murayama, Y.
Yamamoto, M. Kimura, T. Shinozaki, E. Yamamoto, T.
Ishida, A. Isogai, T. Fujii, S. Iizuka, M. Okumura,GOLD2018, Paris (France), July, 2018.
25. Efficient Removal of Trimethylamine to Nitrogen on
Supported Gold Catalysts at Low Temperature, B. An,
M. Lin, T. Ishida, T. Shishido, M. Haruta, T. Murayama,
The 3rd International Symposium on Hydrogen Energy‒
based Society, Tokyo (Japan), August, 2018.
26. Selective Catalytic Oxidation of Low Concentration NH3
by Niobium Oxide Supported Gold Catalyst, M. Lin, B.
An, T. Ishida, T. Shishido, M. Haruta, T. Murayama, The
3rd International Symposium on Hydrogen Energy‒based
Society, Tokyo (Japan), August, 2018.
27. Metal Oxide Supported Gold Nanoparticles for Transfer
Vinylation of Carboxylic Acids, R. Sodenaga, T. Ishida,
T. Honma, M. Haruta, The 9th International Forum on
Chemistry of Functional Organic Chemicals (IFOC-9),
Tokyo (Japan), November, 2018.
28. Oxide Supported Pd, Au and Pt nanoparticles for Soft
Lewis Acid Catalysts, T. Ishida, H. Murayama, E.
Yamamoto, T. Honma, M. Tokunaga, Intenational
Symposium on Catalysis and Fine Chemicals (C&FC)
2018, Bangkok (Thailand), December, 2018.
29. Improvement of enzymatic catalysis in organic solvents via
immobilization on biochar, H. Noritomi, J. Nishigami, N.

■Patents

See the annual report in Japanese (1 articles)■Awards
1. Keito SANO, Annual Meeting on Photochemistry 2018,
The Best Presentation Award for Students, September,2018.
2. Kyosuke ARAKAWA, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Poster Award, September, 2018.
3. Shinsuke, TAKAGI, The Clay Science Society of Japan,
Award 2018, September, 2018.
4. Keito SANO, The 8th CSJ Chemistry, Festa Best Poster
Awards (CSJ Chemistry Festa Awards), October, 2018.
5. Keito SANO, The10th Asian Photochemistry Conference,
The APA-Hamamatsu Photonics Sponsored Scholor,
December, 2018.

24

Uchiyama Laboratory■Members

each droplet has one or zero target DNA. Droplets ejected wereintroduced into capillary (id200- 500 μm), then were flown to
the downstream. The capillary was wrapped 30~40 times aroundthree heating blocks, each of which has same temperatue as PCRamplification. As a result, PCR amplification was carried out
during the flow through the capillary. Finally, determination wasmade by counting fluorescent droplets. We have realized new
on-line digitial PCR system for the first time.

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

1-2 Droplet enhanced fluorescence, principle and application
We found the the droplet with later refractive index thansurrounding media showed drastic increase of fluorescenceintensity and we named the phenomena DEF (droplet enhanced
fluorescence). The phenomena is based upon the multiple
reflection of incident light at the interface between the droplet
and surrounding media.
We have confirm the phenomenon by using droplets
ejectedfrom inkjet, then applied the method to ultra sensitive
determination of single strand DNA, ELISA. The method
showed 5~10 times increase in the sensitivity than conventional
methods.

Sueo KAGAWA
Tech. Assistantroom: 9-290 TEL: +81-42-677-1111 Ext.4872
e-mail: kagawa @tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistantroom: 9-291 TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp

Doctor’s course -2
Master’s course -11
Bachelor 4 -10
Dissertion Ph.D. supporting by JSPS-2(Tsinghua University)
1-3 Application to Capillary electrophoresis
We have developed a new quantitative sample introduction
method for capillary electrophoresis. Inkjet was used for it. And
new method of sample deribatization was developed by using
inkjet. Sample solution and reagent solution was alternately
introduced into the capillary, then these zones were overlapped
for reaction. Finally, delivatized sample was quantitatively
detected.

■Outlines of the Research
1. Development of Small Droplets and Applications
Katsumi Uchiyama, Hulie Zeng
Monodispersive micro liquid droplets not only act as ultra small
reaction place with unique characteristics but also enhance
fluorescence intensity of surrounding media. We utilized inkjet,
which is widely used for the inkjet printer, micro dispensing tool
for analytical chemistry and many other fields, as a generation
tool for monodispersive liquid dorplets. In this study we havedeveloped on-line digital PCR system, new sample introduction
method for capillary electrophoresis, dispensing system for ultra
small amount of liquid for enzyme linked immune sorbent assay,
generation of mono-dispersive polymer particles for drugdelivery system.
1-1 Development of on-line digital PCR system
At first, a certain number of mono-dispersive droplets with
PCR mixture and target DNA were ejected into oil phase.
Concentration of the target DNA was adjusted by diluting until

Appeared on cover page of Analyst25

2. Development of nano/micro chemical pen and its
applications
Katsumi Uchiyama, Hulie Zeng
We have developed micro chemical pen, which enabled
position selective micro chemical fabrication on the suface ofmaterial. The chemical pen enabled the fabrication of silver
nano-wires, metal oxide nano-wires and polymer nano wires.
The device will be used for the assembling tool for chemicalmachine, fabrication of chemical device and functionalizationof micro machine etcs in the future.

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

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

Appeared on rear cover page of Chem. Commun.

3. Single cell operation
Katsumi Uchiyama
One single tumor cell in large tissue was difficult to be detected
when whole tissue was analysed. However, the tumor would
spred to whole tissue in the end. If we can characterize cell insingle cell level, tumor cell will be easily detected and it leads tothe ultra fast diagnosis of tumor and precise study on themechanism of metastasis. In this study, we develop tools for thecharacterization of single cell, extraction of single cell fluid,
measurement of chemicals exposed from a cell by using theprinciple of chemical pen.
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 portable
fluorescence detection system, electrochemical detection systemand surface plasmon resonance sensor were developed using thecompact disk-type microfluidic device. Since these systems do
not need pumps and valves, these systems would be useful foron-site analysis, such as environmental monitoring, food safety
testing and point-of-care testing.

7. Development of Hydrogen Gas Sensor Based on Surface
Plasmon Resonance
Hizuru NAKAJIMA
Recently, power generation system using fuel cell and fuel cell
car are beginning to become popular among ordinary home. The
utilization of hydrogen gas may gradually increase in the future.
In order to use hydrogen gas safely, a high sensitive and selectivehydrogen gas sensor is required since hydrogen gas is easy todiffusive and leaky than other combustible gas. Semiconductor
type snd contact combustion type hydrogen gas sensors havebeen put into practical use. However, the sensors are large-sizedand heavy because of the need of explosion proof construction.
In addition, the sensors respond to other gases because of their
low selectivity. To solve these issues, a novel hydrogen gas
sensor based on surface plasmon resonance (SPR) was
developed using the sensor chip with thin film of hydrogenstorage alloy.

26

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.
13. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system wasconstructed for low level hydrogen measuremtns. Atmospherichydrogen concentration in suburban, urban, and remote sites
were observed.

8.

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

■Papers with Peer Review

1.

2.

3.

4.

5.
9. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
uburban site (Minamiosawa, Tookrozawa, Kyoto). Emission
sources, contribution to ozone formation of each VOC were
estimated.

6.

10. Atmospheric trace species measurements at remote sites
Shungo KATO
Atmospheric carbon monoxide, ozone, and various volatileorganic compounds were continuously observed at remotesites: cape Hedo in Okinawa, Suzu in Ishikawa.

7.

11. Measurements of atmospheric pollutants at mountainsites
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 at the top and at the foot of Mt. Fuji.

8.

12. Atmospheric trace gas measurements using small gas
sensor27

Weifei Zhang, Nan Li, Daisuke Koga, Yong Zhang, Hulie
Zeng, Hizuru Nakajima, Jin-Ming Lin, Katsumi Uchiyama
Inkjet Printing Based Droplet Generation for Integrated
Online Digital Polymerase Chain Reaction
Anal. Chem. 2018, 90 (8), pp 5329–5334
Sifeng Mao, Yong Zhang, Qiang Zhang, Jin-Ming Lin,
Katsumi Uchiyama
Local surface modification at precise position using achemical pen
Talanta187(2018), pp246-251
Yong Zhang, Hulie Zeng, Sifeng Mao, Shun Kondo,
Hizuru Nakajima, Shungo Kato, Carolyn L. Ren, Katsumi
Uchiyama
Reversibly Switching Molecular Spectra
Appl. Mater. Interfaces 2018, 10 (27), pp 23247–23253
Sifeng Mao, Qiang Zhang, Haifang Li, Qiushi Huang,
Mashooq Khan, Katsumi Uchiyama, Jin-Ming Lin
Measurement of Cell-Matrix Adhesion at Single-Cell
Resolution Reveals the Functions of Biomaterials for
Adherent Cell Culture
Anal. Chem. 2018, 90 (15) , pp 9637–9643
Meng Sun , Dan Xu, Sicen Wang , Katsumi Uchiyama
Inkjet-Based Dispersive Liquid–Liquid Microextraction
Method Coupled with UHPLC–MS/MS for theDetermination of Aflatoxins in Wheat
Analytical Chemistry, 2019, 91 (4), pp 3027–3034
Xiangnan Dou, Qiang Zhang, Syed Niaz Ali Shah,
Mashooq Khan, Katsumi Uchiyama, Jin-Ming Lin
MoS2-Quantum Dots Triggered Reactive Oxygen Species
Generation and Depletion: Responsible for Enhanced
Chemiluminescence
Chem. Sci. 2019,10, pp.497-500
Sifeng Mao, Qiang Zhang, Wu Liu, Qiushi Huang,
Mashooq Khan, Wanling Zhang, Caihou Lin, Katsumi
Uchiyama, Jin-Ming Lin
Chemical operations on a living single cell by open
microfluidics for wound repair studies and organelletransport analysis
Chemical Science, 2019,10, pp.2081-2087
Sathiyamurthi Ramasamy, Yoshihide Nagai, Nobuhiro
Takeuchi, Shohei Yamasaki, Koki Shoji, Akira Ida,
Charlotte Jones, Hiroshi Tsurumaru, Yuhi Suzuki, Ayako
Yoshino, Kojiro Shimada , Yoshihiro Nakashima, Shungo
Kato , Shiro Hatakeyama, Kazuhide Matsuda, Yoshizumi
Kajii
Comprehensive measurements of atmospheric OH
reactivity and trace species within a suburban forest near
Tokyo during AQUAS-TAMA campaign
Atmospheric Environment, 184, 166-176, 2018.

4th Asian Symposium for Analytical Sciences (ASAS),
Tohoku University Kwauchi-kita Campus, Sendai , Japan
2. Shungo KATOLong term measurements of CO, O3, and VOCs at Moshiri,
Hokkaido in northern Japan
14th iCACGP Quadrennial Symposium and 15th IGAC
Science Conference, Sunport Takamatsu Convention Center,
Takamatsu, Kagawa
3. Hulie Zeng, Tsuguhiro Kaneko, Hizuru Nakajima, Katsumi
Uchiyama
Droplet Sensitized Fluoresence Emission Detection for
ELISA at Microwell plate2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China, IL7
4. Haifeng Lin, Hulie Zeng, Ning Xu, Hizuru Nakajima,
Shungo Kato, Katsumi Uchiyama
Development of Chemical Nano-sensor Fabricated by Nano
/ Micro-chemical Pen
2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China, IL5
5. Yumi Tanaka, Katsumi Uchiyama
Development of thermally responsive micro valve for μTAS
and microregion-selective surface modification2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China, P46
6. Moeko Osashima, Kazuhiro Morioka, Akihide Hemmi, Hulie
Zeng, Shungo Kato, Katsumi Uchiyama, Hizuru Nakajima
Development of portable ELISA system using pipette tips
2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China, P47

9.

Kasumi Mitsuishi, Masakazu Iwasaki, Masaki Takeuchi,
Hiroshi Okochi, Shungo Kato, Shin-Ichi Ohira, Kei Toda
Diurnal variations and partitioning of atmospheric glyoxal
and methylglyoxal between gas and particles at the groundlevel and in the free troposphere
ACS Earth and Space Chemistry, 2, 915-924, 2018
10. Yasuhiro Sadanaga, Ayana Ishiyama, Ryo Takaji, Atsushi
Matsuki, Shungo Kato, Keiichi Sato, Kazuo Osada, Hiroshi
Bandow
Behavior of total peroxy and total organic nitrateconcentrations at Suzu on the Noto Peninsula, Japan:
Long-range transport and local photochemical production
Atmospheric Environment, 196, 20-26, 2019

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

1. Katsumi Uchiyama
Inkjet Printing Based Droplet Generation for Integrated
Online Digital Polymerase Chain Reaction
The First Symposium for Cell Analysis on
Micro/Nanofluidics, Xijiao Hotel, Beijing, China
2. Katsumi Uchiyama
Position selective fabrication of nano-wire and its
application to sensing device
The 9th Shanghai International Symposium on Analytical
Chemistry, Shanghai New International Expo Center,
Shanghai, China
3. Katsumi Uchiyama
Direct and Regioselective Fabrication of Nano-wires by
Chemical Pen
The 9th International Forum on Chemistry of Functional
Organic Chemicals (IFOC-9), Ichijo Hall, Yayoi
Auditorium, The University of Tokyo, L-12
4. Katsumi Uchiyama
Fabrication of nano-wire by nano-chemical Pen and possible
application to sensing device2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China, PL2
5. Katsumi Uchiyama
Direct and Regioselective Fabrication of Nano-wires by
Chemical Pen for Sensing Device
University of Leicester - Tokyo Metropolitan University
Joint Symposium, University of Leicester, UK
6. Shungo Kato, Hiroshi Okochi, Kazuhiko Miura,
Hitoshi Kamogawa, Yukiko Dokiya
CO, O3, and SO2 observation at the summit of Mt.
Fuji during summer
International Conference on Air Pollution andMonitoring 2019, Kottagaya India＊Domestic
See the annual report in Japanese (20articles)■Awards

1. Moeko Osashima（Master’s degree 2 years）
Poster Award“Development of portable ELISA system using pipette tips”
2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China
2. Yumi Tanaka（Master’s degree 2 years）
Poster Award“Development of thermally responsive micro valve for
μTAS and microregion-selective surface modification”
2018 China-Japan-Korea Symposium on Analytical
Chemistry (CJK 2018), Baixiang Yuanshan Hotel,
Zhangzhou, Fujian, China
3. Takuya Nojo (1st year master's student)
Young Scientist Poster Award“Development of compact disk type fluorescence detection
system capable of real-time measurement”
67th Annual Meeting of the Japan Society for Analytical
Chemistry, Tohoku University
4. Moeko Osashima (2nd year master's student)
Young Scientist Presentation Award“Development of portable ELISA system using pipette tips”■Academic Meeting＊International
1. Weifei Zhang, Daisuke Koga, Jin-Ming Lin, ○Katsumi
Uchiyama
Inkjet Printing Based Droplet Generation for Integrated
Online Digital Polymerase Chain Reaction

28

35th Annual Meeting of the Association of Organic MicroAnalysts, Tokyo Metropolitan University
5. Rio Sakamoto (2nd year master's student)
Young Scientist Poster Award“Development of flow injection analysis system for pH
measurement of seawater”
35th Annual Meeting of the Association of Organic MicroAnalysts, Tokyo Metropolitan University
6. Yumi Tanaka (2nd year master's student)
Young Scientist Poster Award“Regioselective immobilization of temperature-responsive
polymer”
35th Annual Meeting of the Association of Organic MicroAnalysts, Tokyo Metropolitan University
7. Masato Kawaguchi (1st year master's student)
Young Scientist Poster Award“Fabrication of nano sensing device using a micro chemicalpen”
35th Annual Meeting of the Association of Organic MicroAnalysts, Tokyo Metropolitan University
8. Ken Miyashita, Ryo Tanaka, George Hasegawa, Kazuki
Nakanishi, Kazuhiro Morioka, Hulie Zeng, Shungo Kato,
Katsumi Uchiyama, Kazunori Saitoh, Masami Shibukawa,
Hizuru Nakajima“On-line Redox Derivatization Liquid Chromatography
Using a Carbon Monolithic Column”
Young Scientist Paper Award of the Japan Society for
Analytical Chemistry29

Reports from Research Groups
Shishido Laboratory■Members

Au alloy catalysts with a low Pd/Au ratio were highly effective
for the hydrosilylation at an ambient temperature, and thecorresponding β-alkenylsilanes were obtained as a main productin good to high yields.

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

chemistry,

Doctor’s course -3
Master’s course -18
Bachelor 4 -7

■Outlines of the Research

3. Green transformation of organic molecules by transitionmetal catalysts

1. Quantitative Evaluation of the Hydrophobicity Surrounding
Brønsted Acid Sites on Their Catalytic Activity for theHydrolysis of Organic Molecules

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
amides to aldimines to give isoindolinone derivatives. Under
optimized conditions, a series of isoindolinones were obtainedin good to high yields. Detailed investigation on reaction
mechanism revelaed that the formation of ruthenacycle
intermediate was involved during the Ru-catalyzed reaction.

Sulfo-functionalized siloxane gels with a variety of surfacehydrophobicities were fabricated to elucidate the effect of theenvironment surrounding the Brønsted acid site on their catalytic
activity for the hydrolysis of organic molecules. A sulfo group ina highly hydrophobic environment exhibited excellent catalytic
turnover frequency for the hydrolysis of acetate esters with along alkyl chain, whereas not only conventional solid acidcatalysts but also liquid acids showed quite low catalytic activity.
Detailed kinetic studies corroborated that the adsorption ofoleophilic esters at the Brønsted acid site was facilitated by thesurrounding hydrophobic environment, thus significantly
promoting hydrolysis under aqueous conditions.

■Papers with Peer Review
1.

2.

3.

4.

2. Hydrosilylation of allenes over supported alloy nanoparticle
catalysts
An efficient synthetic route to alkenylsilanes involving thehydrosilylation of allenes with supported Pd–Au alloy catalysts
has been developed. The incorporation of Pd atoms into Au
nanoparticles not only remarkably enhanced the catalytic
activity but also drastically changed the product selectivity. Pd–

5.

30

Supported Gold-Palladium Alloy Catalysts for Highly
Efficient Hydrogen Storage System based on Ammonium
Bicarbonate/Formate Redox Equilibrium K. Nakajima, M.
Tominaga, M. Waseda, H. Miura, T. Shishido, ACS
Sustainable Chem. Eng. 2019, in press.
Catalysis of Cu Cluster for NO Reduction by CO:
Theoretical Insight into Reaction Mechanism andExperimental Evidence N. Takagi, K. Ishimura, H. Miura,
T. Shishido, R. Fukuda, M. Ehara, S. Sakaki, ACS Omega
2019, 4, 2596–2609.
Ruthenium-Catalyzed Synthesis of Isoindolinones via
Amide-Directed Addition of Aromatic C-H Bonds to
Aldimines H. Miura, Y. Kimura, S. Terajima, T. Shishido,
Eur. J. Org. Chem. 2019, DOI 10.1002/ejoc.201801755.
Quantitative Evaluation of the Effect of theHydrophobicity of the Environment Surrounding Brønsted
Acid Sites on Their Catalytic Activity for the Hydrolysisof Organic Molecules H. Miura, S. Kameyama, D. Komori,T. Shishido, J. Am. Chem. Soc. 2019, 141, 1636–1645.
The importance of direct reduction in synthesizing highly
active Pt-Sn/SBA-15 for n-butane dehydrogenation L.
Deng, H. Miura, T. Ohkubo, T. Shishido, Z. Wang, S.
Hosokawa, K. Teramura, T. Tanaka, Catal. Sci. Technol.
2019, 9, 947–956.

Reports from Research Groups
6.
7.

8.

9.
10.

11.

12.

13.

Carboxylate-Directed Addition of Aromatic C-H Bond to
Aromatic Aldehydes under Ruthenium Catalysis H. Miura,
S. Terajima, T. Shishido, ACS Catal. 2018, 8, 6246–6254.
Concerted Catalysis by Adjacent Palladium and Gold in
Alloy Nanoparticles for the Versatile and Practical[2+2+2] Cycloaddition of Alkynes H. Miura, Y. Tanaka,
K. Nakahara, Y. Hachiya, K. Endo, T. Shishido, Angew.
Chem. Int. Ed. 2018, 57, 6136–6140.
Generation of Active Ruthenium Catalysts for
Hydroarylation of CC Multiple Bonds from Isolated
Ru(IV)-oxo Species Supported on CeO2 H. Miura, M.
Nagao, S. Hosokawa, T. Shishido, M. Inoue, K. Wada,
Bull. Chem. Soc. Jpn. 2018, 91, 1397–1401.
Selective catalytic reduction of NO with CO and C3H6 over
Rh/NbOPO4 S. Imai, H. Miura, T. Shishido, Catal. Today
2018, DOI 10.1016/j.cattod.2018.07.027.
Hydrosilylation of Allenes over Palladium–Gold Alloy
Catalysts: Enhancing Activity and Switching Selectivity
by the Incorporation of Palladium into Gold Nanoparticles
H. Miura, S. Sasaki, R. Ogawa, T. Shishido, Eur. J. Org.
Chem. 2018, 2018, 1858–1862.
Selective Hydrogenolysis of Tetrahydrofurfuryl Alcohol
over Pt/WO3/ZrO2 Catalysts: Effect of WO3 loading
amount on activity S. Feng, A. Nagao, T. Aihara, H. Miura,
T. Shishido, Catal. Today 2018, 303, 207–212.
Effect of tin on dispersion of platinum on Pt-Sn/SiO2
catalysts for dehydrogenation of lower alkanes L. Deng, H.
Miura, T. Shishido, Z. Wang, S. Hosokawa, K. Teramura,T. Tanaka, J. Catal. 2018, 365, 277–291.
Dynamic Behavior of Rh Species of Rh/Al2O3 Model
Catalyst During Three-Way Catalytic Reaction – An
Operando XAS Study H. Asakura, S. Hosokawa, T. Ina, K.
Kato, K. Nitta, K. Uera, T. Uruga, H. Miura, T. Shishido,
J. Ohyama, et al., J. Am. Chem. Soc. 2018, 140, 176–184.

6.

7.

8.

■Academic Meeting＊International
1.
Supported Gold-Palladium Alloy Catalysts for Highly
Efficient Hydrogen Storage System Based on Ammonium
Bicarbonate/FormateRedox Equilibrium
K. Nakajima, H. Miura, T. Shishido, Gold2018 (Université
Pierre et Marie Curie (UPMC), Paris) (June 14-18), Paris,
France2.
CeO2-supproted Ru catalysts effective for selective
syntheses of fine chemicals
H. Miura, S. Hosokawa, K. Wada, T. Shishido, 3rd
Fundamentals and Application of Cerium Dioxide in
Catalysis (Barcelona) June 25-27, 2018 Barcerona, Spain
3.
Hydrosilylation of unsaturated organic molecules oversupported PdAu catalysts
H. Miura, K. Endo, R. Ogawa, S. Sasaki, T. Shishido,International Symposium on Relations between
Homogeneous and Heterogeneous Catalysis (ISHHC18,
Sydney) July 22-25, 2018 Sydney, Australia
4.
Role of perimeter interfaces between WO3 monolayer
domain and Al2O3 in hydrogenolysis of glycerol by
Pt/WO3/Al2O3 catalysts
T Aihara, H Miura, T Shishido, International Symposium
on Relations between Homogeneous and Heterogeneous
Catalysis 2018 (ISHHC18) July 22-25, 2018, Sydney,
Australia
5.
Steam reforming of dimethyl ether over Cu/ZnO/Al2O3
coupled with H-ZSM-5 hybrid catalysts: Effect of
SiO2/Al2O3 ratio on the activity
E. Kawai, H. Miura, T. Shishido, International Symposium
on Relations between Homogeneous and Heterogeneous
Catalysis (ISHHC18, Sydney) July 22-25, 2018 Sydney,
Australia
6.
[2+2+2] cycloaddition of alkynes over supported Pd-Au
alloy catalysts
Y. Tanaka, K. Nakahara, K. Endo, H. Miura, T. Shishido,International Symposium on Relations between
Homogeneous and Heterogeneous Catalysis (ISHHC18,
Sydney) July 22-25, 2018, Sydney, Australia
7.
[2+2+2] cycloaddition of alkynes over supported Pd–Au
alloy catalysts
H. Miura, Y. Tanaka, K. Nakahara, K. Endo, T. Shishido,
The Eighth Tokyo Conference on Advanced Catalytic
Science and Technology (TOCAT8, Yokohama) August 510, 2018, Yokohama, Japan■Invited Lectures
1.

2.

3.

4.

5.

39th summer seminar of junior society of CatSJ in
Hamamatsu “Specific catalytic function of supported alloy
catalysts” (invited lecture)
Tetsuya Shishido, 2018/8/3, Shizuoka.
86th symposium on Laboratory for Materials andStructures “Specific catalytic function of supported alloy
catalysts with controlled nano structure”
Tetsuya Shishido, 2019/1/24, Tokyo Institute oftechnology.
Surface design chemistry seminar at Kinki University“Efficient heterogeneous catalytic reaction by concerted
catalysis of different atoms on alloy nanoparticles”
Hiroki Miura, 2019/3/7, Kinki University.

Fine chemicals synthesis catalysts seminar 2018,“Efficient molecular transformation by Ru catalysts”(invited lecture)
Hiroki Miura 2018/5/26 TMU Akihabara satellite campus.
1st junior seminar of Hybrid catalysts in innovative area,“Efficient heterogeneous catalytic reaction by concerted
catalysis of different atoms on alloy nanoparticles”
2018/1/30 Nagoya University.
Hiroki Miura 2018/5/27 Yunoyado Komorebi, Ogoto.
Design of High-Performance Alloy catalysts: Enhancing
Activity and Switching Selectivity by the Incorporation ofPalladium into Gold Nanoparticles
T. Shishido, H. Miura, The 2nd Japanese-Spanish
Symposium on Organic Synthesis (May 28th (Mon)-29th(Tue)), Kyoto University, Kyoto, Japan
Supported Gold-Palladium Alloy Catalysts for Highly
Efficient Hydrogen Storage System Based on Ammonium
Bicarbonate/FormateRedox Equilibrium
Tetsuya SHISHIDO, Hiroki MIURA, Kengo NAKAJIMA,
The 2018 International Symposium on Advancement andProspect of Catalysis Science & Technology (25-27th July
2018 at the University of Sydney), Sydney, Australia
Design of High-Performance Alloy Catalysts: Enhancing
Activity and Switching Selectivity by the Incorporation ofPalladium into Gold Nanoparticles
Testuya SHISHIDO, Hiroki MIURA, International
Symposium on Catalysis and Fine Chemicals 2018 (1014th December 2018 at Chulalongkorn University),
Bangkok, Thailand

31

Reports from Research Groups
8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

Role of perimeter interfaces between WO3 monolayer
domain and Al2O3 in hydrogenolysis of glycerol by
Pt/WO3/Al2O3 catalysts
T Aihara, H Miura, T Shishido, The Eighth Tokyo
Conference on Advanced Catalytic Science andTechnology (TOCAT8, Yokohama) August 5-10, 2018
Yokohama, Japan
Preparation of Brønsted acid gel catalysts with highlyhydrophobic surface and their application to acidcatalyzed reactions
S. Kameyama, H. Miura, T. Shishido, The 8th Tokyo
Conference on Advanced Catalytic Science andTechnology (TOCAT8) August 5-10, 2018, Yokohama,Japan
Methanolysis of ammonia borane over supported AuPd
alloy catalyst
M. Tominaga, K. Nakajima, H. Miura, T. Shishido, The
Eighth Tokyo Conference on Advanced Catalytic Scienceand Technology (TOCAT8, Yokohama) August 5-10, 2018,
Yokohama, Japan
Selective conversion of glycerol to acrolein on W-basedsolid acid catalysts
K. Asazuma, H. Miura, T. Shishido, The 8th Tokyo
Conference on Advanced Catalytic Science andTechnology (TOCAT8, Tokyo) August 5-10, 2018, Tokyo,
Japan
Hydrosilylation of Allenes over Palladium-Gold Alloy
Catalyst
S. Sasaki, H. Miura, T. Shishido, The 8th Tokyo
Conference on Advanced Catalytic Science andTechnology (TOCAT8, Tokyo) August 5-10, 2018, Tokyo,
Japan
Methanolysis of ammonia borane over supported AuPd
alloy catalyst
M. Tominaga, K. Nakajima, H. Miura, T. Shishido, The
Third International Symposium on Hydrogen Energybased Society August 22-23, 2018, Tokyo, Japan
Interconversion between bicarbonate and formate oversupported Pd alloy catalyst
M. Waseda, K. Nakajima, H. Miura, T. Shishido, The 3rdInternational Symposium on Hydrogen Energy-based
Society August 23, 2018 Tokyo,Japan
Study on the reaction mechanism of hydrogenolysis on
Pt/WO3/Al2O3 catalysts
T Aihara, H Miura, T Shishido,
48th annual meeting of Japan Petrolium Institute, October
17-18, 2018, Funabori, Japane
Synthesis of Benzo-Fused Heterocycles via CarboxylateDirected C-H Bond Functionalization under Ru Catalysis
H. Miura, S. Terajima, K. Tsutsui, T. Shishido, The
International Symposium on Catalysis and Fine Chemicals
2013 (C&FC2018) December 10-14, 2018, Bangkok,
ThailandCross-cycloaddition of diynes with allenes by supported
PdAu alloy catalysts
Y. Hachiya, H Miura, T. Shishido, The International
Symposium on Catalysis and Fine Chemicals 2018 (C&FC
2018, Bangkok) December 10-14, 2018, Bangkok
Hydrosilylation of Allenes over Palladium-Gold Alloy
Catalyst
S. Sasaki, H Miura, T. Shishido, The International

19.

20.

21.
22.

Symposium on Catalysis and Fine Chemicals 2018 (C&FC
2018, Bangkok) December 10-14, 2018, Bangkok
Ru-catalyzed [3+2] cycloaddition of aromatic amides withiminesY. Kimura, H Miura, T. Shishido, The International
Symposium on Catalysis and Fine Chemicals 2018 (C&FC
2018, Bangkok) December 10-14, 2018, Bangkok
Hydrolysis of organic molecules over Brønsted acid gel
catalyst with hydrophobic surface
S. Kameyama, H. Miura, T. Shishido, The International
Symposium on Catalysis and Fine Chemicals 2013
(C&FC2018) December 10-14, 2018, Bangkok, Thailand
Silylation of aryl chlorides by supported Pd-Au alloy
catalysts
Y. Masaki, H. Miura, T. Shishido, The International
Symposium on Catalysis and Fine Chemicals 2018
(C&FC2018) December 10-14, 2018, Bangkok, Thailand＊Domestic
See the annual report in Japanese (36 articles)■Awards
1.

2.

3.

4.

5.

6.

7.

8.

9.

32

Best Presentation Award "Effect of surfacehydrophobicity of sulfo-functionalized siloxane gel
catalysts on their activities toward ester hydrolysis" Hiroki
Miura 121th CatSJ Meeting (22-23 March 2018, The
University of Tokyo).
Poster Award "Alloying effect of Pd and Au on selectivehydrosilylation of allenes" Suguru Sasaki 121th CatSJ
Meeting (22-23 March 2018, The University of Tokyo).
Poster Award "Hydrolytic desilylation of silyl ethers by
Brønsted acid gel catalysts with highly hydrophobic
surface" Syutaro Kameyama 121th CatSJ Meeting (22-23
March 2018, The University of Tokyo).
Poster Award 1st Prize "Role of perimeter interfaces
between WO3 monolayer domain and Al2O3 inhydrogenolysis of glycerol by Pt/WO3/Al2O3 catalysts"
Takeshi Aihara 18th International Symposium on
Relations between Homogeneous and Heterogeneous
Catalysis (ISHHC18) (22-25 July 2018, ICC Sydney,
Australia).
Poster Award ‘‘Effect of Al2O3-TiO2 support on theacidity of supported WO3 species” Mizuki Saito 39thsummer seminar of junior society of CatSJ in Hamamatsu,
August 3, 2018, Shizuoka.
Poster Award ‘‘Silylation of aryl halides by supported
PdAu alloy catalytsts” Yosuke Masaki 39th summer
seminar of junior society of CatSJ in Hamamatsu, August
3, 2018, Shizuoka.
Best Poster Award “Partial oxidation of methane bysupported Pt catalysts” Atsushi Nishida 16th catalysts
chemistry workshop at Sapporo, September 25, 2018,
Hokkaido
Excellent Poster Award ‘‘Mechanistic investigation onhydrogenolysis over Pt/WO3/Al2O3 catalysts” Takeshi
Aihara 8th CSJ chemistry festa, Funabori. 23-25 October
2018, Tower Hall Funabori
Excellent Poster Award ‘‘Silylation of aryl halides by
supported PdAu alloy catalysts” Yosuke Masaki 8th CSJ
chemistry festa, Funabori. 23-25 October 2018, Tower
Hall FunaboriReports from Research Groups
10.

Excellent Poster Award ‘‘CO2 hydrogenation overphosphate supported Rh catalysts” Junpei Suzuki 8th CSJ
chemistry festa, Funabori. 23-25 October 2018, Tower
Hall Funabori

33

Reports from Research Groups
Shudo Laboratory■Members

electrolyte fuel cell with expanded metal flow fields for evensupply of reactants, The 27th Congress of Japan Institute ofEnergy, August 2018.
2. Presentation Award, Akihiro Ogawa, Effects of addition ofhydrogen and methane on ignition timing in HCCI combustionof diethyl ether, The 38th Congress of Hydrogen Energy System
Society, November 2018.

Toshio Shudo
Professor /Dr. Eng.
Energy Engineering,room: 9-455 TEL: +81-42-677-2715
e-mail: shudot@tmu.ac.jp
Doctor’s course -1
Master’s course -6
Bachelor 4 -1

■Outlines of the Research

1. Performance improvement in polymer electrolyte fuel cell,Toshio Shudo
Because polymer electrolyte fuel cell has higher energy
efficiency and lower power density compared to internal
combustion engine, it is important to improve the performanceof polymer electrolyte fuel cell. This research investigates theeffect of porous metal flow field for even supply of reactants tothe whole area of electrodes.
2. Performance improvement in direct methanol fuel cell.
Toshio Shudo
Direct methanol fuel cell system has higher energy density andlower power density compared to polymer electrolyte fuel cellsystem. This research investigates the effect of porous metal
flow field for enhancing the reactant supply and productremoval at the electrodes.
3. Ignition control in homogeneous charge compression
ignition combustion.
Toshio Shudo
Internal combustion engine has higher power density and lower
energy efficiency compared to fuel cell system. This research
investigates a new combustion system by the compression
ignition of homogeneous fuel-air mixture for achieving higher
thermal efficiency in internal combustion engines.

■Papers with Peer Review

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

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

1. Toshio Shudo, Waste heat recovery in engine systems,
Forum for Engine Waste Heat Recovery, 2018 Annual
Congress of Japan Society of Mechanical Engineers,
September 2018.

■Academic Meeting＊Domestic
See the annual report in Japanese (25 articles)■Patents

1. Toshio Shudo, Ayumu Shimura, Eiichi Mine, Kengo
Kubodera, “Reactant supply flow field”, Japanese Patent
No.6327601, April 2018.

■Awards
1. Poster Award, Shun Fujita, Performance of a polymer
34

Applied Chemistry Colloquium

376th

2018/5/9
Jayaraman Sivaguru (Bowling Green State University, USA)
“Effects of manufactured Nanoparticles on inflammation”

377th

2018/5/25
Saulius Juodkazis (Swinburne University of Technology, Australia)“Nanoscale light control for sensor applications and photonics”

378th

2018/9/10
Jin-ming Lin (Tsinghua University, China)“Development of chip-mass spectrometry for Single Cell analysis”

379th

2018/9/18
Jean-Pierre Pereira-Ramos (Institut de Chimie et des Materiaux ParisEst, Centre National de la Recherche Scientifique, France)“Development of chip-mass spectrometry for Single Cell analysis”

Rita Baddour-Hadjean (Institut de Chimie et des Materiaux Paris-Est,
Centre National de la Recherche Scientifique,“The γ'-V2O5 polymorph as an Attractive 2D cathodic material for lithiumand sodium-ion batteries”
380th

2018/9/21
Bunsho Ohtani (Hokkaido University, Institute for Catalysis, Japan)“Fingerprint of powder”

381th

2018/10/20
Elisabeth Lojou (National Center for Scientific Research, France)“Enzyme electrical connection for enzymatic fuel cells”

382nd

2018/11/30
Saburo Hosokawa (ESICB, Kyoto University, Japan)“Oxygen Storage Property and Catalytic Performance of Sr-Fe Mixed
Oxide”

35

Annual Report 2018

Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry for Environmental Sciences
April 1, 2019