Faculty of Environmental Sciences

Department of Applied Chemistry

Annual Report 2016

IndexReports from Research Groups
Kawakami Laboratory

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1

Masuda Laboratory

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８

Setaka Laboratory

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１０

Haruta Laboratory

▪▪▪▪▪

１２

Kanamura Laboratory

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１６

Takagi Laboratory

▪▪▪▪▪

２０

Yamaguchi Laboratory

▪▪▪▪▪

２３

Uchiyama Laboratory

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２６

Kubo Laboratory

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３１

Shishido Laboratory

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３４

Reports from Research Groups
Kawakami Laboratory
membranes was analyzed by utilizing thespectroscopy and gas adsorption measurements.

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

129Xe-NMR

Biochemistry,

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 pearl-necklace shapes.

Manabu TANAKA
Assistant Professor / Dr. Eng.
Polymer Chemistry, Polymer Electrolytes, Nanofibers, Polymer
Membranes
Rm. 9-639, +81-42-677-1111 Ext. 4586
tanaka-manabu@tmu.ac.jp

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

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

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 tried to improve their performances via theacid/base layer-by-layer surface modification process of thenanofibers to increase the effective conductive pathways at theinterface of the nanofibers and the matrix polymer (Figure 2).
The novel nanofiber composite membrane showed ca. ten times
higher proton conductivity than the conventional composite
membranes under low humidity conditions, which are assumed
as future fuel cell operation conditions.

Fidelis SIMANJUNTAKSpecially-appointed Assistant Professor / Dr. Eng.
Catalyst Chemistry, Complex ChemistryRm. 9-649, +81-42-677-1111 Ext. 4973
fidelis@tmu.ac.jp
Doctor’s course -1
Master’s course -15
Bachelor 4 -9

■Outlines of the Research
1. Study of Functional Polymer Membrane
Hiroyoshi KAWAKAMI, Masafumi YAMATO,
Manabu TANAKA
Membrane-based gas separations have tremendous potential
as energy-efficient alternatives or removal material ofgreenhouse gasses, such as carbon dioxide (CO2). Recently, we
have reported that novel composite membranes composed of
the fluorinated polyimide or polymers of intrinsic
microporosity (PIM) and surface-modified silica nanoparticles
exhibit high gas permeability and selectivity.
In this year, we focused on new types of nanoparticles,
especially pearl-necklace shaped silica nanoparticles that haveoriginally inter-connected structures (Figure 1). By using thesenanoparticles, we have succeeded in fabricating novel polymer
composite membranes with excellent CO2 permeability ranked
at the highest level in the world. Furthermore, the mechanism
for the improvement of CO2 permeability in these composite

Figure 2. Schematic illustration of the polymer electrolytecomposite membranes based on the layer-by-layer
surface-modified nanofibers.
3. Study of Electrospun Nanofibers
Hiroyoshi KAWAKAMI, Manabu TANAKA

1

Reports from Research Groups
Recently, nano-scale fibers prepared through an electricallycharged jet of polymer solution/melt (electrospinning) havereceived a lot of attention. Nanofibers have several inherent
characteristics including high surface area, unique optical andphysicochemical properties originated from the nano-size, andalignment of polymer chains in the nanofibers. The diameter ofnanofiber is one of the most important factors to effect on such
unique characteristics. Ultrafine nanofibers with their diameters
less than 50 nm were also obtained.
In this year, we mainly focused on the fabrication of lithium
ion conductive polymer nanofibers and their composite
membranes for the secondary battery applications (Figure 3).
The novel lithium ion conductive nanofiber composite
membranes showed higher lithium ion conductivity than thecorresponding membranes without the nanofibers. It was
revealed that the improvement of the conductivity was derived
not only from the intrinsic high ion conductivity of thenanofibers themselves but also from the suppression of
crystallization of the matrix polymer at low temperatures. Then,lithium ion batteries using the nanofiber composite membranes
were prepared and evaluated to demonstrate successful
fabrication of all-solid-state secondary batteries.

5. Study of Epigenetics Engineering
Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA,
Riku KUBOTA
The development and maintenance of an organism isorchestrated by a set of chemical reactions that switch parts ofthe genome off and on at strategic times and locations.
Epigenetics is the study of these reactions and the factors that
influence them.
In this year, we have prepared epigenetics control carrier(EpC) carrier for novel therapy for diabete. The EpC carrierenhanced the number of insulin-secreting cells. Besides, wehave synthesized novel block polymer targeting histone for
artificial control of chromatin structure. The block polymer
provided the potential to re-activate the inactivated gene
expression which is involved in pathogenesis of severe
diseases.

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, Riku KUBOTA,
Fidelis SIMANJUNTAK

6. Study of Free Radical Control by SOD Mimic
Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA,
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 investigated catalytic activity ofsupramolecular bimetallic complex composed of metallo
porphyrin, metallo bis(bipyridine) and cucurbit [10] uril
(CB[10]). The complex can be prepared from variety of metallo
porphyrin and metallo bis(bipyridine). Furthermore, thesupramolecular bimetallic complex exhibited catalytic
reduction of carbon dioxide (CO2) and oxidation of water(H2O).

Superoxide dismutase (SOD) is well known to efficiently
dismute superoxide radicals as most important antioxidant.
We demonstrated that a water-soluble cationic Mn-prophyrinwith SOD activity exhibited anticancer activity as well as
antioxidative activity.
In this year, we have prepared novel biodegradable
nanoparticle having capacity of gene expression andantioxidation(MndMImP3P). The resulting nanoparticle
exhibited remarkable antioxidative activity. The mechanistic
study of the antioxidative activity suggested that Mn-porphyrin
was accumulated in mitochondria and suppressed reduction of
mitochondrial membrane potential.

Two-electron redox catalyst

Cucurbit[10]uril

Metallo-bisbipyridine

Metallo-porphyrins

M=Cu, Co, Fe etc

M=Mn, Fe, Co etc

Multifunctional＆ multifunctional redox catalyst
CO2 reduction

H2 production
2H+

CO, HCOOH,
CH3OH etc

H2

CO2

O2

Oxygen reduction

H2O

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

Figure 4. Multi-electron redox reactions by supramolecular
bimetallic complex.

2

Reports from Research Groups
7. Materials for Drug Delivery Systemclay hybrid gel was developed. POM observation revealed
anisotropy of the hybrid gel prepared in a magnetic field.
Anisotropy of the hybrid gel was increased by adding otherclay which was hardly aligned by a magnetic field, resulting in
improvement of mechanical properties of the gel.

Shoichiro ASAYAMA, Hiroyoshi KAWAKAMI
To improve human health and quality of life (QOL), we
have designed new biomaterials for drug delivery system(DDS). The resulting carriers for DDS such as nucleic acid
(pDNA, siRNA), protein, and Zn2+ are expected to satisfy
unmet medical needs (Figure 7).
In this year, by use of our cholesterol end-modifiedpoly(ethylene glycol) (Chol-PEG), we have established novel
noncovalent PEGylation methods for liquid-phase (DDS) andsolid-phase (Biocompatible materials) biomaterials. As DDS,
we have succeeded in the insulin PEGylation for in vivo
diabetes therapy.
As biocompatible materials, we havesucceeded in the surface PEGylation of poly(propylene).
Furthermore, we are focusing on the mono-ion complex and
Zn2+ delivery.

■Papers with Peer Review
1. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,“Structure-activity relationship between Zn2+-chelatedpoly(1-vinylimidazole) and gene transfection”, Journal of
Inorganic Biochemistry, in press.
2. Motoyuki Matsuho, Riku Kubota, Shoichiro Asayama,
Hiroyoshi Kawakami, “Lactoferrin-modified nanoparticle
loading potent antioxidant Mn-porphyrin exhibits enhanced
antioxidative activity in in vitro intranasal brain delivery
model”, Journal of Materials Chemiatry B, in press (DOI:
10.1039/C6TB02599D).
3. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami “Improvement in characteristics of a Nafion
membrane by proton conductive nanofibers for fuel cellapplications”, Journal of Membrane Science, 530, 65–72(2017).
4. Manabu Tanaka, Yasushi Takeda, Takeru Wakiya, Yuta
Wakamoto, Kaori Harigaya, Tatsunori Ito, Takashi Tarao,
Hiroyoshi Kawakami, “Acid-doped polymer nanofiber
framework: Three-dimensional proton conductive network forhigh-performance fuel cells”, Journal of Power Sources, 342,
125-134 (2017).
5. Tsukasa Watanabe, Manabu Tanaka, Hiroyoshi Kawakami,“Anion conductive polymer nanofiber composite membrane:
Effects of nanofibers on polymer electrolyte characteristics”,
Polymer International, 66, 382-387 (2017).
6. Tsukasa Watanabe, Manabu Tanaka, Hiroyoshi Kawakami,“Fabrication and electrolyte characterization of uniaxiallyaligned anion conductive polymer nanofibers”, Nanoscale, 8,19614-19619 (2016).
7. Yutaro Asaba, Shoichiro Asayama, Hiroyoshi Kawakami,“Design of epigenetics control carrier for simultaneoustransfection of histone acetyltransferase with histone
deacetylase inhibitor to continuous histone acetylation”,
Polymer Journal, 48, 561-564 (2016).
8. Gang Wang, Kota Yamazaki, Manabu Tanaka, Hiroyoshi
Kawakami, “Polymer electrolyte characteristics of Sulfonatedblock-graft polyimide membranes: Influence of block ratio”,
Journal of Photopolymer Science and Technology, 29, 259-263(2016).
9. Takashi Nishiyama, Takayuki Sumihara, Yasutaka Sasaki,
Eriko Sato, Masafumi Yamato and Hideo Horibe, Crystalline
structure control of poly (vinylidene fluoride) films by theantisolvent addition method, Polymer Journal, 48, 1035-1038(2016).
10. Yu Nabetani, Akino Uchikoshi, Souki Miyajima, Syed
Zahid Hassan, Vivek Ramakrishnan, Hiroshi Tachibana,
Masafumi Yamato, Haruo Inoue, Synthesis of double-wallnanoscrolls intercalated with polyfluorinated cationic surfactant
into layered niobate and their magnetic alignment, Physical
Chemistry Chemical Physics, 18, 12108-12114 (2016).

Figure 7. Delivery to in vivo unexplored space by themono-ion complex (MIC).
8. Processing of feeble magnetic materials under a magnetic
field
Masafumi YAMATO
Controls of higher-order structure of feeble magnetic
materials by using a magnetic field have been studied in orderto improve some properties and to reveal new functions of thematerials. The following was examined in this year. The mixed
(a)

(b)

Stress / kPa

60

0T
3T

40

■Reviews
1. Manabu Tanaka, “Development of ion conductive nanofibers
for polymer electrolyte fuel cells”, Polymer Journal, 48, 51-58(2016).

20
0
0

100
200
Strain / %300■Books
1. Shoichiro Asayama, See the annual report in Japanese (2017)
2. Masafumi Yamato, Improvement of thermal properties onheat radiation and high heat-resistant materials and technology
for heat measure, Technical information institute, p.p. 66-71

Figure 8. POM images of organic/inorganic hybrid gel
prepared in a magnetic field of 3 T (a) and stress-strain curvesof the gel (b).

3

Reports from Research Groups
38th Annual Meeting of The Membrane Society of Japan,
Japan, (Waseda University), P-20S (May 2016) (in Japanese)
3. Sakura Taneichi, Shoichiro Asayama, Yoichi Negishi,
Hiroyoshi Kawakami, “Breakthrough for PEG dilemma of the
pDNA/PEG mono-ion complex exhibiting further migration”,
The 16th Gene Delivery Symposium，P-30 (May, 2016) (inJapanese)
4. Shoichiro Asayama, Atsushi Nohara, Yoichi Negishi, andHiroyoshi Kawakami, Plasmid DNA Mono-Ion Complexes
with Poly(ethylene glycol) for In Vivo Diffusive Gene Delivery,
10th World Biomaterials Congress, Final Program, p. 158,
P.0015 (May, 2016)
5. Yutaro Asaba, Risa Shimazaki, Kazuhiko Nakabayashi,
Shoichiro Asayama, and Hiroyoshi Kawakami, Control of
Epigenetics Modification by Lipid-Coated Biodegradable
Nanoparticles for the Novel Cancer Therapy, 10th World
Biomaterials Congress, Final Program, p. 221, P.2148 (May,2016)
6. Masafumi Yamato, Ryusuke Takayama, Naofumi Naga,
Higher-Order structure of Polypropylene/Ni Composite and its
Electrical Property，65th Annual meeting of society of polymer
science of Japan，May 2016, Kobe, Japan (in Japanese)
7. Emika Narazaki, Motoyuki Matsuho Shoichiro Asayama,
Hiroyoshi Kawakami, See the annual report in Japanese (May2016)
8. Ryosuke Shinohara, Yutaro Asaba, Kazuhiko Nakabayashi,
Risa Shimazaki, Shoichiro Asayama and Hiroyoshi Kawakami,Control of cancer cell transformation by histone acetylation
using epigenetics control carrier, 65th SPSJ Annual Meeting,
Kobe, Japan (May, 2016) (in Japanese)
9. Sakura Taneichi, Shoichiro Asayama, Yoichi Negishi,
Hiroyoshi Kawakami, “Effect of an ester group on thebiodegradability of the pDNA/PEG mono-ion complex
exhibiting further migration”, Polymer Preprints, Japan Vol. 65,
No. 1 (May, 2016) (in Japanese)
10. Yuma Yokokawa, Misaki Ouchi, Kazuhiko Nakabayashi,
Shoichiro Asayama, Hiroyoshi Kawakami, Intranuclear
delivery and chromatin structure relaxation by various
polyanion-beta-cyclodextrin conjugates, Polymer Preprints,
Japan, Vol.65, (Kobe International Conference Center, Kobe
international exhibition Hall)2G17 (May, 2016) (in Japanese)
11. Kana Nagashima, Shoichiro Asayama, Hiroyoshi
Kawakami, Non-covalent Insulin PEGylation by using
cholesterol end modified PEG, The 32nd Annual Meeting of
the Japan Society of Drug Delivery System, Japan, P.139 (July,2016) (in Japanese)
12. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,
See the annual report in Japanese (July 2016)
13. Ryosuke Shinohara, Yutaro Asaba, Risa Shimazaki,
Shoichiro Asayama and Hiroyoshi Kawakami, Suppression ofcancer metastasis by histone acetylation using epigenetics
control carrier, The 32nd Annual Meeting of Japan Society ofDrug Delivery System, Shizuoka, Japan, Abstract, P.178 (June,2016) (in Japanese)
14. Eiko Ito, Noki Sakaguchi, Manabu Tanaka Hiroyoshi
Kawakami, Gas permeation property of mixed matrix
membranes containing surface-modified silica Nanoparticles,
The Annual Meeting of the Society of Fiber Science andTechnology, Japan, (Tower Hall Funabori), 3F05, Abstractp.(June 2016) (in Japanese)
15. Eiko Ito, Manabu Tanaka, Masafumi Yamato, Hiroyoshi
Kawakami, The syntheses of PIM type polymers and theirapplication to polymer gas separation membranes, The Annual
Meeting of the Society of Fiber Science and Technology,
Japan(Tower Hall Funabori), 2P211 (June 2016) (in Japanese)
16. Yuri Kameyama, Manabu Tanaka, and Hiroyoshi
Kawakami, Preparation and gas permeation evaluation ofpolyimide
compositemembranes
containing
novel
surface-modified nanoparticles, The Annual Meeting of theSociety of Fiber Science and Technology, Japan, (Tower Hall(2017) (in Japanese).
3. Masafumi Yamato, Orientation control of fillers by using
magnetic fields, Engineering materials, 64，p.p. 57-61 (2016)(in Japanese).
4. Masafumi Yamato, Kohki Takahashi, Kazuo Watanabe,Control of micro phase-separated structure by using magnetic
ionic liquid, 2015 Annual report of high field laboratory forsuperconducting materials in institute for materials research at
Tohoku university，p.p. 156-157 (2016) (in Japanese).
5. Atsushi Mori, Masafumi Yamato, Kohki Takahashi,
Structural anisotropy in silica gels prepared in magnetic fieldfrom viewpoint of alignment transition, 2015 Annual report ofhigh field laboratory for superconducting materials in institutefor materials research at Tohoku university，p.p.132-134 (2016)(in Japanese).
6. Hiroyoshi Kawakami, Development of all-solid-state
secondary battery composed of ion conductive nanofiber,
Technical Information Institute Co. Ltd. P.p 134-139 (2016) (inJapanese).

■Invited Lectures
1. Shoichiro Asayama, See the annual report in Japanese(December 2017)
2. Masafumi Yamato, Thermal and magnetic properties ofpolymer, 2016 Basic seminar of polymer science for young
engineers, Oct. 2016, Hiratsuka, Japan (in Japanese).
3. Masafumi Yamato, Development of composite materials byusing magneto-process, 60th Seminar of research group on
plastic films, Mar. 2017, Tokyo, Japan (in Japanese).
4. Manabu Tanaka, Ion Conductive Polymer Nanofibers:
Fabrication, Characterization, and Fuel Cell Applications,International Symposium on Polymer Chemistry (Changchun,
China), IL-3-27 (September 2016)
5. Hiroyoshi Kawakami, The future society built by hydrogenenergy, May 2017, Tokyo Metropolitan Government (inJapanese).
6. Hiroyoshi Kawakami, Medical revolution by chemistry,
Huly 2017, Yumenavi (in Japanese).
7. Hiroyoshi Kawakami, CCS application by using innovative
CO2 separation membrane with nao-space, June 2017, TIC(in Japanese).
8. Hiroyoshi Kawakami, Hydrogen society and fuel cell, June
2017, Waseda University (in Japanese).
9. Hiroyoshi Kawakami, Acid-doped polymer nanofiber
framework for high-performance fuel cells, EMN Meeting on
Power Sources 2016 (Bali, Indonesia) (Augsut 2016).
10. Hiroyoshi Kawakami,Innovative CO2 separation membranewith nao-space, The 65th Symposium on Macromolecules,
Kanagawa University, September 2016 (in Japanese).
11. Hiroyoshi Kawakami, Nanofiber Composite Ultra-thin
Polymer Electrolyte Membrane for Fuel Cells, IGEM2016(Kuala Limpur Malaysia) (October 2016).
12. Hiroyoshi Kawakami, Development of all-solid-state
secondary battery composed of ion conductive nanofiber,
March 2017, Technical Information Institute Co. Ltd. (inJapanese).

■Academic Meeting
1. Riku Kubota，Hideaki Taniguchi，Shoichiro Asayama，
Hiroyoshi Kawakami，Antioxidative supramolecular system
based on Mn-porphyrin derivatives, The 6th annual meeting of
ALA and Porphyrin Research Society (University of Tokyo),p.32 (April 2016).
2. Yuri Kameyama, Manabu Tanaka, and Hiroyoshi Kawakami,
Gas permeation property evaluation of polyimide composite
membranes containing novel surface-modified nanoparticles,4

Reports from Research Groups
Funabori), 2P212 (June 2016) (in Japanese)
17. Yuri Kameyama, Manabu Tanaka, Hiroyoshi Kawakami,
Gas permeation property of polyimide composite membrane
containing novel surface-modified nanoparticles, The Annual
Meeting of the Society of Fiber Science and Technology, Japan,(Tower Hall Funabori), 3F04 (June 2016) (in Japanese)
18. Risa Sakaguchi, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation of proton conductive blend nanofiber composite
membranes and characterization of their fuel cell properties,
The Annual Meeting of the Society of Fiber Science andTechnology, Japan, (Tower Hall Funabori), (June 2016) (inJapanese)
19. Risa Sakaguchi, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and electrolyte characteristics of acid/base polymer
blend nanofibers, The Annual Meeting of the Society of Fiber
Science and Technology, Japan, (Tower Hall Funabori), (June2016) (in Japanese)
20. Masafumi Yamato, Shoma Mochizuki, Noriyuki Hirota,
Hiroyoshi Kawakami, Kohki Takahashi, Birefringence of
Nanocomposite Gels polymerized in a Magnetic Field, 7thInternational Workshop on Materials Analysis and Processingin Magnetic Field, (Providence, USA) (June 2016)
21. Eizo Ushijima, Yuji Iwata, Masafumi Yamato, Patterningof nanoparticles using a magnetic modulator, 7th International
Workshop on Materials Analysis and Processing in Magnetic
Field, June 2016, (Providence, USA) (June 2016)
22. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami, Development of Proton Conductive Nanofiber
Frameworks for Polymer Electrolyte Fuel Cells, The 10th
Conference of Aseanian Membrane Society (Nara KasuganoInternational Forum IRAKA), PO1-011 (July, 2016)
23. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami, Fabrication and Characterization of Nafion
Composite Membrane Containing Sulfonated Polyimide
Nanofibers for Fuel Cell Applications, The 10th Conference ofAseanian Membrane Society (Nara Kasugano International
Forum IRAKA), PO1-017 (July, 2016)
24. Eiko Ito, Yuki Kudo, Manabu Tanaka, Masafumi ,Kawakami , High CO2 permeability of mixed matrix
membranes containing surface-modified silica nanoparticles,
2016 AMS-10, PO2-022, Japan(Nara Kasugano International
Forum IRAKU), Abstract p.96 (July 2016)25. Sakura Taneichi, Shoichiro Asayama, Yoichi Negishi,
Hiroyoshi Kawakami, “Molecular design of pDNA/PEG
mono-ion complex for PEG dilemma breakthrough”, 45rd
Symposium on Biomedical Polymer, Japan, p.61 (July, 2016)(in Japanese)
26. Emika Narazaki, Motoyuki Matsuho Shoichiro Asayama,
Hiroyoshi Kawakami, See the annual report in Japanese (July2016)
27. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,
See the annual report in Japanese (July 2016)28. Hideaki Taniguchi, Riku Kubota, and Hiroyoshi Kawakami,
Preparation of Polymer-bound Mn-porphyrins with Hydrogen
Peroxide Dismutation Activity, International Seminar on Green
Energy Conversion 2016, p.114 (August, 2016)29. Yuki Kudo, Manabu Tanaka, Hiroyoshi Kawakami,
Mixed Matrix Membranes Containing Surface-modified Silica
Nanoparticles for Gas Separation, The 1st International
Symposium on Hydrogen Energy-based Society, Japan,
Abstract, p10 (August, 2016)
30. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami, Proton Conductive Nanofiber Frameworks:
Development and Characterization for Polymer Electrolyte
Fuel Cells, The 1st International Symposium on Hydrogen
Energy-based Society (Tokyo Metropolitan University), P11(August, 2016)
31. Riku Kubota, Taiga Takabe, Hideaki Taniguchi, Hiroyoshi
Kawakami, Catalytic oxygen reduction by water-solublesupramolecular complex, The 66th Symposium on Japan
Society of Coordination Chemistry (Fukuoka University)(September 2016).
32. Masafumi Yamato, Shoma Mochizuki, Noriyuki Hirota,and Hiroyoshi Kawakami, Birefrigence of clay mixed nanocomposite gel polymerized in a magnetic field, 65h Symposiumof Macromolecules, University of Kanagawa, (1T17)(September, 2016) (in Japanese)
33. Manabu Tanaka, Takeru Wakiya, Takahito MAkinouchi,
Takahiro Ogura, Hiroyoshi Kawakami, Construction of
Nanofiber Frameworks with Continuous Proton Conductive
Pathways and Their Fuel Cell Applications, 65th Symposiumon Macromolecules, Japan, 2X08 (September 2016) (inJapanese)
34. Riku Kubota, Hiroyoshi Kawakami, Catalytic oxygen
reduction of novel water-soluble supramolecular system, The
65th Symposium on Macromolecules (Kanagawa University)(September 2016).
35. Tsukasa Watanabe, Manabu Tanaka, and Hiroyoshi
Kawakami, Preparation and evaluation of ion conductive
polymer nanofiber framework for all-solid-state lithium ion
battery, 65th Symposium on Macromolecules, Japan, Vol. 65,
No. 2, p. 39 (1X18) (September 2016) (in Japanese)
36. Yuki Kudo, Manabu Tanaka, Masafumi Yamato, Hiroyoshi
Kawakami, Analysis of the CO2 permeation mechanism ofcomposite membranes containing surface-modified silica
nanoparticles, 65th Symposium of Macromolecules, 2Pa071(September, 2016) (in Japanese)
37. Takushi Shimane, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi Kawakami, Preparation of nanofiber framework
composite electrolyte membranes based on lithium ion
conductive polymer nanofibers for future secondary battery
applications, The 65th Symposium of Macromolecules, 3Pa049(September, 2016) (in Japanese)
38. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami,
Fabrication
andcharacterizationsofsurface-modified nanofiber framework composite membranes
for proton conductivity enhancement, The 65th Symposium on
Macromolecules, Kanagawa University, 3Pb052 (September,2016) (in Japanese)
39. Eiko Ito, Manabu Tanaka, Masafumi Yamato, Hiroyoshi
Kawakami, Preparation and gas permeability evaluation ofpolymer composite membranes composed of PIM type
polymers and surface-modified nanoparticles, 65th Symposiumon Macromolecules, Japan(Kanagawa University), 2Pb072,
Abstract p.53 (Sep. 2016) (in Japanese)
40. Yuri Kameyama, Manabu Tanaka, Hiroyoshi Kawakami,
Influence of the particle structures on the gas permeation
characteristics
ofcompositemembranes
containing
surface-modified nanoparticles, 65th Symposium on
Macromolecules, Japan, (Kanagawa University), 2Pa073 (Sep.
2016) (in Japanese)
41. Yuri Kameyama, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation and gas permeability evaluation of polymer
compositemembranes
containing
surface-modified
heteromorphic
nanoparticles,
65th
SymposiumonMacromolecules, Japan, (Kanagawa University), 1M14 (Sep.
2016) (in Japanese)
42. Risa Sakaguchi, Manabu Tanaka, Hiroyoshi Kawakami,
Preparation of acid/base blend polymer nanofibers and theirfuel cell application, 65th Symposium on Macromolecules,(Kanagawa University), (Sep. 2016) (in Japanese)
43. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,
See the annual report in Japanese (September 2016)
44. Ryosuke Shinohara, Shoichiro Asayama and Hiroyoshi
Kawakami, Epigenetics control by biodegradable nanoparticles
coated with alkyl amine, 64th Symposium on Macromolecules,
2Pc109 (September, 2016) (in Japanese)
45. Takabe Taiga, Taniguchi Hideaki, Kubota Riku, Kawakami
Hiroyoshi, Catalytic properties of novel water-solublesupramolecular device utilizing Cucurbit[10] cavity, 65th
Symposium on Macromolecules (Kanagawa University),
2Pa089 (September, 2016) (in Japanese)5

Reports from Research Groups
The 57th Battery Symposium, 1G06, Makuhari Messe(November, 2016) (in Japanese)
60. Takushi Shimane, Yuta Inafune, Tsukasa Watanabe,
Manabu Tanaka, Hiroyoshi Kawakami, Preparation of
nanofiber framework composite electrolyte membranes basedon lithium ion conductive solid polymer nanofibers for futuresecondary battery applications, The 57th Battery Symposium,
1G05, Makuhari Messe (November, 2016) (in Japanese)
61. Takahito Makinouchi, Risa Sakaguchi, Manabu Tanaka,
Hiroyoshi
Kawakami,
Fabrication
and
Fuel
Cell
Characterizations of Nanofiber Framework-based Electrolyte
Membranes Bearing High Proton Conductive Pathway at Inside
and Surface of the Nanofibers, The 57th Battery Symposium,
1F09, Makuhari Messe (November, 2016) (in Japanese)
62. Motoyuki Matsuho, Riku Kubota, Shoichiro Asayama, andHiroyoshi Kawakami, Lactoferrin-Modified Nanoparticle
Loading Potent Antioxidant Mn-Porphyrin Exhibits Enhanced
Antioxidative Activity in in vitro Intranasal Brain Delivery
Model, 23rd Annual Meeting of the Society for Free Radical
Biology 2016 (November, 2016)63. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,
See the annual report in Japanese (November 2016)
64. Shoichiro Asayama, Sakura Taneichi, Yoichi Negishi,
Hiroyoshi Kawakami, “Breakthrough for PEG dilemma of the
pDNA/PEG mono-ion complex with in vivo gene expression.”,The 38th Annual Meeting of the Japanese Society for
Biomaterials, Japan, 2P-061 (November, 2016) (in Japanese)
65. Yuta Inafune, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi Kawakami, Fabrication of solid electrolyte based onlithium ion conductive nanofiber framework for bipolar stacked
battery application, The 85th Musashino area polymer
association, Kougakuin University, P02 (Nov.2016) (inJapanese)
66. Takahiro Ogura, Takeru Wakiya, Manabu Tanaka, andHiroyoshi Kawakami, Preparation of composite thinmembranes consisted of acid-doped nanofiber frame works andtheir influence to fuel cell electrolyte membrane, 85thMusashino area polymer forum, Kogakuin University, Japan,
P05 (November, 2016) (in Japanese)
67. Shun Nakazawa, Kazunori Hara, Tsukasa Watanabe,
Manabu Tanaka, and Hiroyoshi Kawakami, Preparation oflithium single-ion-conducting nanofiber composite electrolyte
membranes and their application to secondary batteries, 85thMusashino area polymer association, Kogakuin University,
Japan, (P12) (Nov. 2016) (in Japanese)
68. Hiroto Mikami, Yuri Kameyama, Manabu Tanaka,
Hiroyoshi Kawakami, Gas permeability evaluation ofpolyimide composite membranes containing mixed silica
nanoparticles with different morphologies. 65th symposium ofMacromolecules, Kanagawa University, Japan, P16 (November,2016) (in Japanese)
69. Masafumi Yamato, Shoma Mochizuki, Noriyuki Hirota,and Hiroyoshi Kawakami, Large anisotropy of nano composite
gel originating in orientation of hectrite induced by magneticalignment of montmorillonite 11th Magneto-Science Society ofJapan , National Institute for Materials Science, Abstractp.80-81 (P-17) (November, 2016) (in Japanese)
70. Shoichiro Asayama, Atsushi Nohara, Yoichi Negishi, andHiroyoshi Kawakami, Mono-Ion Complex for In Vivo Plasmid
DNA Delivery, 3rd International Conference on Biomaterials
Science in Tokyo (ICBS2016), Program, p. 131 (November,
2016)
71. Yuki Kudo, Manabu Tanaka, Masafumi Yamato, Hiroyoshi
Kawakami, CO2 permeability evaluation and analysis of PIM-1
composite membranes containing surface-modified silica
nanoparticles, 54th Symposium on Polymer and Water, Japan,
p. 10 (December, 2016) (in Japanese)
72. Takahito Makinouchi, Manabu Tanaka, Hiroyoshi
Kawakami,
Fabrication
andcharacterizationsofsurface-modified nanofiber framework composite membranes
for fuel cell operation at low humidity, The 54th Symposium

46. Sakura Taneichi, Shoichiro Asayama, Yoichi Negishi,
Hiroyoshi Kawakami, “in vivo Diffusion Ability of
Futher-Migrating pDNA/PEG Mono-ion Complexes without
PEG Dillema.”, 65th Symposium on Macromolecules,
Kanagawa University, Japan, 2Pc101 (Sep. 2015) (in Japanese)
47. Yuma Yokokawa, Shoichiro Asayama, Hiroyoshi
Kawakami, Synthesis and evaluation of beta-CD-modified
anionic polymer for inhibition and degradation of amyloid beta
aggregation., Polymer Preprints, Japan, Vol.65, (Kanagawa
University)2Pf108 (September, 2016) (in Japanese)
48. Kohe Arima, Satoshi Hamada, Kazuhiko Nakabayashi,
Shoichiro Asayama, Hiroyoshi Kawakami, Control of DNA
methylation by epigenetics control carrier in cancer cell, 65th
Symposium on Macromolecules, 2Pc103(September, 2016) (inJapanese)
49. Emika Narazaki, Shoichiro Asayama, Hiroyoshi Kawakami,
See the annual report in Japanese (September 2016)
50. Yuta Inafune, Tsukasa Watanabe, Manabu Tanaka,
Hiroyoshi Kawakami, Preparation of polymer electrolytecomposite membranes based on lithium ion conductive
nanofibers, The 65th Symposium on Macromolecules,
Kanagawa University, 3Pb048 (Sep.2016) (in Japanese)
51. Takahiro Ogura, Takeru Wakiya, Manabu Tanaka, andHiroyoshi Kawakami, Preparation and characterization ofcomposite thin membranes consisted of acid-doped nanofiber
frame works, 65th Symposium of Macromolecules, Kanagawa
University, Japan, 3Pa051 (September, 2016) (in Japanese)
52. Kosuke Chikuma, Mai Kusatsu, Kazuhiko Nakabayashi,
Shoichiro Asayama, Hiroyoshi Kawakami, Regulation of cellcharacter targeting histone methylation site by epigenetics
control carrier, 65th Symposium on Macromolecules,
Kanagawa University, Japan, 2Pd108, (September, 2016) (inJapanese)
53. Taiga Nagakura, Mizuki Sakata, Shoichiro Asayama, andHiroyoshi Kawakami, Enhancement of cell proliferation by
Zn2+/pDNA co-delivery system, 65th Symposium on
Macromolecules, Kanagawa University, Japan, Abstract p.57
(2Pd102) (Sep. 2016) (in Japanese)
54. Shun Nakazawa, Kazunori Hara, Tsukasa Watanabe,
Manabu Tanaka, and Hiroyoshi Kawakami, Preparation oflithium single-ion-conducting nanofiber framework and theirapplication to secondary batteries, 65th Symposium on
Macromolecules, Kanagawa University, Japan, Abstract p.61
(3Pb050) (Sep. 2016) (in Japanese)
55. Hiroto Mikami, Yuri Kameyama, Manabu Tanaka,
Hiroyoshi Kawakami, CO2 permeability evaluation ofpolyimide composite membranes containing mixed silica
nanoparticles with different morphologies. 65th symposium ofMacromolecules, Kanagawa University, Japan, 2Pb074(September, 2016) (in Japanese)
56. Hideaki TANIGUCHI, Taiga TAKABE, Riku KUBOTA,
Hiroyoshi KAWAKAMI, Synthesis and catalytic application of
a novel water-soluble supramolecule composed of
Fe-porphyrin/Fe(bpy)2/Cucurbit[10], The 66th Conference ofJapan Society of Coordination Chemistry (Fukuoka University),
1PF-03, (September, 2016) (in Japanese)
57. Taiga Takabe, Hideaki Taniguchi, Riku Kubota, Hiroyoshi
Kawakami, Synthesis of novel water-soluble dinuclear
complex-induced supramolecular utilizing Cucurbit[10] cavity
and application for catalyst ， The 66th Japan Society of
Coordination Chemistry Symposium (Fukuoka University)，
2PF-17 (September, 2016) (in Japanese)
58. Manabu Tanaka, Takeru Wakiya, Takahiro Ogura,
and
Fuel
Cell
Hiroyoshi
Kawakami,
Fabrication
Characterization of Polymer Electrolyte Composite Membranes
Based on Acid-doped Nanofiber Framework with Densification
and Thinning Processes, The 57th Battery Symposium, 1F08,
Makuhari Messe (November, 2016) (in Japanese)
59. Tsukasa Watanabe, Manabu Tanaka, Hiroyoshi Kawakami,
Lithium Ion Conductive Nanofibers Framework Composite
Electrolyte Membrane for All-Solid-Type Secondary Batteries,

6

Reports from Research Groups
on Polymer and Water Japan, P13, Tokyo Institute ofTechnology (December, 2016) (in Japanese)
73. Shoichiro Asayama, Mizuki Sakata, Hiroyoshi Kawakami,
See the annual report in Japanese (March 2017)

54th Symposium on the Interaction between Polymer andWater and Separation Science, Tokyo Institute of Technology(December 2016)■Patents
1. Hiroyoshi Kawakami, Shoichiro Asayama, Shohei
Yamaguchi, Motoyuki Matsuho, Yutaro Asaba, See the annual
report in Japanese.
2. P2016-102287A, Nanofiber, nanofiber assembly, composite
membrane, solid polymer electrolyte, and lithium ion battery,
Hiroyoshi Kawakami, Manabu Tanaka, Tsukasa Watanabe
3. Shoichiro Asayama, Hiroyoshi Kawakami, Kana Nagashima,
See the annual report in Japanese.
4. P2016-82423, Fabrication process of gas separation
membrane, Hiroyoshi Kawakami, Manabu Tanaka, Yuri
Kameyama, Azusa Osawa, Tadayuki Isaji, Takamasa Kikuchi
5. Hiroyoshi Kawakami, Shoichiro Asayama, Yutaro Asaba,
Motoyuki Matsuho, Ryosuke Shinohara, See the annual reportin Japanese.
6. P2016-110367, Composite nanofiber and electrolyte
membrane, Hiroyoshi Kawakami, Manabu Tanaka, Risa
Sakaguchi
7. P2016-163160, Multielectron redox catalyst, Hiroyoshi
Kawakami, Riku Kubota, Hideaki Taniguchi, Taiga Takabe
8. P2016-162455, Surface-modified nanofiber, electrolyte
membrane, fabrication process of electrolyte membrane,
membrane electrode assembly, and polymer electrolyte fuelcell, Hiroyoshi Kawakami, Manabu Tanaka, Takahito
Makinouchi
9. P2016-163081, Gas separation membrane containing variant
silica nanoparticles, Hiroyoshi Kawakami, Manabu Tanaka,
Yuri Kameyama, Yuki Kudo, Hiroto Mikami, Tadayuki Isaji,
Kazutoshi Kodata, Takamasa Kikuchi
10. P2016-211648, Polymer electrolyte membrane and fuel cell,
Hiroyoshi Kawakami, Manabu Tanaka, Tsukasa Watanabe
11. P2016-162456, Fabrication process of electrolyte
membrane and battery materials, Hiroyoshi Kawakami,
Manabu Tanaka, Tsukasa Watanabe■Awards
1. Shoichiro Asayama, the Tokyo U-club, See the annual reportin Japanese (May 2016)
2. Yuri Kameyama, Gas permeation property evaluation ofpolyimide
compositemembranes
containing
novel
surface-modified nanoparticles, The student poster award, 38th
Annual Meeting on The Membrane Society of Japan, Waseda
University (May 2016)
3. Yuri Kameyama, Preparation and gas permeation evaluationof polyimide composite membranes containing novel surfacemodified nanoparticles, The excellent poster award, The
Annual Meeting on The Society of Fiber Science andTechnology, Tower Hall Funabori (June 2016)
4. Yuki Kudo, Analysis of the CO2 permeation mechanism ofcomposite membranes containing surface-modified silica
nanoparticles, The excellent poster award, 65th Symposium on
Macromolecules, Kanagawa University (September 2016)
5. Takahito Makinouchi, Fabrication and characterizations ofsurface-modified nanofiber framework composite membranes
for proton conductivity enhancement, The excellent poster
award, 65th Symposium on Macromolecules, Kanagawa
University (September 2016)
6. Yuma Yokokawa, synthesis and evaluation of β-CDmodified anionic polymer for inhibition and degradation ofamyloid β aggregation, The excellent poster award, 65th
Symposium on Macromolecules, Kanagawa University(September 2016)
7. Yuki Kudo, CO2 permeability evaluation and analysis of
PIM-1 composite membranes containing surface-modified
silica nanoparticles, The excellent student presentation award,
7

Reports from Research Groups
Masuda Laboratory
Ordered pillar array and hole array patterns were fabricatedby nanoimprinting using anodic porous alumina. Patterned
surface prepared by this process could be used for theantirefrection surface and surper hydrophobic surface.

■Members
Hideki Masuda
Professor/ Dr. Eng.
Electrochemistry, Nano Fabrication, Functional ElectrodeRm. 9-147, +81 426 77 2843
masuda-hideki@tmu.ac.jp(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 canbe used 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 toimprove 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 theanodization conditions. Metal and semiconductor nanohole
array structures have been also fabricated using an anodic
porous alumina as a template. For the replacement of theordered hole-array structure with other materials we developed
a two-step replication process in which formation of a
replicated negative and subsequent preparation of a replicatedpositive give the nanohole structure identical to that of motherstructure of anodic orous alumina. Metal (Au, Pt, Ni) andsemiconductor (TiO2, ZnO, CdS) nanohole arrays have been
fabricated using the two-step process. Detailed conditions forthe 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,
Formation of porous Al particles by anisotropic anodic
etching
Electrochem. Commun., in press.
2. Takashi Yanagishita, Atsushi Kato, and Hideki Masuda
Preparation of Ideally Ordered Through-Hole Anodic
Porous Alumina Membranes by Two-Layer Anodization
Jpn. J. Appl. Phys., 56, 035202 (2017).
3. Ryoohei Takakura, Tomoya Oshikiri, Kosei Ueno, Toshiaki
Kondo, Hideki Masuda, and Hiroaki Misawa
Water Splitting Using a Three-dimensional Plasmonic
Photoanode with Titanium Dioxide Nano-tunnels
Green Chem., in press.
4. Takashi Yanagishita and Hideki Masuda
Facile Preparation of Porous Alumina Through-Hole Masks
for Sputtering by Two-Layer Anodization
AIP Adv., 6, 085108 (2016).

SEM image of anodic porous alumina(2) Preparation of Ordered Nanostructures by Nanoimprinting
Using Ordered Anodic Porous Alumina Molds
Hideki MASUDA, Takashi YANAGISHITA

5. Toshiaki Kondo, Shota Hirano, Takashi Yanagishita, Nhat
Truong Nguyem, Patric Schmuki, and Hideki Masuda

8

Reports from Research Groups
Two-Dimensional Photonic Crystals Based on Anodic
Porous TiO2 with Ideally Ordered Hole Arrangement
Appl. Phys. Express, 9, 102001 (2016).

3. Hideki Masuda, Toshiaki Kondo, and Takashi Yanagishita
Micro- and Nanostructures for High Efficiency Energy
Conversion by Using Anodic Porous Alumina
11th International symposium on Electrochemical Micro &Nanosystem Technologies (EMNT 2016)，2016/8，Brussel

6. Toshiaki Kondo, Sanami Nagao, Shota Hirano, Takashi
Yanagishita, Nhat Truong Nguyem, Patric Schmuki, andHideki Masuda
Fabrication of Ideally Ordered Anodic Porous TiO2 by
Anodization of Pretextured Two-Layered Metals
Electrochem. Commun., 7, 100 (2016).

4. Hideki Masuda, Toshiaki Kondo, Takashi Nakazono, andHideki Masuda
Preparation of Ordered Semiconductor Nanorod Arrays
Using Anodic Porous Alumina
Energy, Material & Nanotechnology Meeting on Smart &Multifunctional Material, 2016/8，Belrine

7. Toshiaki Kondo, Sanami Nagao, Takashi Yanagishita, andHideki Masuda
Formation of Porous Anodic TiO2 with Square Nanoholes
by Pretexturing Process
J. Electrochem. Soc., 163, E206 (2016).

5. Takashi Yanagishita and Hideki Masuda
Preparation of Ordered Anodic Porous Alumina
Through-Hole Membrane and Its Applications
PRiME 2016/230th ECS Meeting, 2016/10, Hawaii

8. Toshiaki Kondo, Naoya Kitagishi, Tatsuro Fukushima,
Takashi Yanagishita, and Hideki Masuda
Fabrication of Aluminum Nanowires by Mechanical
Deformation of Al Using Anodic Porous Alumina Molds
Mater. Express, 6, 363 (2016).
9. Takashi Yanagishita and Hideki Masuda
Preparation of ordered Anodic Porous
Through-Hole Membrane and Its Applications
ECS Transactions, 75, 21 (2016).

6. Hideki Masuda, Takashi Yanagishita, and Toshiaki Kondo
Fabrication of Highly Ordered Anodic Porous Alumina and
Its Applications to Fanctional Nanodevices
PRiME 2016/230th ECS Meeting, 201/10，Hawaii

Alumina

7. Hideki Masuda
Functional Optical Devices Based on Anodizing Process
The 3rd Korea-Japan Joint Symposium for ARS & ESS，2016/11, Koria

10. Takashi Yanagishita, Takeshi Hidaka, Mari Suzuki, andHideki Masuda
Polymer lenses with antireflection structures prepared using
anodic porous alumina molds
J. Vac. Sci. Technolo. B, 34, 021804 (2016).

＊Domestic
See the annual report in Japanese (9 articles)■Academic Meeting＊International
1. Toshiaki Kondo, Takashi Yanagishita, Hideki Masuda,
Three-dimensional waveguide obtained using anodic
porous alumina
2016 MRS Fall Meeting, 2016/11，Boston

11. Takashi Yanagishita, Syota Ueno, Keisuke Taniguchi, andHideki Masuda
Fabrication of Porous Si Particles by Barrel Anode Etching
Chem. Lett., 45, 708 (2016)＊Domestic
See the annual report in Japanese (39 articles)

12. Takashi Takei, Haruko Miyamoto, Sueo Kagawa, andHirohisa Yoshida
Approach to Thermal Analysis of Undergraduate
Experiments for Applied Chemistry
Netsu Sokutei, 43, 7 (2016)■Patents
See the annual report in Japanese (4 articles)■Awards
See the annual report in Japanese (2articles)■Reviews and Books
See the annual report in Japanese (6 articles)■Invited Lectures＊International
1. Hideki Masuda, Toshiaki Kondo ,Takashi Nakazono andTakashi Yanagishita
Growth of Ordered ZnO Nanorods Arrays Using Anodic
Porous Alumina Templates
229th ECS Meeting, 2016/5，San Diego
2. Toshiaki Kondo, and Hideki Masuda
Formation of Metal Nanostructure Array and Its
Application to Plasmonic Devices
International Workshop on Nanostructure-Based Chemistry
and Light-Energy Conversion，2016/6，Tokyo

9

Reports from Research Groups
Setaka Laboratory
mechanism
into
a
new
gear
system,abis(9-triptycyl)difluorosilane derivative, is achieved by thereversible attachment of a fluoride ion.

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

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

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

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

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

Figure. A phenyldisilane which exhibits CT fluorescence.

■Papers with Peer Review
1. Facile Synthesis of a 2,5-Bis(silyl)selenophene-1,1-dioxide
and its Photophysical Properties, T. Masuda, Y. Inagaki, H.
Momma, E. Kwon, W. Setaka, New J. Chem, 40, 8593-8599(2016).
2. Molecular Gyrotops with a Five-Membered Heteroaromatic
Ring: Synthesis, Temperature-Dependent Orientation of
Dipolar Rotors inside the Crystal, and its Birefringence Change,
T. Masuda, J. Arase, Y. Inagaki, M. Kawahata, K. Yamaguchi, T.
Ohhara, A. Nakao, H. Momma, E. Kwon, W. Setaka, Cryst.
Growth Des., 16, 4392-4401 (2016).

Figure. Structure of molecular gyrotop and birefringencechange.

■Invited Lectures
1. Yusuke Inagaki, Molecular arrangements and synamics in a
Crystalline State, The first workshop for young organic chemist,
2016.11.9-10, Kyoto University
2. Wataru Setaka, Effects of Cage Size on Rotational Dynamics
andFluorescence
Properties:
A
Study
of
Naphthalenediyl-Bridged Molecular Gyrotops, 2016.5.20-21,
The 6th Symposium on Stimuli-responsive Chemical Species
for the Creation of Functional Molecules, 2017.3.6-7.,
Hiroshima University

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-declutch■Academic Meeting＊International
1. Watasu Setaka
Dielectric Properties of Crystalline Molecular Gyrotops with a
Dipolar Rotor
The 2nd International Symposium on Stimuli-responsive
Chemical Species for the Creation of Functional Molecules,
10

Reports from Research Groups
2017.3.6-7., Hiroshima University, Higashihiroshima, Japan
2. Watasu Setaka
Phenylene-Bridged Macrocage Compounds as MolecularGyrotops in Crystalline StateThe 2016 Asian Crystallographic Association Conference(AsCA), 2016.12.3-8., Hanoi University of Science andTechnology, Hanoi, Vietnam (MS11.O03)
3. Miyako Tsurunaga, Yusuke Inagaki, Watasu Setaka
A Novel Thiophene-Dioxide Bridged Molecular Gyrotop as a
Candidate for Dielectric Material
The 1st International Symposium on Hydrogen Energy-based
Society, 2016.8.26-27, Tokyo Metropolitan University, Japan.
4. Kohei Sato, Yusuke Inagaki, Watasu Setaka
p-Benzoquinone-Bridged Macrocages as Potential Electron
Carriers
The 1st International Symposium on Hydrogen Energy-based
Society, 2016.8.26-27, Tokyo Metropolitan University, Japan.
5. Watasu Setaka
Synthesis and Structure of a Selenophene-bridged Macrocage
as a Molecular Gyrotop
The 13th International Conference on the Chemistry of
Selenium and Tellurium (ICCST-13), 2016.5.23-27,
Nagaragawa Convention Center, Gifu, Japan＊Domestic
See the annual report in Japanese (10 articles)■Awards
1. Miyako Tsurunaga received the excellent poster award at 6th
CSJ Chemistry Festa, the Chemical Society of Japan (14-16
October 2016, Funabori (Tokyo)). The title of her presentation
was “Synthesis of Novel Thiophene-dioxide Bridged MolecularGyrotops and their Dynamic Properties in Crystalline State".
2. Mr. Kazuma Okamura received Excellent Oral Presentation
Award and Chemistry Letters Young Award at the 43rd
Symposium on Main Group Element Chemistry (Dec. 8-10,
2016, Sendai Citizen Hall, Sendai). The title of his talk was"Synthesis and dynamics of germanium-linked molecular gears
and their 5-coordinated derivatives".

11

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

the size of Au particles. Au/NbOx (SI) exhibited high catalytic
activity (Fig. 1) and recorded 91% conversion at 28 °C.

TOF(20℃) / s

-1

0.04

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

0.03
0.02
0.01
0

Tamao ISHIDA
Project Professor /Dr. Eng.
Catalysis Chemistry,room:F-203 TEL: +81-42-677-2360
e-mail: tamao@tmu.ac.jp

SI

SG

DR

DP

0 1 2 3 4 5 6 7 8
Mean diameter / nm

Fig.1 Relationships between gold particle size of Au/NbOx andturnover frequency (TOF) for CO oxidation at 20 °C.
A size dependency of Au/Cs4SiW12O40 prepared by SI on CO
oxidation was examined. The catalytic activity significantly
decreased with an increase in the size of Au particles. The result
suggested that a deposition of Au clusters smaller than 2 nm onto
Cs4SiW12O40 is essential to show high catalyitc activity (Fig. 2).
100

2.0 nm80

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

10.7 nm
60
40
20
0
-80

-40
0
40
80
Temperature / °C
Fig. 2 Catalytic activity for CO oxidation on Au/Cs4SiW12O40.

Takuya YOSHIDA
Project Assistant Professor /Dr. Sci.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360
e-mail: tyoshida@tmu.ac.jp
Dien Xuan LUONG
Project Assistant Professor /Dr. Sci.
Catalysis Chemistry,room:F-201 TEL: +81-42-677-2360
e-mail: dien.luongxuan@hust.edu.vn

Master’s course -1
Research student-1■Outlines of the Research
1. Gas Phase Reactions by Metal Oxide-Supported Gold
Catalysts
Toru MURAYAMA, Takuya YOSHIDA, Takashi FUJITA, Dien
Xuan LUONG, Masatake HARUTA

Fig. 3 O2-TPD spectra of Au/ZnO
Oxygen vacancy at Au–metal oxide interface plays animportant role for CO oxidation at low temperature. To clarify
the effect of the interaction between Au and metal oxides
regarding to the formation of oxygen vacancy, catalytic activityof Au/ZnO was examined by verifying the calcination
atmosphere. Au/ZnO calcined in H2 followed by O2 calcination(H2-573K) exhibited remarkably higher catalytic activity thanthat calcined in O2 (O2-523K). We also found that the reaction
mechanism of Au/ZnO (H2-573K) for CO oxidation changed atGold nanoparticles were deposited onto niobium oxide (NbOx)
prepared by hydrothermal method. We examined several kind of
preparation methods and found that sol immobilization (SI) was
suitable to deposit Au nanoparticles with a mean diameter of 3
nm. SI was superior to deposition-precipitation (DP), depositionreduction (DR), and solid grinding (SG) in terms of minimizing

12

Reports from Research Groups
lower than –20 °C. According to the oxygen temperature
programmed desorption (O2-TPD) profiles (Fig. 3), a desorption
peak at low temperature (353 K) was observed in Au/ZnO (H2573K). This result implies that the calcination atmosphereaffects the formation of oxygen vacancy at Au–oxide interface;calcination in H2 and then O2 might form active oxygen species
that works at low temperatures.

respectively. These values were in a good agreement with thehigh-angle annular dark field transmission electron microscopy(HAADF-STEM) observation. As a results, MW drying was
superior method to produce the smallest Au clusters.
Solid grinding (SG) method is a useful preparation for inert
supports to deposit Au clusters and simple, because Au can bedeposited by just grinding the Au precursor, Me2Au(acac), andsupports at room temperature under air followed by calcination.
However, Me2Au(acac) is expensive and hardly obtained.
Therefore, alternative Au precursors, which can be applied to SG,
was studied. As a result, Au(TPy)(TFA)2, Au(TPy)boroxing,
IPrAuOH, Au-thiomalic acid complex were found to be potential
precursors (Fig. 5). In contrast, Au was aggregated when
Au(TPy)Cl2 was used, suggesting that the presence of halogen
as a ligand accelerated the aggregation of Au.

2. Liquid Phase Reactions by Supported Metal Nanoparticle
Catalysts
Tamao ISHIDA, Ayako TAKETOSHI, Masatake HARUTA
Ullmann coupling of iodobenzene catalyzed by supported Au
NPs was studied using various kinds of metal oxide supports.
Metal oxides having redox properties themselves, such as CeO2,
Co3O4, MnO2, showed lower or poor catalytic activity than othersupports. Conversion increased with the acidity of metal oxides,
but selectivity decreased due to the formation of benzene as aby-product. As a result, amphoteric oxides, such as Al2O3, gave
the highest biphenyl yields (Fig. 4). We also examined the size
dependency and found that suitable Au particle size depend on
the kinds of supports; smaller Au particles showed higher
activity for Au/ZnO, but larger ones were better for Au/SiO2.

Fig. 5 Scope of organogold complexes for solid grinding.
4. Synergistic Effects of Gold Nanoparticle Catalysts with
Biofunctional Materials
Jun-ichi NISHIGAKI, Takashi FUJITA, Masatake HARUTA
We
developed
thecatalytic
reaction
havingsynergistic/complementary effects by putting biological enzyme
catalyst and artificial Au NPs catalyst together. NADH andNAD+ work as coenzymes that are comsumed to reduce/oxidize
substrates. Au NPs (1.4~4.2 nm) deposited on nanodiamond andmetal oxides can oxidize NADH to NAD+ using O2 as an oxidant.
Addition of thsese Au catalysts to dehydrogenase enzymeic
oxidation reaction allows reproducing NAD+ from spent NADH
to proceed enzymatic oxidation. This system requires only O2
as an additional reactant, which gives the potential fordeveloping resourse conservation and low emvirommental
damage catalytic systems (Scheme 2). Optimization of reaction
conditions is ongoing to improve yields.

Fig. 4 Relationship between electronegativity of supports andbifhenyl yield for Ullman coupling.
Aliphatic ethyl esters are an important class of fine chamicals
in application to fragrance and flavors. Oxidative esterificationof aldehyde to ethyl ester was examined using octanal as a modelcompound (Scheme 1). The targest ester was obtained in highyield when Au was deposited as clusters samller than 2 nm onto
ZnO, Al2O3, Co3O4. We found that these catalysts worked
efficiently under high concentrations in the aim of industrial
applications.

Scheme 2. Catalytic transformation of NADH to NAD+ by using
gold catalysts.
Scheme 1. Synthesis of ethyl octanoate from octanal.

As an additional result, Au clusters deposited on basic
metal oxides, such as hydrotalcite and CeO2, catalyzed the
reduction of NAD+ to NADH with H2 (1 MPa) at low
temperature (37˚C), suggesting that the Au catalysts can also be
used as a coenzyme reproducing system in a dehydrogenase
reduction processs (Scheme 3).

3. Preparation of Supported Gold Clusters
Ayako TAKETOSHI, Dien Xuan LUONG, Tamao ISHIDA,
Masatake HARUTA
We have studied a development of catalyst preparation metods
using microwave (MW). Drying methods, oven, freeze-drying(FD), and MW, were compared by means of the chemical stateof Au after drying and the size of Au particles using X-ray
absorption spectrometry. In case of Au/Al2O3, Au(III)completely remained after FD and MW drying. In contrast, ca.
50% of Au(III) was reduced to Au(0) after oven drying. Afterthe reduction with H2, Au(III) was completely reduced in allcases. The size of Au particles were estimated by curve-fitting
analyses to be 2.3, 1.9, and 1.6 nm for oven, FD, and MW drying,

Scheme 3. Hydrogenation of NAD+ to NADH by using gold
catalysts for glucose oxidation with GDH.

13

Reports from Research Groups
For application of supported Au nanoparticles (NPs) into
nanomedicine, cytotoxicity of several kinds of supported Au
NPs for HeLa cells (human cell line derived from cervical cancer
cells). Although SiO2 did not show cytotoxicity, the depositionof Au onto SiO2 improved the cytoxicity. On the other hand, nodifference was observed for TiO2 with or without Au NPs. The
deposition of Au NPs affected the cytotoxicity depending on themetal oxide supports. Relationships between cytotoxicity andacid-base properties of support surface will be discussed in thenear future.

11.

12.

■Papers with Peer Review
1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

13.

T. Murayama, W. Ueda, M. Haruta, "Deposition of Gold
Nanoparticles on Niobium Pentoxide with Different
Crystal Structures for Room-Temperature Carbon
Monoxide Oxidation", ChemCatChem 2016, 8, 2620–
2624.
T. Fujita, M. Horikawa, T. Takei, T. Murayama, M. Haruta,"Correlation between catalytic activity of supported gold
catalysts for carbon monoxide oxidation and metal-oxygenbinding energy of the support metal oxides", Chin. J. Catal.
2016, 37, 1651–1655.
T. Murayama, M. Haruta, "Preparation of gold
nanoparticles supported on Nb2O5 by deposition
precipitation and deposition reduction methods and theircatalytic activity for CO oxidation", Chin. J. Catal. 2016,
37, 1694–1701.
H. Arai, T. Yoshida, E. Nagashima, A. Hatayama, S. Horie,
S. Matsunaga, K. Nomiya, “Silver- and Acid-Free
Catalysis by Polyoxometalate-Assisted Phosphanegold(I)Speciesfor
HydrationofDiphenyacetylene”,
Organometallics 2016, 35, 1658–1666.
E. Nagashima, T. Yoshida, S. Matsunaga, K. Nomiya,“The effect of counteranions on the molecular structures ofphosphanegold(I)clustercations
formedbypolyoxometalate (POM)-mediated clusterization”, Dalton
Trans. 2016, 45, 13565–13575.
T. Ishida, K. Kume, K. Kinjo, T. Honma, K. Nakada, H.
Ohashi, T. Yokoyama, A. Hamasaki, H. Murayama, Y.
Izawa, M. Utsunomiya, M. Tokunaga, "Efficient
Decarbonylation of Furfural to Furan Catalyzed by ThreeAtom Palladium Clusters supported on Zirconia",
ChemSusChem 2016, 9, 3441–3447.
H. Ando, D. Kawamoto, H. Ohashi, Y. Kobayashi, T.
Ishida, Y. Okaue, M. Tokunaga, T. Yokoyama“Characterization of gold and nickel in precursor of
supported Au catalyst”, Adv. X-ray. Chem. Anal., Japan,
2016, 47, 111–118 (in Japanese).
Z. Zhang, Q. Wu, T. Hashiguchi, T. Ishida, H. Murayama,
M. Tokunaga, “Allylic C–H acetoxylation of terminal
alkenes over TiO2 supported palladium nanoparticles using
molecular oxygen as the oxidant”, Catal. Commun. 2016,
87, 18–22.
D. Kawamoto, H. Ando, H. Ohashi, Y. Kobayashi, T.
Honma, T. Ishida, M. Tokunaga, Y. Okaue, S. Utsunomiya,
T. Yokoyama, “Structure of a Gold(III) Hydroxide andDetermination of Its Solubility”, Bull. Chem. Soc. Jpn.
2016, 89, 1385–1390.
T. Murayama, K. Nakajima, J. Hirata, K. Omata, E. J. M.
Hensen, W. Ueda, “Hydrothermal Synthesis of a Layeredtype W-Ti-O Mixed Metal Oxide and its Solid Acid
Activity”, Catal. Sci. Technol. 2017, 7, 243–250.

14.

15.

16.

17.

18.

19.

S. Ishikawa, D. Jones, S. Iqbal, R. Christian, D. J. Morgan,
D. J. Willock, P. Miedziak, J. K. Bartley, J. Edwards, T.
Murayama, W. Ueda, G. J. Hutchings, “Identification of
the catalytically active component of Cu-Zr-O catalyst for
the hydrogenation of levulinic acid to γ-valerolactone”,
Green Chem. 2017, 19, 225–236.
Y. Goto, K.-i. Shimizu, K. Kon, T. Toyao, T. Murayama,
W. Ueda, “NH3-efficient ammoxidation of toluene byhydrothermally synthesized layered tungsten-vanadium
complex metal oxides”, J. Catal. 2016, 344, 346–353.
S. Ishikawa, T. Murayama, M. Kumaki, M. Tashiro, Z.
Zhang, A. Yoshida, W. Ueda, “Synthesis of Trigonal Mo–
V–M3rd–O (M3rd = Fe, W) Catalysts by Using StructureDirecting Agent and Catalytic Performances for Selective
Oxidation of Ethane”, Top. Catal. 2016, 59, 1477–1488.
T. Murayama, B. Katryniok, S. Heyte, M. Araque, S.
Ishikawa, F. Dumeignil, S. Paul, W. Ueda “Role ofcrystalline structure in allyl alcohol selective oxidation
over Mo3VOx complex metal oxide catalysts”,
ChemCatChem 2016, 8, 2415–2420.
Z. Zhang, S. Ishikawa, Y. Tsuboi, M. Sadakane, T.
Murayama, W. Ueda, “New crystalline complex metaloxides created by unit-synthesis and their catalysis basedon porous and redox properties”, Faraday Discuss. 2016,
188, 81–98.
T. Murayama, N. Kuramata, W. Ueda, “Hydrothermal
Synthesis of W-Ta-O Complex Metal Oxides by
Assembling MO6 (M = W or Ta) Octahedra and Creationof Solid Acid”, J. Catal. 2016, 339, 143–152.
Z. Zhang, H. Yoshikawa, Z. Zhang, T. Murayama, M.
Sadakane, Y. Inoue, W. Ueda, K. Awaga, M. Hara,“Synthesis of Vanadium-Incorporated, PolyoxometalateBased Open Frameworks and Their Applications for
Cathode-Active Materials”, Eur. J. Inorg. Chem. 2016,
2016, 1242–1250.
Y. Goto, K.-i. Shimizu, T. Murayama, W. Ueda,“Hydrothermal synthesis of microporous W-V-O as anefficient catalyst for ammoxidation of 3-picoline”, Appl.
Catal. A: Gen. 2016, 509, 118–122.
Q. He, S. J. Freakley, J. K. Edwards, A. F. Carley, A. Y.
Borisevich, Y. Mineo, M. Haruta, G.J. Hutchings, C. J.
Kiely, “Population and hierarchy of active species in goldiron oxide catalysts for carbon monoxide oxidation”,
Nature Commun. 2016, 7, 12905.

■Reviews
1.

T. Ishida, H. Koga, M. Okumura, M. Haruta, “Advances inGold Catalysis and Understanding the Catalytic
Mechanism”, Chem. Rec. 2016, 16, 2278–2293.

See the annual report in Japanese (4 articles)■Books1.

K. Nomiya, T. Yoshida, S. Matsunaga, “Formation of
Phosphanegold(I) Cluster Cations Mediated by
Polyoxometalates, Molecular Structurres and Catalysis for
Organic Transformations”, in: Aaron P. Roberts (Eds.),
Polyoxometalates: Properties, Structures and Synthesis,
Nova Science Publishers, New York, 2016, pp. 213–242.

■Invited Lectures
1.

14

T. Ishida, “Oxidation Reactions of Organic Compounds

Reports from Research Groups
Catalyzed by Gold Nanoparticles”, Dalian Institute ofChemical Physics, China, 2017.3.13
See the annual report in Japanese (2 lectures)

5.

■Academic Meeting＊International (oral)
1.
H. Murayama, Y. Yamamoto, T. Hasegawa, M. Tone, T.
Ishida, A. Isogai, T. Fujii, M. Okumura, T. Fujitani, T.
Honma, M. Tokunaga, “Adsorptive Reduction of Dimethyl
Trisulfide from Japanese Sake by Supported Noble Metal
Nanoparticles”, FUJIHARA Seminar-70, International
Symposium on New Development of Physical Organic
Chemistry: Construction of Chemical Principles
Determining Structures, Reactions, and Properties 70,
Fukuoka, 2016.4.20
2.
T. Fujita, "CO oxidation on metal oxide-supported gold
catalysts: Correlation between the catalytic activity andmetal-oxygen binding energy of supports", TMU-Yantai
Univ. Joint Workshop, Tokyo Metropolitan University(TMU), 2016.10.5
3.
T. Yoshida, "Low Temperature CO Oxidation over
Polyoxometalate-Supported Gold Clusters", TMU-Yantai
Univ. Joint Workshop, TMU, 2016.10.6
4.
J. Nishigaki, "Oxygen Oxidation of NADH by Au Cluster
Catalyst for Biocatalyst-hybrids Systems", TMU-Yantai
Univ. Joint Workshop, TMU, 2016.10.6
5.
H. Murayama, Y. Yamamoto, T. Hasegawa, M. Tone, E.
Yamamoto, T. Ishida, A. Isogai, T. Fujii, M. Okumura, T.
Fujitani, T. Honma, M. Tokunaga, “Removal of Aged
Odor from Japanese Sake with Supported Gold and Silver
Nanoparticles by Chemical Adsorption”, C&FC2016(International Symposium on Catalysis and Fine
Chemicals 2016), Taipei, Taiwan, 2016.11.12
6.
T. Murayama, M. Haruta, “Development of Gold
Nanoparticulates Catalyst Deposited on Metal Oxides
Synthesized by Hydrothermal Process”, International
Conference on Catalysis and Chemical Engineering,
Baltimore, USA, 2017.2.22
7.
A. Taketoshi, T. Ishida, M. Haruta, “Oxidative
Esterification of Octanal by Gold Nanoparticulate
Catalysts”, TMU-Yantai Univ. Joint Workshop, Yantai,
China, 2017.3.15
8.
T. Murayama, M. Haruta, “Gold Nanoparticulate Catalysts
deposited on Nb2O5”, TMU-Yantai Univ. Joint Workshop,
Yantai, China, 2017.3.15“Effect of metal oxide support in gold catalysts for CO
oxidation”，The 1st International Symposium on Hydrogen
Energy-based Society, TMU, 2016.8.27
M. Mino, T. Murayama, M. Haruta, “NH3-SCR of no on
Vanadium Oxides at Low Temperature”, International
Conference on Catalysis and Chemical Engineering,
Baltimore, USA, 2017.2.23＊Domestic (oral)
See the annual report in Japanese (11 articles)＊Domestic (poster)See the annual report in Japanese (14 articles)■Patents
1.

2.

＊International (Poster)
1. H. Murayama, T. Hasegawa, M. Tone, Y. Yamamoto, T.
Ishida, T. Honma, M. Tokunaga, “Silica supported Au
nanoparticles prepared by impregnatoin method using Au
amino acid complexes”, The French Conference on
Catalysis 2016 (FCCat16), Frejus, France, 2016.5.25-26
2. T. Murayama, M. Haruta, "Deposition of gold nanoparticles
on "solid acid" metal oxide", The 16th International
Congress on Catalysis (ICC-16), Beijing, China, 2016.7.5
3. J. Nishigaki, M. Haruta, "Oxidation of NADH by
Supported Au Clusters for Biocatalyst-hybrid Systems",
The 16th International Congress on Catalysis (ICC-16),
Beijing, China, 2016.7.7
4. T. Fujita, M. Horikawa, T. Takei, T. Murayama, M. Haruta,

15

E. Kiyonaga, K. Hikino, K. Morita, M. Haruta, T.
Murayama, M. Mino, “Thermal power system”, JP6077190,
January 20, 2017 Registered, The Chugoku Electric Power
Co., Tokyo Metropolitan University
M. Haruta, T. Ishida, D. X. Luong, “Producation of gold
composite materials”, JP2017-042768, March 7, 2017
Applied, Tokyo Metropolitan University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

Galvanostatic plating/stripping
Symmetric cell

EnergyChemistry,

Koichi KAJIHARA
Associate Professor /Ph.D.
Inorganic Chemistry, Functional Material Chemistry,
Inorganic Materials/Physical Properties
room:9-246 TEL: +81-42-677-2827
e-mail: kkaji@tmu.ac.jp

Fig. 2 Dissolution/deposition behavior of magnesium in various
electrolyte systems.

Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,Batteries and Fuel Cells
room:9-233 TEL: +81-42-677-2826
e-mail: munakata@tmu.ac.jp

2. 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 temperaturesof ~ 150 °C under non-humidified conditions was promoted. A
prototype fuel cell was developed based on a new electrolyte
system with ionic liquids, and its operation was succeeded at
160 ° C without humidification (Fig. 3).

Doctor’s course -8
Master’s course -17
Bachelor 4 -8

■Outlines of the Research
1. Research on Rechargeable batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of new rechargeable batteries with high energy
density and excellent safety was promoted in order to realize asustainable society based on the effective use of energy, in which
we particularly investigated the use of lithium metal with ~ 10times higher capacity than that of currently-used graphite as an
anode material. In addition, we investigated the use of solid
electrolytes instead of conventional liquid ones to explore newbattery designs (Fig. 1).
Fig. 3 I-V and I-W curives of the developed prototype fuel cellat 160 °C without humidification.
3. Research on optical and electrical properties of inorganicoxides and related materials
Koichi KAJIHARA
Fundamental properties of inorganic oxides, in particular, their
optical and electrical properties, were studied to fully utilize thefunctionalities of oxides. Environmentally-friendly syntheticroutes to prepare polysilsesquioxane (PSQ) liquids without using
cosolvent (e.g. alcohols and other organic solvents) weredeveloped. This finantial year we found that the liquid-liquid
phase separation is not essential for the preparation of PSQ
liquids (Fig. 4). We also examined photchemical reactions andphotoluminescence of interstital Cl2 molecules and related
interstitial chlorine species in synthetic silica glasses, which areimportant for optical materials of photolithography, andidentified a new interstitial molecule ClClO (Fig. 5).

Fig. 1 Photograph of all-solid-state battery developed by using asolid electrolyte.
The fundamental reserch on rechargeable magnesium batteries
was also promoted, in which the electolyte system appropriate
for reversible dissisolution/deposition of magnesium metal wasparticularly investigated (Fig. 2).

Fig. 4 Synthtesis of polysilsesquioxane liquids.

16

Reports from Research Groups
7. Kiyoshi KANAMURA, Yuto YAMADA, Koji ANNAKA,
Natsuko NAKATA, Hirokazu MUNAKATA, Electrochemical
Evaluation of Active Materials for Lithium Ion Batteries by One(Single) Particle Measurement, Electrochemistry, 84, 2016, pp.
759-765.
8. Erqing Zhao, Furui Ma, Yongcheng Jin, Kiyoshi Kanamura,
Pechini synthesis of high ionic conductivity Li1.3Al0.3Ti1.7(PO4)3
solid electrolytes: The effect of dispersant, Journal of Alloys andFig. 5 Reactions of interstitial chlorine-related species insynthetic silica glass.

Compounds, 680, 2016, pp. 646-653.

■Papers with Peer Review

Yongcheng Jin, Jing Wang, Lan Xiang, Hirokazu Munakata,

1. Wenchao Yan, Jicheng Jiang, Wei Liu, Deye Sun, Erqing Zhao,

Kiyoshi Kanamura, Synthesis and Evaluation of Microspherical

Yongcheng Jin, Kiyoshi Kanamura, Effect of precipitators on theLi1.2Mn0.54Co0.13Ni0.13O2 through Carbon Dioxides-assisted Co-

morphologies

precipitation Method for Lithium-ion Battery, Electrochimica

andelectrochemical

properties

9. Wenchao Yan, Jicheng Jiang, Wei Liu, Xiao Yan, Deye Sun,of

Li1.2Mn0.54Ni0.13Co0.13O2 via rapid nucleation and post-

Acta, 212, 2016, pp. 16-24.

solvothermal method, Electrochimica Acta, 224, 2017, pp 161-

10. Shaoyin Zhu, Yanqing Wang, Jicheng Jiang, Xiao Yan, Deye

170.

Sun, Yongcheng Jin, Cewen Nan, Hirokazu Munakata, Kiyoshi

2. Kei NISHIKAWA, Nobuyuki ZETTSU, Katsuya TESHIMA,

Kanamura, Good Low-Temperature Properties of Nitrogen-

KiyoshiElectrochemical

Enriched Porous Carbon as Sulfur Hosts for High-Performance

Characteristics in the Individual Needle-like LiCoO2 Crystals

Li–S Batteries, ACS Applied Materials and Interfaces, 8, 2016,

Synthesized by Flux Growth, Electrochemistry, 85, 2017, pp. 72-

pp. 17253-17259.

76.

11. Shaoyin Zhu, Jiaojiao Yu, Xiao Yan, Erqing Zhao, Yanqing

3. Toshihiko Mandai, Yasuhiro Akita, Shunsuke Yagi, Minato

Wang, Deye Sun, Yongcheng Jin, Kiyoshi Kanamura, Enhanced

Egashira, Hirokazu Munakata, Kiyoshi Kanamura, A keyelectrochemical performance from cross-linked polymeric

concept of utilization of both non-Grignard magnesium chloride

network as binder for Li–S battery cathodes, Journal of Applied

and imide salts for rechargeable Mg battery electrolytes, Journal

Electrochemistry, 46, 2016, pp. 725-733.

of Materials Chemistry A, 5, 2017, pp. 3152-3156.

12. Soichiro KAWAKAMI, Hirokazu MUNAKATA, Yasuhiro

4. Jungo WAKASUGI, Hirokazu MUNAKATA, Kiyoshi

AKITA,

KANAMURA, Thermal Stability of Various Cathode Materials

Optimization of Silicon Nanoparticle Anodes, Electrochemistry,

against Li6.25Al0.25La3Zr2O12 Electrolyte, Electrochemistry, 85,

84, 2016, pp. 243-253.

2017, pp. 77-81.

13. Mao Shoji, Hirokazu Munakata and Kiyoshi Kanamura,

5. Yuta Maeyoshi, Shohei Miyamoto, Yusaku Noda, Hirokazu

Fabrication of All-Solid-State Lithium-Ion Cells Using Three-

Munakata, Kiyoshi Kanamura, Effect of organic additives on

Dimensionally Structured Solid Electrolyte Li7La3Zr2O12 Pellets,characteristics of carbon-coated LiCoPO4 synthesized by

Frontiers in Energy Research, 4, 2016, article 32.

hydrothermal method, Journal of Power Sources, 337, 2017, 92-

14. Yuko Fukuda, Koichi Kajihara, Shiori Kakinoki, Junhyeok

99.

Jang,

6. Hidetoshi Abe, Masaaki Kubota, Miyu Nemoto, Yosuke

alkylsilsesquioxane)

Masuda, Yuichi Tanaka, Hirokazu Munakata, Kiyoshi Kanamura,hydrolytic polycondensation of n-alkyltrialkoxysilanes: effects

High-capacity thick cathode with a porous aluminum currentof liquid-liquid phase separation during aging and alkyl chain

collector for lithium secondary batteries, Journal of Power

length on structure and viscosity, Dalton Trans. 45, 2016, 15532-

Sources, 334, 2016, 78-85.

15540.

KANAMURA,

Intrinsic

17

Kiyoshi

Hirohisa

KANAMURA,

Yoshida,liquids

Characterization

KiyoshipreparedKanamura,byandPoly(n-cosolvent-freeReports from Research Groups
15. Linards Skuja, Koichi Kajihara, Krisjanis Smits, Andrejs

7. K. Nishikawa, C. Li, K. Kanamura, Advanced Single Particle

Silins, Hideo Hosono, Luminescence and Raman detection of

Measurement Technique for Fundamental Study of First

molecular Cl2 and ClClO molecules in amorphous SiO2 matrix,

Charging Mechanism of One Silicon Particle, PRiME2016

J. Phys. Chem. C 121, 2017, DOI: 10.1021/acs.jpcc.6b13095.

230th ECS Meeting, October 2016, Honolulu, Hawaii, USA.
8. S. Lim, Y. Yamada, S. S. Kim, K. Kanamura, Electro Chemical■Reviews

Properties of Hard Carbon Single Particles for Anode in Sodium

See the annual report in Japanese (6 articles)

Ion Batteries, PRiME2016 230th ECS Meeting, October 2016,■BooksSee the annual report in Japanese (2 articles)

Honolulu, Hawaii, USA.

■Invited Lectures

9. Y. Maeyoshi, S. Miyamoto, H. Munakata, and K. Kanamura,See the annual report in Japanese (12 articles)

Electrochemical Characterization of Carbon-Coated LiCoPO4■Academic Meeting

Synthesized By Hydrothermal Method Using Various Carbon＊International

Sources, PRiME2016 230th ECS Meeting, October 2016,

1. K. Kanamura, T. Kimura, M. Shoji, and H. Munakata, All

Honolulu, Hawaii, USA.

Solid State Battery with LLZ Solid Electrolyte and Li Metal

10. J. Wakasugi, H. Munakata, K. Kanamura, Formation of an

Anode, IMLB2016 International Meeting on Lithium Battery,

Intermediate Layer Between Lithium Metal and Li7La3Zr2O12 toJune 2016, Chicago, Illinois, USA.

Reduce Its Interfacial Resistance, PRiME2016 230th ECS

2. Mao Shoji, Takashi Narushima, Takeshi Kimura, Hirokazu

Meeting, October 2016, Honolulu, Hawaii, USA.

Munakata, Kiyoshi Kanamura, Investigation of Li source

11. M. Haibara, K. Ouchi, H. Munakata, K. Kanamura,influence on the sinterability of garnet-type solid electrolyte

Preparation of Polyimide Separator with 3-DimensionallyLi6.25Al0.25La3Zr2O12, 229th ECS MEETING, May 2016,

Ordered Macroporous Structure Using Polystyrene Sphere

Sandiego, USA.

Template for Lithium Metal Secondary Battery, PRiME2016

3. Takeshi KIMURA, Kyoko KOZUKA, Naoto SAITO, Mao230th ECS Meeting, October 2016, Honolulu, Hawaii, USA.

SHOJI, Takashi NARUSHIMA, Hirokazu MUNAKATA,

12. K. Kozuka, K. Nitta, M. Shoji, T. Kimura, H. Munakata, K.

Kiyoshi KANAMURA, Formation of LiCoO2 / Li3BO3

Kanamura, Formation of Positive Composite Electrode By

Composite Cathode on Al doped Li7La3Zr2O12 Solid-State

Aerosol Deposition Method for All-Solid-State Rechargeable

electrolyte by Aerosol Deposition Method, 229th ECS

Lithium Batteries, PRiME2016 230th ECS Meeting, October

MEETING, May 2016, Sandiego, USA.

2016, Honolulu, Hawaii, USA.

4. L. Skuja, K. Kajihara, K. Smits, H. Hosono, Interstitial

13. S. Kikuchi, S. Hashizume, H. Munakata, K. Kanamura,

Chlorine Molecules in SiO2 Glass, 11th International

Preparation of Electrolyte Membrane Composite Composed of

Symposium on SiO2, Advanced Dielectrics and Related Devices,

Ionic Liquid and Porous Polyimide for Non-Humidified

June 2016, Nice, France

Intermediate-Temperature Fuel Cell, PRiME2016 230th ECS

5. M. Suda, K. Kajihara, K. Kanamura, Sol−gel-derived

Meeting, October 2016, Honolulu, Hawaii, USA.

silica−(Gd,Pr)PO4 transparent glass-ceramics applicable to14. K. Sasaki, H. Munakata, and K. Kanamura, Investigation of

narrow-band UVB phosphors, The 9th International Symposium

Various Factors for Capacity Fading of Li-Rich Solid Solution

on Inorganic Phosphate Materials (ISIPM-9), September 2016,

Cathode, PRiME2016 230th ECS Meeting, October 2016,

Tokyo, Japan

Honolulu, Hawaii, USA.

6. H. Yamashita, T. Ogami, K. Kanamura, Effects of the carbon

15. S. Miyamoto, Y. Noda, H. Munakata, K. Ohira, S. Yoshida,sources on the electrochemical properties of LiMn0.8Fe0.2PO4/C

D. Shibata, K. Kanamura, Cycle Performance of Metal-

for lithium-ion batteries, The 9th International Symposium on

Substituted LiCoPO4 of Coarse Particles, PRiME2016 230th

Inorganic Phosphate Materials (ISIPM-9), September 2016,

ECS Meeting, October 2016, Honolulu, Hawaii, USA.

Tokyo, Japan

16. T. Omura, Y. Yamada, Y. Noda, S. Miyamoto, H. Munakata,18

Reports from Research Groups
K. Ohira, S. Yoshida, D. Shibata, K. Kanamura, Evaluation of Fe＊Domestic
See the annual report in Japanese (22 articles)

Substitution Effect on the Electrochemical Properties of
LiMnPO4 By Single Particle Measurement, PRiME2016 230th■Awards

ECS Meeting, October 2016, Honolulu, Hawaii, USA.

1. Mayu Suda, Sol–gel-derived silica–(Gd,Pr)PO4 transparent
glass-ceramics applicable to narrow-band UVB phosphors,
Young Scientist Presentation Award, The 9th International
Symposium on Inorganic Phosphate Materials, ISIPM-9, Sep.
25-28, 2016, Tokyo Metropolitan University, Tokyo

17. H. Abe, M. Nemoto, M. Kubota, K. Imazawa, H. Munakata,K. Kanamura, Importance and Possibility of the First Discharge
for High Energy Lithium Metal Anode Rechargeable Battery,PRiME2016 230th ECS Meeting, October 2016, Honolulu,
Hawaii, USA.
18. H. Inoue, Y. Akita, H. Munakata, K. Kanamura, Investigationof Discharge Products of Mg-Air Battery with Non-Aqueous
Ether-Based Electrolytes, PRiME2016 230th ECS Meeting,
October 2016, Honolulu, Hawaii, USA.
19. Kiyoshi Kanamura, Development of Next Generation
Batteries with Li Metal Anode, IMSE2016, October 2016,
Qingdao University of Science and Technology, Qingdao, China.
20. K. Honda, H. Munakata, K. Kanamura, Characteristic
Evaluation of the Cathode for Lithium Sulfur Battery and Its
Application to Magnesium Sulfur Battery, IMSE2016, October
2016, Qingdao University of Science and Technology, Qingdao,
China.
21. Y. Shibata, S. Kondo, T. Asai, T. Takagi, H. Munakata, K.
Kanamura1,

Developmentof

Quasi-solid

Composite

Electrolytes for Improving Electrochemical Properties of 3Dstructured Batteries, IMSE2016, October 2016, Qingdao
University of Science and Technology, Qingdao, China.
22. Jie Yu, Shojiro Kikuchi, Hirokazu Munakata, Kiyoshi
Kanamura, Development of proton-conducting ionic liquid/three-dimensionally ordered macroporous polyimide composite
membrane for non humidified intermediate temperature fuelcells, The 57th Battery Symposium in Japan, November 2016,
Makuhari, Chiba, Japan.
23. K. Kajihara, S. Yamaguchi, M. Suda, K. Kanamura, Highlytransparent efficient silica−REPO4 glass-ceramic phosphorsprepared by cosolvent-free sol−gel method,CerSJ-GOMD

Joint Symposium on Glass Science and Technologies, November
2016, Kyoto, Japan
24. H. Munakata, K. Kozuka, K. Nitta, M. Shoji, T. Kimura, K.
Kanamura, Cathode Fabrication on Li6.25Al0.25La3Zr2O12 Solid
Electrolyte by Aerosol Deposition Method, The 8th Ge-It-Jp
Meeting of Electrochemists, Decemmber 2016, Chiba, Japan.

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

Chemistry,

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

Fig.2. Realtime observation of the energy transfer between dyes
adsorbed on the clay surface.

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

Doctor’s course -1
Master’s course -13
Bachelor 4 -8

■Outlines of the Research
Our group challenges to control photochemical reactions
such as electron and energy transfer, by controlling theorientation and alignment of dyes on the inorganic surfaces.
Recently, organic/inorganic hybrids composed of porphyrins
and layered materials have been the subject of intensive
investigations to explore their novel properties andfunctionalities. We found out that a precise matching of
distances between the negatively charged sites on the clay
mineral layers and that between the positively charged sites inthe dye molecule is one of the most important factors todetermine the structure of the clay–dye complex. We havetermed this the “Size-Matching Rule” Our goal is finding out a
new methodology to control molecular assembly structure andrealizing functionalized photochemical reaction systems suchas an artificial light harvesting system.
1. Research on Artificial light harvesting system
Shinsuke TAKAGI, Tetsuya SHIMADA
The quantitative excited energy transfer reaction between
cationic porphyrins on an anionic clay surface was successfully
achieved. The efficiency reached up to ca. 100% owing to the“Size- Matching Rule” that is our original technique. It was
revealed that the important factors for the efficient energy
transfer reaction are (i) suppression of the self-quenching
between adjacent dyes, and (ii) suppression of the segregatedadsorption structure of two kinds of dyes on the clay surface.
These findings indicate that the clay/porphyrin complexes arepromising and prospective candidates to be used forconstruction of an efficient artificial light-harvesting system.
Especially when phthalocyanine was used as energy acceptor,
light harvesting type energy transfer was realized.

Fig.3. An example of our methodology to control the adsorption
structure of dyes on the clay surface by using a suitable clay species.

3. Research on Transparent Clay Membrane Systems
Shinsuke TAKAGI, Tetsuya SHIMADA
Cationic porphyrin was successfully intercalated intotransparent clay membrane by developing the new strategy forthe sample preparation conditions. When water : ethanol = 1 :
2 (v : v) was used as solvent for porphyrin penetration process,high density intercalation of porphyrin into the clay membrane
was achieved. In the interlayer space, porphyrin molecules do
not aggregate owing to inter-charge distance matching effect(size-matching effect), even at high density condition.
Judging from XRD and absorption measurements, theorientations of the porphyrins in the clay layers should bealmost parallel to the clay nanosheet as monolayer. Because thefluorescence quantum yield did not depend on its loading level,
it is turned out that intercalated TMPyP in the clay film keeps
the photo-activity even under the high density conditions.

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

20

Reports from Research Groups
10.

Fig.4. Humidity-responsive transparent membrane of clay with
MgTMPyP prepared by the new method.

11.
4. Research on Novel Hybrid Complex of Semiconductor
Nano-Sheet and Dye
Shinsuke TAKAGI, Tetsuya SHIMADA
A semiconductor nano-sheet was focused as our new
research target in addition to the "insulator" clay nano-sheet.
We expected we effectively extend our distinctive research
about clay-dye hybridization methodology in order to create
new materials with good electron transfer property for artificial
photosynthesis system. We synthesized a novel TiO2 nano-sheet(TNS) and characterized it in detail. We observed adsorption
behavior of porphyrin dyes on the TNS and photochemicalinteraction between the dyes and the TNS.

12.

■Books1.

■Papers with Peer Review
1.

2.

3.

4.

5.

6.

7.

8.

9.

4734-4740 (2017).
Unique Fluorescence Behavior of Dyes on the Clay
Minerals Surface: Surface Fixation Induced Emission(S-FIE), D. Tokieda, T. Tsukamoto, Y. Ishida, H. Ichihara,
T. Shimada, S. Takagi, J. Photoch. Photobio. A (Invited
Feature Articele), in press.
“Size-Matching Effect” in Cationic Porphyrin-Titania
Nanosheet Complex, A. Sonotani, T. Shimada, S. Takagi,
Chem. Lett., in press.
Photoinduced electron transfer in layer-by-layer thin solid
films containing cobalt oxide nanosheets, porphyrin, andmethylviologen, R. Sasai, Y. Kato, W. Soontornchaiyakul,
H. Usami, A. Masumori, W. Norimatsu, T. Fujimura, S.
Takagi, Phys. Chem. Chem. Phys., in press.

Inorganic Nanosheets and Nanosheet-Based Materials(Chapter 1.&14. ), S. Takagi, Springer (2017).
+2 articles in Japanese (See the annual report in Japanese)

Photophysical Properties and Adsorption Behaviors ofNovel Tri-Cationic Boron(III) Subporphyrin on Anionic
Clay Surface, T. Tsukamoto, T. Shimada, S. Takagi, ACS
Appl. Mater. Interfaces, 8, 7522–7528 (2016).
Kinetic analysis by laser flash photolysis of porphyrin
molecules' orientation change at the surface of silicate
nanosheet, M. Eguchi, T. Shimada, H. Inoue, S. Takagi, J.
Phys. Chem. C, 120, 7428–7434 (2016).
Room Temperature Phosphorescence from a Guest
Molecule Confined in Restrictive Space of an Organic–
Inorganic Supramolecular Assembly, Y. Ishida, T.
Shimada, E. Ramasamy, V. Ramamurthy, S. Takagi,
Photochem. Photobiol. Sci., 15, 959-963 (2016).
Sequential energy and electron transfer in athree-component system aligned on a clay nanosheet, T.
Fujimura, E. Ramasamy, Y. Ishida, T. Shimada, S. Takagi,
V. Ramamurthy, Phys. Chem. Chem. Phys., 18,5404-5411 (2016).
Supramolecular surface photochemistry: cascade energy
transfer between encapsulated dyes aligned on a clay
nanosheet surface, T. Tsukamoto, E. Ramasamy, T.
Shimada, T. Takagi, V. Ramamurthy, Langmuir, 32,
2920-2927 (2016).
Photo-induced morphological winding and unwinding
motion of nanoscrolls composed of niobate nanosheetswith a polyfluoroalkyl azobenzene derivative, Y.
Nabetani, H. Takamura, A. Uchikoshi, S Z. Hassan, T.
Shimada, S. Takagi, H. Tachibana, D. Masui, Z. Tong, H.
Inoue, Nanoscale, 8, 12289-12293 (2016).
Energy Transfer among Three Dye Components in a
Nanosheet-Dye Complex: An Approach To Evaluating
the Performance of a Light-Harvesting System, Y. Ohtani,
S. Kawaguchi, T. Shimada, S. Takagi, J. Phys. Chem. C,
121, 2052-2058 (2017).
Adosorption And Photochemical Behavior Of
Mono-Cationic Porphyrin Onto Synthetic Saponite, S.
Wakayama, S. Takagi, T. Shimada, Clay Science, 20, 1-3(2017).
Trapping of excess energy in a nano-layered
microenvironment to promote chemical reactions, V.
Ramakrishnan, Y. Nabetani, D. Yamamoto, T. Shimada, H.
Tachibana, H. Inoue, Phys. Chem. Chem. Phys., 19,■Invited Lectures
1.

2.

3.

4.

5.

6.

7.

Unique Photochemical Behavior of Dyes on the Inorganic
Surfaces and Their Application to Artificial
Photosynthesis, S. Takagi, International Symposium on
Novel Chemistry and Engineering, Rayong (Thailand),
June, Invited lecture, 2016.
Sequential Energy and Electron Transfer Reaction in
Organic Capsule Molecules – Inorganic Nanosheet
Complexes, S. Takagi, International Symposium on
Novel Chemistry and Engineering, Rayong (Thailand),
June, Invited lecture, 2016.
Construction of Nano Structured Materials Aiming at
Artificial Light Harvesting System, S. Takagi, UK-Japan
Solar Driven Fuel Synthesis Workshop: Materials,
Understanding and Reactor Design, Tokyo (Japan), June,
Invited lecture, 2016.
Surface-Fixation Induced Emission of Dyes on Inorganic
nanosheets, S. Takagi, HKUST Department of Chemistry
Symposium, Hong Kong (China), November, Invitedlecture, 2016.
Nanostructure Control and Photochemistryof
Nanosheet-dye Complexes, S. Takagi, Annual Meeting on
Photochemistry 2016, Tokyo (Japan), September, Invitedlecture, 2016.
Photochemical Epoxidation With Light Harvesting
Functionality On The Inorganic Surfaces, S. Takagi, T.
Tsukamoto, D. Tatsumi, T. Shimada, 2017 International
Conference on Artificial Photosynthesis (ICARP2017) ,Kyoto (Japan), March, 2017.
Environment-responsive materials composed by dyes andlayered compounds, S. Takagi, The 1st International
Workshop on Chromogenic Materials and Devices,
Tsukuba (Japan), March, 2017.
+1 article in Japanese (See the annual report in Japanese)■Academic Meeting＊International
1.
A construction of artificial light-harvesting system withenergy migration functionality of xanthene derivative on
the inorganic nano-sheet, Y. Ohtani, T. Shimada, S.
21

Reports from Research Groups

2.

3.

4.

5.

6.

7.

8.

Photosynthesis, Exellent Poster Award，March，2017.

Takagi, XXVIth IUPAC Symposium on Photochemistry ,Osaka (Japan), April, 2016.
How to control collision reactions on the clay surface forhydrogen production ,N. Morita, Y. Ohtani, T.
Shimada, S. Takagi
The 1st International Symposiumon Hydrogen Energy-based Society ,Tokyo (Japan) ,August ,2016 .
Surface-fixation induced emission (S-FIE) of dyes on theclay surface, S. Takagi, The 3rd Asian Clay Conference(ACC-2016), Guangzhou (China), November, 2016.
Enhanced emission of stilbazolium derivatives on ananionic clay surface, N. Kudo, D. Tokieda, T. Tsukamoto,T. Shimada, S. Takagi, The 3rd Asian Clay Conference(ACC-2016), Guangzhou (China), November, 2016.
Enhanced Emission of Dyes on an Anionic Clay Surface:
Surface-fixation Induced Emission (S-FIE), S. Takagi, T.
Shimada, Asian Photochemistry Conference (APC) ,Nanyang (Singapore), December, 2016.
Construction of Clay-dye Membrane Aiming at
Environment Responsive Light-harvesting System, H.
Nishina, S. Hoshino, Y. Ohtani, T. Shimada, S. Takagi,
Asian Photochemistry Conference (APC) , Nanyang(Singapore), December, 2016.
Novel Photo-oxygenation Reaction with Light-harvesting
Functionality Through the Active Species Transfer on the
Clay Surface, S. Suzuki, D. Tatsumi, T. Tsukamoto, T.
Shimada, S. Takagi, Asian Photochemistry Conference(APC) , Nanyang (Singapore), December, 2016.
The construction of inorganic－organic complexes bysemiconductor nanosheets, K. Sano, A. Sonotani, D.
Tatsumi, T. Shimada, S. Takagi, H. Inoue, 2017
International Conference on Artificial Photosynthesis(ICARP2017) , Kyoto (Japan), March, 2017

＊Domestic
See the annual report in Japanese (40 articles)■Awards
1.

2.
3.

4.

5.

6.

7.

8.
9.

Amane SONOTANI, The 67th Divisional Meeting on
Colloid & Interface Chemistry, International Symposium,
Best Poster Award, September, 2016.
Nana KUDO, The Clay Science Society of Japan Student
Research Encouragement Award, September, 2016.
Shunpei SUZUKI, The Clay Science Society of Japan
Student Research Encouragement Award, September,
2016.
Haruka NISHINA, The Clay Science Society of Japan
Student Research Encouragement Award, September,
2016.
Nana KUDO, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Presentation Award, September, 2016.
Keito SANO, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Poster Award, September, 2016.
Masahiro TABUCHI, Summer seminar of Forum on
Low-dimensional photofunctional Materials, Excellent
Poster Award, September, 2016.
Shinsuke TAKAGI, TMU Leading Professor, November,
2016.
Keito SANO, 2017 International Conference on Artificial

22

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

Oxidation

Recognition,

the dinuclear complex showed NIR luminescence fromneodymium by UV light irradiation and NIR luminescencefrom ruthenium by visible light irradiation. It was found thatmost of the dinuclear complex dissociated to mononuclear
complexes in acetone.

Catalyst,c) Synthesis of macrocyclic multinuclear complexes, their
inclusion behavior, and its application to photocatalyst:
Utilizing the mononuclear ruthenium complex with a tridentate
ligand containing a 4,4’-bipyridyne moiety as a bridging
moiety as the unit, we have found that the macrocyclic
trinuclear, molecular triangle, and tetranuclear complexes,
molecular square were effectively obtained by self-assembly.
We have already reported that two molecules of aromaticcompound were included in the cavity of molecular square.
This time, we found that two molecules of cationic anthraceneamide derivatives were included. Then the photodimerizationof anthracene amide derivatives by visible light irradiation has
been examined in the presence of the square, and thedimerization was found to be accelerated by the square up to
TON more than 200. It was assumed that the square catalyzed
the photodimerization as the sensitizer since anthracene
derivative was not excited by visible light. It was revealed thatthe molecular square not only showed the inclusion behavior
but also worked as the photocatalyst, that is, light-harvesting
host.

Novel

Master’s course -6
Bachelor 4 -2 (Foreign student 1)■Outlines of the Research
1. Development of Photofunctional Ruthenium Complexes
Motowo YAMAGUCHIa) Switching function of ligand photodissociation: New
mixed-ligand type ruthenium complex with a terpyridine-type
ligand derivative having imidazolyl groups which wasreversibly protonated and deprotonated by acid and base has
been synthesized and the control of its ligand photodissociation
reaction has been examined. The reversible protonation anddeprotonation was affirmed, then the ligand photodissociation
reaction has been examined in acetone. It was found that therate of photo-induced dissociation reaction of the complex was
considerably inhibited by a factor of a hundred in the presenceof base. The high regulation of the rate of the reaction was
successfully attained by acid and base. Thus the imidazolylgroups introduced to the terpyridine-type ligand of the complex
was found to be the useful switch being controllable by theaddition of acid and base, and its capability has been improved
very much in the control of the rate of ligand dissociation of thecomplex. Further studies for its application are in progress.

Fig.2 Inclusion phenomena of the Ru4 molecular squared) Synthesis of macrocyclic tetranuclear complexes and their
inclusion behavior: Utilizing the mononuclear ruthenium
complex with a tridentate ligand containing a pyrazine moiety
as a bridging moiety as the unit, we have found that themacrocyclic tetranuclear complex, molecular square, wereselectively obtained by self-assembly. We have examined avariety of reaction conditions, and found out that the reaction in
2-methoxyethanol at 120 °C successfully gave rise to themacrocyclic tetranuclear ruthenium complex in good yield. It
was found that a rod-like anion, such as a thiocyanide ion or an
azide ion, or a spherical ion, such as a halide ion, was includedin the cavity of the macrocyclic tetranuclear ruthenium
complex, and the inclusion behavior has been examined by 1H
NMR and DOSY spectra. Furthermore, electrochemical studies
have been done by CV and DPV. It was found that themacrocyclic tetranuclear ruthenium complex was oxidized inthree steps. In case of DPV studies in the presence of halide ion,
it was revealed that the included chloride or bromide ion wasprotected from anodic oxidation.

Fig.1 Control of the ligand photodissociation by eternal stimuli

2. Development of Novel Ionic Aggregation-Induced
Emission and Solid-State Flurophores
Kiyoshi SATO
Aggregation-induced emission (AIE) phenomenon has attracted
great attention. Although a large number of AIE-active
compounds based on Tang’s AIE fluorogens (AIEgens) havebeen reported in the last decade, most of them are neutral. Ionicb) Synthesis of heterodinuclear ruthenium-neodymium
complex and its photochemical behavior: New heterodinuclear
ruthenium-neodymium complex has been synthesized by using
the ruthenium complex having a bridging ligand. The
mononuclear neodymium complex showed luminescence in thenear-infrared (NIR) region by ultra-violet light irradiation but
no luminescence by visible light irradiation. On the other hand,23

Reports from Research Groups
	
 
	
 

	
 

fluorophores have advantages for the design of AIEgens since
their solubility and emission properties could be tuned by bothof the cation and anion. In particular, changes of the counterions would significantly influence the solid-state fluorescence,
because the size and shape of counter ion and the interactions
between ion-pair could affect the crystal packing structures. In
this study, propeller-shaped pentaphenylimidazolium salts offive different counter anions were investigated as a novel ionic
AIEgen and solid-state fluorophore. They show AIE activity
with remarkable differences on their counter anions andanion-depended solid-state fluorescence. These AIE-active andsolid-state emissive ionic organic dyes have a promisingfeature for practical application as bio-imaging probes andenergy-saving luminescent displays or light sources.

＊International
1. Sakurako
TAMAI,
Kiyoshi
SATO,
MotowoYAMAGUCHI, Synthesis of Ruthenium-neodymium
Dinuclear Complex and Control of the Ligand Exchange,
International Symposium on Lanthanide Coordination
Chemistry (ISLCC), June, 2016, Sagamihara, Japan.
2. Motowo YAMAGUCHI, Synthesis, Inclusion Behavior,and Sensitizing Ability of Macrocyclic Tetranuclear
Ruthenium Complexes: Light-harvesting Host, 42ndInternational Conference on Coordination Chemistry(ICCC 2016), July, 2016, Brest, France.
3. Motowo YAMAGUCHI, Photofunctional Ruthenium
Complexes: Catalyst, Switching, and Light-harvesting
Host, The 23rd International SPACC Symposium, Nov.,
2016, Okayama, Japan.

3. Synthesis and Properties of Polycyclic Azonia Aromatic
Compounds by Multiple Photocyclization
Kiyoshi SATO
Nitrogen-doped graphenes have been the subject of recent
attention because they exhibit good electro-catalytic activity forthe oxygen reduction reaction of fuel cells. Polycyclic azonia
aromatic compounds, in which some bridgehead carbon atoms
are replaced by quaternary nitrogen atoms, represent a newclass of N-doped graphenes with additional properties such as
good solubility for polar solvents and high fluorogence. We
have recently developed a facile synthetic strategy to preparenovel diazonia derivatives of hexabenzoperylene, a non-planar
nano-scaled cationic N-doped graphene, by using multiple
photo-induced
dehydrocyclizationof
1,2,6-triphenylpyridinium derivatives. In the present research, thephotoreactions of the bis-bridged 1,2,4,6-tetraphenyl-	 pyridinium cations with alkyl chains (n = 2 and 3) and two
dimethyl derivatives were newly investigated in order to clarify
the scope and limitations of this reaction. The photo-irradiation
to bis-ethylenebridged (n = 2) and N-(3,5-dimethyl)phenyl
derivatives gave the biscyclized photoproducts. In contrast, thereactions of the derivatives with longer alkyl chain bridged (n =3) or 3,5-dimethyl on the pyridinium ring were terminated at
monocyclization probably because the conformations of themonocyclized products are unfavorable for the second
cyclization. In addition, when the irradiation time of thephotoreaction of bis-ethylenebridged (n = 2) derivative waslengthened, unprecedented photo-dehydrogenation occurredand a seven aromatic ring fused compound was yielded as the
final photoproduct. These reactions would be expected to beefficient synthetic methods for electro-active and luminescentorganic materials.

Fig.4 Photobiscyclization of 1,2,6-Triphenylpyridinium Cations■Papers with Peer Review
Reinvestigation

of

the

Photoreaction	 ■Academic MeetingFig.3 Crystal Structure of Ionic AIEE dye

1.

	
 

1,4-Bis(2,4,6-triphenylpyridinio)benzene: Synthesis of a
Diazonia Derivative of Hexabenzoperylene by Multiple
Photocyclization, K. Sato, Y. Seki, S. Suga, Y. Ikeda, M.
Yamaguchi, J. Photochem. Photobiol., A, 331, 8-16
(2016)

of24＊Domestic
4. Kento AOSHIMA, Aya HAMAZAKI, Kiyoshi SATO,
and Motowo YAMAGUCHI, Inclusion Behavior andElectrochemical
Propertyof
Pyrazine-bridged
Macrocyclic Tetranuclear Ruthenium Complexes, 66th
Conference on Coordination Chemistry of Japan, Sept.,
2016, Fukuoka. (in Japanese)
5. Shota SHIBATA, Ryota MORIYAMA, Kiyoshi SATO,
and Motowo YAMAGUCHI, Inclusion Behavior andPhotodimerization of Anthracene Derivative to
Macrocyclic Tetranuclear Ruthenium Complex ， 66th
Conference on Coordination Chemistry of Japan, Sept.,
2016, Fukuoka. (in Japanese)
6. Ako KOBAYASHI, Kiyoshi SATO, and Motowo
YAMAGUCHI, Synthesis of Ruthenium-neodymium
Dinuclear Complex and The Luminescence Behavior，
66th Conference on Coordination Chemistry of Japan,
Sept., 2016, Fukuoka. (in Japanese)
7. Motowo YAMAGUCHI, Ako KOBAYASHI, Tomofumi
EGUCHI, Taiga MASANO, Kiyoshi SATO, Switching ofphotochemical ligand release on ruthenium complexes byacid and base, 66th Conference on Coordination
Chemistry of Japan, Sept., 2016, Fukuoka. (in English)
8. Sachio KIMURA, Motowo YAMAGUCHI, and Kiyoshi
SATO, Solid-State Fluorescence and Aggregation-Induced
Emission Enhancement of Pentaphenylimidazolium Salts，27th Symposium on Physical Organic Chemistry, Sept.
2016, Hiroshima. (in Japanese)
9. Moe TORII, Motowo YAMAGUCHI, and Kiyoshi SATO,
Synthesis and Properties of Azoniahexabenzoperylene byMultiple Photocyclization, 27th Symposium on PhysicalOrganic Chemistry, Sept. 2016, Hiroshima. (in Japanese)
10. Kengo NOZAKI, Motowo YAMAGUCHI, and Kiyoshi
SATO, Synthesis and Photophysical Chacterization of
2,6-Diarylpyridiniums, 27th Symposium on PhysicalOrganic Chemistry, Sept. 2016, Hiroshima. (in Japanese)
11. Moe TORII, Motowo YAMAGUCHI, and Kiyoshi SATO,
Synthesis and Properties of Non-Planar Polycyclic Azonia

Reports from Research Groups
	
 
	
 
12.

13.

14.

15.

	
 

Aromatic Compounds, 6th CSJ Chemistry Festa, Nov.
2016, Tokyo (in Japanese)
Kengo NOZAKI, Motowo YAMAGUCHI, and Kiyoshi
SATO, Influence of Substituents and Steric Structure on
the Fluorescence Property of 1,2,4,6-Tetraphenylpyridinium, 6th CSJ Chemistry Festa, Nov. 2016, Tokyo(in Japanese)
Sachio KIMURA, Motowo YAMAGUCHI, and Kiyoshi
SATO, Aggregation-Induced Emission Enhancement andSolid-State Fluorescence of Pentaphenylimidazolium Salts，
97th Annual Meeting of Chemical Society of Japan, Mar.
2017, Yokohama. (in Japanese)
Moe TORII, Motowo YAMAGUCHI, and Kiyoshi SATO,
Photobiscyclization of Bridged 1,2,6-Triohenylpyridinium
Cations, 97th Annual Meeting of Chemical Society ofJapan, Mar. 2017, Yokohama. (in Japanese)
Kengo
NOZAKI,
YurikoTAKEI,
MotowoYAMAGUCHI, and Kiyoshi SATO, Rational Design of
Novel
Fluorescent
1,2,4,6-Tetraphenylpyridinium
Derivatives, 97th Annual Meeting of Chemical Society ofJapan, Mar. 2017, Yokohama. (in Japanese)

25

	
 

	
 

Reportss from Re
esearch Groups
Uchiyamma Laboraatory■Members
Katsumi UCH
HIYAMA
Professor /Dr. Pharmacol.
Analytical Cheemistry, Micro Chemistry, Miccro-TAS, Laserr
spectrometry
4877
room: 9-339 TEL: +81-42-6677-1111 Ext.4
e-mail: uchiyaama-katsumi@ttmu.ac.jp

havee developed ultra small sam
mple introductio
on method forr
capiilly gas chrom
matography annd capillary electrophoresis.
e.
Currrently, the teechnique is aapplied to on-line samplee
pre-concentration for capillaryy electrophorresis and too
liquid-liquid extracction.

AJIMA
Hizuru NAKA
Associate Proff. / Dr.Eng.
Analytical Cheemistry, Micro--TAS, Chromatography,
Electrophoresiis, Chemical sensor, Bio sensoorroom: 9-343 TEL: +81-42-6677-1111 Ext.44882
e-mail: nakajim
ma-hizuru @tm
mu.ac.jp
Shungo KATOOAssociate Proff. / Dr.Eng.
Atmospheric C
Chemistry, Anaalytical Chemisttry, Geochemisttry
room: 9-338 TEL: +81-42-6677-1111 Ext.4
4875
e-mail: shungoo @tmu.ac.jp

2. Development
Dof Ultra Small Droplet ELISA
A Using Inkjett
MicrochipM
KatsumiK
UCHIYAMA and Huu-lie ZENG
EnzymeElinkedd immunoSorbeent assay (ELIISA), which iss
baseed upon the antigen-antiboddy reaction, is
i one of theesenssitive determinaation methods for protein. EL
LISA is usuallyy
carried out with miicro titer plate w
with 96 holes anda this enablesssimu
ultaneous deterrminations for vvarious samplees on the plate..
How
wever, in order to complete thee whole assay process,p
it takessmucch time and som
metimes compleex procedure is necessary. Inn
ordeer to solve thee problem, wee have develop
ped ultra smalll
reacction chamber with small droplet formeed by ink-jetttechhnology. The system realizedd acceralation ofo ELISA assayy
timee and drastic red
duction of reageents and samplee consumption.

Hidetaka NOR
RITOMI
Assistant Proff. / Dr.Eng.
Colloid Chemistry, Biocatalyyst Chemistry, Chemical
C
Engineering
room: 9-148 TEL: +81-42-6677-1111 Ext.4
4838
mi @tmu.ac.jp
e-mail: noritom
Hu-lie ZENG
Assistant Proff. / phD
Analytical Cheemistry, Micro--TAS
room: 9-344 TEL: +81-42-6677-1111 Ext.4
4883
e-mail: zeng-hhulie @tmu.ac.jjp
Meng SUN
Specially Appointed Associatte Prof. / phD
Analytical Cheemistryroom: 9-344 TEL: +81-42-6677-1111 Ext.4
4883
sunmeng@tmuu.ac.jp
WA
Sueo KAGAW
Tech. Assistannt
room: 9-290 TEL: +81-42-6677-1111 Ext.44872
e-mail: kagaw
wa @tmu.ac.jp
AMOTO
Haruko MIYA
Tech. Assistannt
room: 9-291 TEL: +81-42-6677-1111 Ext.44873
e-mail: miyam
moto-haruko @jjmj.tmu.ac.jp

Dof Micro Chemicaal Pen
3. Development
Katssumi UCHIYAM
MA
We have developedd a new micro cchemical pen, whichw
enabledodification of thhe surface of maaterials. The
micrro chemical mo
pen feeded reactionn reagent and caatalyst onto thee material
surfface that was plaaced in a liquidd and formed micro raction
region (sub microm
meter to micro mmeter). Chemical pattern was
med by scanningg the pen with xx,y stage. This tooltwill beform
appllied to the arranngement tool foor molecular maachine and its
micrro expression of the function, hhighly function
nalization of
micrro machines and micro total annalysis system.

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

■Outlines of the Research
1. Developmennt of Ultra Smaall Sample Injecction Method U
Using
Inkjet Microochip
Katsumi UC
CHIYAMA andd Hu-lie ZENG
Ink-jet techhnology, whichh enables handdling of ultra ssmallliquid sampless, has been appplied not only to printer butt also
various fields such as chem
mistry and mateerial sciences. We
26

Reportss from Re
esearch Groups
200(mm
m
EL
SPF

EL
&

L
LPF
9 PD
9CH&
I/V&

50(mm
50(mm
95g

PC

9CH

6. Development
D
off Chemiluminesscence Analysiss System Usingg
OrganicO
Photodiiodes as Photo D
Detector
HizuruH
NAKAJIIMA
Chemiluminesce
Cence method ennables high sensitive detectionnof trrace componen
nts in environm
mental and biollogical samplesssincce the method does not requuire a light sorrce and is nott
affected by backg
ground noise dderived from th
he light sorce..
How
wever, it is difficult to apply thhe chemilumineescence methodd
for on-siteoanalysiss since a photoomultiplier tubee typically usedd
as photo detector inn the method is large-size and very expensivee.
In th
his study, organ
nic photodiodess (OLEDs) werre fabricated onn
a microfluidicmdev
vice and then a novel chem
miluminescencee
anallysis system was
w developed using the OL
LEDs-integratedd
micrrofluidic device. The system was successfu
ully used in thee
deteermination of hydrogenhperoxxide based onn the enhancedd
chem
miluminescencee using luminoll.
Reagent②

4. Developmeent of Micro Total Analysis System Usinng aCompact D
Disk-type Microofluidic Devicee
Hizuru NA
AKAJIMA
We have ddeveloped a floow-based ELIS
SA system usiing a
microfluidic ddevice. Howevver, many pum
mps and valvess are
required for m
multiple immunnoassays, whichh affect total sizze ofthe analytical system. In thiis study, we deeveloped a soluution
sending methood based on thhe centrifugal force generateed byrotation of a compact disk-ttype microfluid
dic device. A nnovelsurface plasm
mon resonance sensor, a fluo
orescence deteection
system and an electrochhemical detecttion system weredeveloped usiing the compaact disk-type microfluidicmdeevice.
Since pumps aand valves are unnecessary, thhese systems w
would
be useful fo
for on-site annalysis, such as environm
mentalmonitoring, foood safety testinng and point-of--care testing.

Data logger

Dark boxPC①

Syringe pump

OPD

I/V converrsion amplifier

Injector

Light receivinngsectionPower supply

Reagent
①

②

②

H2O2

Samp
ple

①

•

0.1 M Tris-HCl (pH 8.5)

•
•
•
•

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

Sample•0-16.6 mM
m H2O2 (500 μL)

Flow rate : 100
0 μL/minDofo Portable E
ELISA System for Infectionn
7. Development
DiseaseD
Diagnoosis
HizuruH
NAKAJJIMA
TropicalTarea-sppecific infectioon diseases su
uch as denguee
feveer and chikung
gunya fever arere menaced to society in theeworld since the viruses, which caause these infeection diseases,,are easily spread on a global sscale by globaalization of theeeconnomy. In orderr to minimize the damage ofo the infectionn
diseeases, a rapid diiagnostication aand a non-proliferation for theeviru
uses are very immportant. Howevver, these counttermeasures forr
the danger is not sufficientsin devveloping countries because off
the economic andd technical prroblems. In thiststudy, wee
deveeloped a simplle, portable andd inexpensive ELISA systemmthat can be used for rapid antiibody test in the field. Theeporttable ELISA syystem was succcessfully used ini the antibodyy
testss for measles an
nd rubella virusses.

5. Developm
ment of Fluoreescence Analy
ysis System U
Using
Organic Light Emitting Diodes
D
as Light Source
Hizuru NA
AKAJIMA
The microffluidic lab-on-aa-chip has prov
vided a platforrm to
conduct chem
mical and biochhemical analysiis in a miniatuurized
format. A com
mmon detectionn method for laab-on-a-chip is laser
induced fluoreescence. Howevver, the method
d is not suitablle foron-site analyssis because of the size, weig
ght and cost o f theperipheral devvices such as lasersland miccroscopes. We havesucceeded in iincorporating a light-emitting diode (LED) annd an
optical fiber iinto a polymeric microfluidicc device in ordder tominiaturize thhe total size of the detectionn system. Receently,
organic light emitting dioodes (OLEDs)) have been very
successful forr lightweight full-colorfflat panelpdisplays. The
OLEDs have a flat surface, which makes it easy to inteegratewith microfluuidic devices andaflexible too fabricate intoo therequired size aand shape by phhotolithographyy techniques. Inn thisstudy, we devveloped a noveel portable fluo
orescence deteection
system usingg OLEDs as light source. The system was
successfully uused in the meassurement of IgA
A in human salivva.

27

Reportss from Re
esearch Groups
8. Developmeent of surface plasmonpresonannce sensor usinng an
optical fibber prepared byb electroless displacement gold
plating metthod
Hizuru NAK
KAJIMA
Optical fibeer-type surface plasmon reson
nance (SPR) seensor
has some atttractive advanttages such as small volum
me ofanalytes, minniaturization ofo senser systtem and poteential
capacity for reemote sensing. However,H
it is time-consumingtg andvery costly too form ideal thiickness of goldd thin film for SPR(ca.50 nm) oonto the circuular cylinder shaped fiber core,
precisely. In this study, a simple and low-cost methodd for
fabricating an optical fiber forf SPR sensor was proposed.. The
method was bbased on the electrolessenick
kel plating andd thesubsequent dissplacement gold plating on thee core of the oppticalfiber. The senssitivity and resoolution of the SPR sensor usinng the
fabricated opptical fiber wasw
comparable to that off thecommercially available SPR sensors. The sensor was
successfully uused in the meassurement of IgA
A in human salivva.

12. Atmospheric trrace species meeasurements at remote
r
sites
Shun
ngo KATO
Atm
mospheric carbon monoxide, ozzone, and various volatileorgaanic compoundss were continuoously observed at remotesitess: cape Hedo in Okinawa, Mosshiri in Hokkaiddo, Suzu in
Ishik
kawa.

13. Application
Aof biomassbcharcooal powder to sttress resistanceoff proteins
Hidetaka
H
NORIT
TOMI
To reduce greenho
ouse gas emissiions, biomass charcoal
powwder was preparred from forestrry residues, whiich are carbon
neuttral, and was ussed as a protein carrier. We fou
und that
biom
mass charcoal powderpimparts high heat stress resistanceand organic solvent stress resistannce to proteins. This result
wou
uld be expected to the applicatiions to biosenso
ors, bioreactorss,
bioffuel cells, and soo on.

■Paapers with Peeer Review
1. Fengming
F
Chenn, Luyao Lin, JJie Zhang, Ziyyi He, Katsumii
Uchiyama,U
Jin-M
Ming Lin
Single-Cell
S
Analysis Using Droop-on-Demand Inkjet Printing
anda Probe Electrrospray lonizatiion Mass Specttrometry
Anal.
A
Chem., 2016, 88, pp 43544–4360
2. Jianmin Yang, Daisuke
D
Kataggiri, Sifeng Mao, Hulie Zeng,,
HizuruH
Nakajimaa, Shungo Katoo, Katsumi UchiyamaInnkjet printing basedbassembly of thermorespo
onsivecore-shellcpolym
mer microcapsuules for controlled drug releaseJoournal of Materrials Chemistry B, 2016,4, pp.4
4156-4163
3. JieJ Zhang, Fen
ngming Chen, Z
Ziyi He, Yuann Ma, Katsumii
Uchiyama,U
Jin-M
Ming LinA novel approacch for precisely controlled mulltiple cellpatterningpin microfluidic chipss by inkjet printting and thedetectiondof drug
g metabolism aand diffusion
Analyst,A
2016, 141, pp2940-29447
4. Shungo Kato, Yasuhiro Shhiobara, Katsum
mi Uchiyama,,
KazuhikoK
Miurra, Hiroshi Okoochi, Hiroshi Koobayashi, Shiroo
HatakeyamaH
C O3, and SO
O2 Measuremen
nts at the
Atmospheric CO,
Summit of Mt..Fuji during thee Summer of 20
013
AerosolA
and Air Quality Reseaarch, 2016, 16, pp.2368-2377
5. Jiie Zhan, Koji Fuurui, Hizuru Naakajima, Noriak
ki Kaneki,
RyoichiR
Ishimatssu, Koji Nakanoo, Toshihiko Immato, Akihide
Hemmi
H
Development
Dofo a Portable Surface Plasm
mon Resonancee
SensorS
with Mu
ulti-Sensing Poiints Based on th
he Linear CCD
D
SensorS
AnalyticalA
Scien
nces, 2016, 32(66), pp.673-679
6. HulieH
Zeng, Daissuke Katagiri, T
Taisuke Ogino, Hizuru
Nakajima,N
Shung
go Kato, Katsum
mi Uchiyama
DropletD
Enhanceed Fluorescencee for Ultrasensiitive Detection
Using
U
InkjetAnalyticalA
Chem
mistry, 2016, 88 (12), pp 6135––6139
7. Hidetaka
H
Noritommi, Shunichi Ku
Kurihara, Nobuy
yuki Endo,
Satoru Kato, Kattsumi Uchiyamma

9. Measurements of VOCs att urban and subu
urban sites
Shungo KA
ATO
Volatile Orgaanic Compoundds (VOCs) were observed at uurbansite (Kagurazaaka, Tokyo Scieence Universityy) and suburbann site
(Minamiosawaa, Tokyo Mettropolitan Univ
versity). Charaacters(average concentration level,, emission sourrces, contributioon toozone formattion) of VOCs were compaared at urban andsuburban sitess.
10. Measurem
ments of atmospheric pollutantss at mountain siites
Shungo KA
ATO
Carbon monnoxide, ozone, and sulferdioxide were observved atsummit of Mtt. Fuji during summer. Theree was no influuence
from local polllution source anda typical air at
a remote site duuring
summer was observed. Plumme from volcan
no was observeed at
Mt. Fuji.
11. HO lifettime and trace gas speciess measurementts in
sub-urbann forest area
Shungo K
KATO
Hydroxyl raddicals (OH) conntribute to photoochemical
production of tropospheric ozzone. OH lifetimme (OH reactivvity)and various traace gas species were observed at suburban fororest
area (FM-Tamma), suburban off Tsukuba city, and suburban oof
Tokyo. Verticaal distribution ofo trace gases were
w observed onn theflux tower at fforest area.

28

Reports from Research Groups
Effect of adsorption condition on thermal stability ofproteins adsorbed onto biomass charcoal powderInternational Journal of GEOMATE, 2016, Vol.11, Issue23,
pp.2123-2128
8. Sifeng Mao, Chiho Sato, Yuma Suzuki, Jianmin Yang, Hulie
Zeng, Hizuru Nakajima, Ming Yang, Jin-Ming Lin, Katsumi
Uchiyama
Microchemical Pen: An Open Microreactor for
Region-Selective Surface Modification
ChemPhysChem, 2016,17, pp.3155-3159
9. Weifei Zhang, Sifeng Mao, Jianmin Yang, Hulie Zeng,
Hizuru Nakajima, Shungo Kato,Katsumi Uchiyama
The use of an inkjet injection technique in immunoassays byquantitative on-line electrophoretically mediatedmicroanalysis
Journal of Chromatography A, 1477 (2016) pp.127–131
10. Xiangnan Dou, Yongzan Zheng, Katsumi Uchiyama, Jin‐
Ming Lin
Fluorescent Carbon Nanoparticle: Mimic of Hydrogen
Peroxide Property for Chemiluminescence System
Chem. Commun, 2016, 52, pp.14137-14140
11. Akihito Korenaga, Fengming Chen, Haifang Li, Katsumi
Uchiyama, Jin-Ming Lin
Inkjet automated single cells and matrices printing system
for matrixassisted laser desorption/ionization mass
spectrometry
Talanta, 162(2017) pp.474-478
12. Hidetaka Noritomi, Jumpei Nishigami, Nobuyuki Endo,
Satoru Kato, Katsumi Uchiyama
Organic solvent-resistant properties of proteins adsorbed
onto biomass charcoal powderInternational Journal of GEOMATE, 2017, Vol. 12, Issue 30,
pp.140-145
13. Akira Ida, Misaki Okajima, Iori Kishimoto, Weijia Wu,
Ramasamy Sathiyamurthi, Yoshihiro Nakashima, Shungo
Kato, Satoru Chatani, Yoko Yokouchi, Motonori Okumura,
Yoshizumi Kajii
OH Reactivity Measurement and Chemical Analyses of
BVOCs Emitted from Sugi
J. Jpn. Soc. Atmos. Environ., 2016, Vol.51, No.2, pp.132-143
14. Sathiyamurthi Ramasamy, Akira Ida, Charlotte Jones,
Shungo Kato, Hiroshi Tsurumaru, Iori Kishimoto, Shio
Kawasaki,Yasuhiro Sadanaga, Yoshihiro Nakashima, Tomoki
Nakayama,Yutaka Matsumi, Michihiro Mochida, Sara
Kagami, Yange Deng, Shuhei Ogawa, Kaori Kawana,
Yoshizumi Kajii
Total OH reactivity measurement in a BVOC dominatedtemperate forest during a summer campaign, 20142016, Atmospheric Environment, 131, pp.41-54
15. K. Shimada, A. Takami, S. Kato, Y. Kajii, S. Hasegawa, A.
Fushimi, A. Shimizu, N. Sugimoto, C. K. Chan, Y. P. Kim, N.
H. Lin, S. Hatakeyama
Characteristics of carbonaceous aerosols in large-scale Asian
wintertime outflows at Cape Hedo, Okinawa, Japan, Journalof Aerosol Science, 2016, 100, pp.97-107■Invited Lectures
1. Hulie Zeng, Daisuke Katagiri, Hizuru Nakajima, Katsumi
Uchiyama
Droplet Enhanced Fluorescence for Ultrasensitive Detection
Using 2 Inkjet
2016 China-Japan-Korea Symposium on Analytical
Chemistry(CJK2016), K08
2. Katsumi Uchiyama
Analytical application of ink jet
Proc. of the 65th annual meeting of the Japan Society for
Analytical Chemistry D1006＊ (in Japanese)
3. Katsumi Uchiyama
Nano/ Micro fabrication of chemical structure by microchemical pen
Proc. of the 84th annual meeting of the Electrochemical
Society of Japan 2017 [ S12. The Latest Development in
Chemical Sensors ] Toku3U10 (in Japanese)■Academic Meeting＊International
1. ○Daisuke Katagiri, Hulie Zeng, Hizuru Nakajima, Katsumi
Uchiyama
Inkjet printing based assembly of thermoresponsive
core-shell polymer microcapsules for controlled drug release2016 China-Japan-Korea Symposium on Analytical
Chemistry (CJK2016), Wuyi University, Wuyishan，China,
P18
2. ○Yong Zhang, Sifeng Mao, Hulie Zeng, Hizuru Nakajima,
Katsumi Uchiyama
Synthesizing polymer lines with a microfluidic
mixing-based chemical pen
2016 China-Japan-Korea Symposium on Analytical
Chemistry (CJK2016), Wuyi University, Wuyishan，China,
P12
3. ○Weifei Zhang, Sifeng Mao, Jianmin Yang, Hulie Zeng,
Hizuru Nakajima, Katsumi Uchiyama
The use of an inkjet injection technique in immunoasays byquantitative on-line electrophoretically mediatedmicroanalysis (EMMA)
2016 China-Japan-Korea Symposium on Analytical
Chemistry (CJK2016), Wuyi University, Wuyishan，China,
P28
4. ○Xiangnan Dou, Katsumi Uchiyama, Jinming Lin
Fluorescent Carbon Nanoparticle:Mimic of Hydrogen
Peroxide Property for Chemiluminescence System
2016 China-Japan-Korea Symposium on Analytical
Chemistry (CJK2016), Wuyi University, Wuyishan，China,
P06
5. ○Chiho Sato, Sifeng Mao, Hulie Zeng, Shungo Kato,
Hizuru Nakajima, Katsumi Uchiyama
The development of micro-fluidic chemical pen for region
selective modification
RSC Tokyo International Conference 2016, Makuhari-Messe,
Chiba, C09
6. ○H.Noritomi, J.Nishigami, N.Endo, S.Kato, K.Uchiyama
Organic Solvent Resistance of Proteins Adsorbed Biomass
Charcoal Powder
Second International Conference on Science, Engineering■Books
1. Katsumi Uchiyama
Generation of Ultra-small Droplets by an Inkjet and Its
Application to Chromatography
Bunsekikagaku sougouronbunnenkantokusyu "super" vol.65,
No.1, pp.1-11(2016)
2. Shungo Kato
Measurement of mountain ozone and carbon monoxide - Mt.
Fuji-.
Ridai scientific forum, 2016 August (number 387 ).
Page 6-7

29

Reports from Research Groups
and Environment (SEE-Osaka2016), Osaka International
House Foundation, Osaka city, 2654
7. Kazuhiro Morioka, ○Hizuru Nakajima, Akihide Hemmi,
Hulie Zeng, Shungo Kato, Katsumi Uchiyama
Development of Portable Fluorescence Detection System
Using an Organic Photodiode Array Detector
PITTCON2017, Chicago, USA, 230-30P＊Domestic
See the annual report in Japanese (30 articles)■Awards
1. Mao Asada (Master's course 2years)
Student judge special prize
Development of Surface Plasmon Resonance Sensor Usinga DVD-R.
Proc. of the 65th annual meeting of the Japan Society for
Analytical Chemistry (Hokkaido University) (in Japanese)
2. Ryo Takahashi (Master's course 2years)
TopicsDevelopment of Fluorescence Analysis System Using a
Compact Disk-type Microfluidic Device and Its Application
to Infection Disease Diagnosis
Proc. of the 76th symposium of the Japan Society for
Analytical Chemistry (Gifu Pharmaceutical University)(in Japanese)30

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
Yan J. Mulyana
Associate Professor / Ph.D.
Coordination Chemistry, Photochemistryroom: 9-149 TEL: +81-42-677-2823
e-mail: ymulyana@tmu.ac.jp
4. Visible Light-induced Water Splitting with Photosensitizing
Dye
Name: Yuji Kubo and Yan J. Mulyana
There is an urgent need for creating new energy materials
capable of producing hydrogen fuel from water as analternative to the use of fossil fuels. Our research is concernedwith creating bio-inspired energy materials, namely photoelectrochemical (PEC) cells, which are capable of harvesting
light energy to drive the water splitting process. The
construction of the devices involves the synthesis of organicand inorganic materials, which can be assembled withappropriate semiconductors such as titanium oxide (TiO2) andindium tin oxide (ITO) nanoparticles.

Ryuhei Nishiyabu
Assistant Professor / Dr. Eng.
Supramolecular Chemistry, Organic Chemistry, Matetials
Chemistryroom: 9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: ryuhei@tmu.ac.jp
Doctor’s course -3
Master’s course -13
Bachelor 4 -7

■Outlines of the Research
1. Synthesis of Dyes Applicable to Dye-Sensitized Solar Cells
Name: Yuji Kubo
Due to our interest in the development of functional dyes that
can absorb longer wavelength of radiations, synthesis andcharacterization of π-extended dibenzo-boron-dipyrromethenes(dibenzo-BODIPYs) have been investigated. For the approach,the related sensitizers applicable to dye-sensitized solar cells
are worthwhile to be investigated. In this study,
dibenzo-BODIPYs with a phenothiazinylcyanoacrylic acidgroup and rhodamine groups have been newly prepared,
respectively.
2. Synthesis of Selenophene-containing Dyes
Name: Yuji Kubo
Selenium is relatively more polarizable and softer than sulfur,
due to its size. Although the low oxidation potential leads toelectrondonating
propertyofselenium-containing
π-conjugation to endow it with promising OFET materials, theproposal of emissive compounds with selenium are limited
because of the heavy atom effect. On another front, there has
been increasing demand for the development of dyes withstableexcitedtripletstates.
In
thisstudy,
selenophene-substituted BODIPY (Se-BDP) has been newly
synthesized

5. Synthesis of a 1-hydroxy-2,3,1-benzodiazaborine-containing
π-conjugated system
Name: Yuji Kubo and Ryuhei Nishiyabu
A
1-hydroxy-2,3,1-benzodiazaborine
conjugatedwith
1,8-naphthalimide was synthesized. Its fluorescence wasdramatically affected by the nature of the solvent. In particular,
the use of DMSO, which has a relatively high donor number,
led to a remarkable decrease in the fluorescence intensity,
possibly due to intermolecular hydrogen-bonding interactions.
The presence of the hydroxyl group on boron led to asolvent-driven colorimetric response towards anions; highselectivity for fluoride ion over other anions in DMSO, andresponded to acetate ion and fluoride ion in THF.

3. Construction of Triplet-Triplet Annihilation-Based
Upconversion Molecular Systems
Name: Yuji Kubo
Triplet-triplet
annihilation-based
photonupconversion(TTA-UC) have attracted increasing attentions as promising
methods for energy conversion from low-energy excitation tohigher energy light because of various applications involving
solar cells, photocatalysts, and so on. However, TTA-UC is ahighly oxygen sensitive process, resulting in a low efficiency inthe presence of oxygen. In this study, a Co complex was used
to overcome such difficulty, which is known as an oxygen
scavenger. Subsequently, we found that the addition of the Co
complex into the solution of Pt(II) porphyrin (PtOEP) as asensitizer and 9,10-diphenylanthracene (DPA) as an annihilator
led to significant quenching of UC emission, whereas
phosphorescence emission due to the sensitizer almost
remained.

6. A zinc-coordinated boronate dipyrrin as a chemodosimeter
toward hydrogen peroxide
Name: Yuji Kubo and Ryuhei Nishiyabu
To develop a chemodosimeter for the visual detection ofhydrogenperoxide,adipyrrin
dye
with

31

Reports from Research Groups
6. T. Minami, F. Emami, R. Nishiyabu, Y. Kubo and P.
Anzenbacher, Jr., Quantitative analysis of the modeled
ATP hydrolysis in water by a colorimetric sensor array,
Chem. Commun., 2016, 52, 7838-7841.
7. 2,3-Naphtho-fused BODIPYs as near-infrared absorbingdyes, S. Yamazawa, M. Nakashima, Y. Suda, R. Nishiyabu,
Y. Kubo, J. Org. Chem., 2016, 81, 1310−1315.
8. Water-dispersible boronate nanoparticles as support
materials for noble metals in the hydrogenation of levulinicacid to γ-valerolactone, Y. Kubo, D. Kakizaki, M. Kogo, Y.
Magatani, Supramol. Chem. (Special Issue ofSupramolecular Chemistry in Honor of Jonathan Sessler's
60th Birthday), 2016, 28, 91−97.

4-pinacolborylbenzyloxy groups was synthesized. An ethanol
solution of the dye was reddish-violet in color. The addition ofhydrogen peroxide into the solution induced a remarkable color
change from reddish-violet to blue. . For practical applications,the related drop-cast paper strips were fabricated to visuallydetect hydrogen peroxide vapor.

■Book Chapter
See the annual report in Japanese for other book chapter (onechapter).
1. Boronate microparticles: preparation, characterisation, andfunctionalization, Y. Kubo, R. Nishiyabu, Boron; Sensing,
Synthesis and Supramolecular Self-Assembly, Monographin Supramolecular Chemistry, M. Li, J. S. Fossey, T. D.
James (Eds), The Royal Society of Chemistry, Cambridge,
2016, p.p. 361−388.

7. Synthesis of Tetraphenylethylene-Containing Boronate
Macrocycles and their Self-Assembly
Name: Yuji Kubo
There has been growing interest in π-conjugated moleculeswith aggregation-induced emission (AIE) capability, whichhave prompted chemists to develop new luminescent systems
in materials science. To develop hierarchical supramolecules
based on boronate esterification, sequential dehydration ofdi(boronicacid)-appended
tetraphenylethylene
withditrimethylolpropane was investigated■Invited Lectures
See the annual report in Japanese for other invited lectures (twopresentations).
1. A Boronatedipyrrin-based chemosensors for visual
detection of hydrogen peroxide, Y. Kubo, O12B, 2ndInternational Caparica Conference on Chromogenic andEmissive Materials, Lisbon, Portugal, September 5, 2016.
2. Materials, medicine and energy: measuring the versatilityof metal complexes, J. Yan Mulyana,11th Joint Conferenceof Chemistry in conjunction with the 4th Regional
Biomaterials Scientific Meeting, Plenary Session II,
Purwokerto, Central Java, Indonesia, 16 September 2016.

8. Surface Modification of Polyvinyl Alcohol Sponge with
Boronic Acids to Develop Functional Porous Materials.
Name: Yuji Kubo and Ryuhei Nishiyabu
Surface modification of a polyvinyl alcohol sponge withfunctionalized boronic acids to develop porous materials
applicable for multicolor emission, chemical sensing and 3D
cell culture.

■Academic Meeting＊International
1. Photoelectrochemical water splitting using organic dyes，O. Suryani・Y. Mulyana・Y. Kubo，P1，The 1st International
Symposium on Hydrogen-based Society，August 27, 2016,
Hachioji
2. New ruthenium complex for dye-sensitized photoelectrochemical water splitting, I. Purnama, Y. Mulyana, Y.
Kubo, P2, The 1st International Symposium on
Hydrogen-based Society，August 27, 2016, Hachioji■Papers with Peer Review
1. R. Nishiyabu, S. Iizuka, S. Minegishi, H. Kitagishi, and Y.
Kubo, Surface modification of polyvinyl alcohol spongewith functionalized boronic acid to develop porous
materials for multicolor emission, chemical sensing and 3D
cell culture, Chem. Commun., accepted.
DOI: 10.1039/C7CC00490G
2. K. Sakakibara, Y. Takahashi, R. Nishiyabu and Y. Kubo, A
Zn2+-coordinated boronatedipyrrin as a chemodosimeter
toward hydrogen peroxide, J. Mater. Chem. C, accepted.
DOI: 10.1039/C7TC00405B (Journal of Materials
Chemistry C HOT papers)
3. Y. Satta, R. Nishiyabu, T. D. James and Y. Kubo, A
containing
1-hydroxy-2,3,1-benzodiazaborineπ-conjugated system: synthesis, optical properties andsolvent-dependent response toward anions, Tetrahedron,accepted.
4. Y. Kubo and R. Nishiyabu, White-light emissive materials
based on dynamic polymerization in supramolecularchemistry, Polymer, in press.
DOI:10.1016/j.polymer.2016.12.082
5. R. Nishiyabu and A. Shimizu, Boronic acid as an efficientanchor group for surface modification of solid polyvinyl
alcohol, Chem. Commun., 2016, 52, 9765-9768. (Insideback cover)＊Domestic
See the annual report in Japanese for other presentations (16presentations).
1. Photoelectrochemical water splitting using organic dyes, O.
Suryani・Y. Mulyana・Y. Kubo, 3A06, Annual Meeting on
Photochemistry 2016, The University of Tokyo (Komaba
Campus), Tokyo, 2016, Sep 8th
2. New ruthenium complex for dye-sensitized photoelectrochemical water splitting, I. Purnama, Y. Mulyana, Y.
Kubo, 3P075, Annual Meeting on Photochemistry 2016,
The University of Tokyo (Komaba Campus), Tokyo, 2016,
Sep 8th
3. Organic and inorganic materials for light-poweredhydrogen production from water, Y. Mulyana, Y. Kubo,
3A07, Annual Meeting on Photochemistry 2016, The
University of Tokyo (Komaba Campus), Tokyo, 2016, Sep
8th
4. Water-Dispersible Boronate Microparticles for Aiming at
Preparation of Chemosensors with Multicolor Fluorescence
Emission, PRATOMO Uji・NISHIYABU Ryuhei・KUBO

32

Reports from Research Groups
Yuji, 2B6-36, The 97th CSJ Annual Meeting (2017), Keio
University (Hiyoshi Campus), Yokohama, 2017 Mar 17th
5. Synthesis of a Phenothiazine-Dibenzo-BODIPY Conjugate
Applicable to Dye-Sensitized Solar Cells, Şule Erten-Ela,Takuro Asaba, Yuji Kubo, The 97th CSJ Annual Meeting(2017), Keio University (Hiyoshi Campus), Yokohama,2017 Mar 17th
6. Visible light-Induced Water Splitting with Rhodanine
Containing Dibenzo-BODIPY, Okta Suryani, Yuta
Higashino, Jacob Yan Mulyana, Yuji Kubo, Masayoshi
Kaneko, Koichiro Shigaki, 3A6-06, The 97th CSJ Annual
Meeting (2017), Keio University (Hiyoshi Campus),
Yokohama, 2017 Mar 18th

■Patents
See the annual report in Japanese (6 patents).

■Awards
1. Kaori Sakakibara，2017 Journal of Materials Chemistry C
HOT papers (Sakakibara, Y. Takahashi, R. Nishiyabu and Y.
Kubo, A Zn2+-coordinated boronatedipyrrin as achemodosimeter toward hydrogen peroxide, J. Mater. Chem.
C, accepted. DOI: 10.1039/C7TC00405B)

33

Reports from Research Groups
Shishido Laboratory■Members

However, this is still a challenging subject, especially the
reduction of NOx (NO and NO2) into N2 without PGM.
We studied characterization and catalytic performance of nickel
aluminate-based catalysts (NiAl2O4), which possess a highsurface area and thermal stability. The catalytic activity wasevaluated using test reactions of NO, CO, and C3H6 undervarious simulated exhausts with different air-to-fuel ratios. As aresult, NiAl2O4 showed moderate NO reduction activity in awide oxygen concentration. The isolated hexacoordinated Ni of
NiAl2O4 can react with NO without reductant agent. Supported
Pd promote Ni2+ reduction to Ni metal and the Cu in NiAl2O4
activated CO oxidation.

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,

Lidan Deng
Assistant Professor /Dr. Eng.
Catalysis Science
room:9-538 TEL: +81-42-677-2851 (Ext. 4958)
e-mail: deng-dan@tmu.ac.jp
Doctor’s course -1
Master’s course -14
Bachelor 4 -9

■Outlines of the Research
1. Development of supported alloy nanoparticle catalysts
effective for hydrogen starage-evolution cycles
Tetsuya Shishido, Hiroki Miura
Recently, hydrogen fuel battery attracts much attentions thanks
to its high energy efficiency. Therefore, hydrogen carriersystems enables safe and stable transportation of hydrogen isstrongly required. In this year, we investigated hydrogenation ofammonium hydrogen carbonate/ dehydrogenation of ammonium
formate reversible system, and found that supported PdAu alloy
catalysts showed high activity. Furthermore, these catalysts werealso effective for methanolysis ammonia borane. Spectroscopic
investigation revealed charge transfer from Pd to Au, andcoordination environment around Pd atom of PdAu alloys
remarkably affected their catalytic activity.

3. Green transformation of organic molecules by transitionmetal catalysts
Hiroki Miura, Tetsuya Shishido
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
benzamide to internal alkynes to give isoindolinone derivatives.
Under optimized conditions, a series of isoindolinones wereobtained in good to high yields. Furthermore, we also found that
supported PdAu catalysts were iffective for hydrosilylation ofinternal alkynes, unsaturated ketones and allenes under mild
reaction conditions to afford the corresponding organosiliconcompounds in high yields.

■Papers with Peer Review
1. Supported Palladium–Gold Alloy Catalysts for Efficient andSelective Hydrosilylation under Mild Conditions with
Isolated Single Palladium Atoms in Alloy Nanoparticles as
the Main Active Site, H. Miura, K. Endo, R. Ogawa, T.
Shishido, ACS Catal. 2017, 7, 1543–1553.
2. Ruthenium-catalyzed Addition of Aromatic Amides toInternal Alkynes and Subsequent Intramolecular Cyclization
for the Atom-Economical Synthesis of Isoindolinones, H.
Miura, S. Terajima, K. Tsutsui, T. Shishido, J. Org. Chem.
2017, 82, 1231–1289.
3. Iridium-Catalyzed Synthesis of Acylpyridines by [2+2+2]
Cycloaddition of Diynes with Acyl Cyanides, T. Hashimoto,
K. Kato, R. Yano, T. Natori, H. Miura, R. Takeuchi, J. Org.
Chem. 2016, 81, 5393–5400.
4. Intermolecular [2+2+1] Carbonylative Cycloaddition of
Aldehydes with Alkynes, and Subsequent Oxidation to

2. Metal-oxide based catalysts effective for converstion of
exhaust gas from vehicles
Tetsuya Shishido, Hiroki Miura
The reduction of the amount of PGM or the development of
replaceable materials have been investigated extensively.

34

Reports from Research Groups
Gamma-Hydroxybutenolides by a Supported Ruthenium
Catalyst, H. Miura, K. Takeuchi, K.; Shishido, T. Angew.
Chem. Int. Ed. 2016, 55, 278.
5. Synthesis of Niobium Oxide Nanoparticles with Plate
Morphology Utilizing Solvothermal Reaction and Their
Performances for Selective Photooxidation, K. Tamai, S.
Hosokawa, K. Teramura, T. Shishido, T. Tanaka, Appl. Catal.
B, 2016, 182, 469.

5.

6.

■Invited Lectures
1.

2.

3.

4.
5.

6.

7.

8.

“Selective C-N and C-O coupling reactions over niobiumoxide photocatalyst”, T. Shishido, A. Noda, Y. Ohno, S.
Shimada, H. Miura, S. Hosokawa, K. Teramura, T. Tanaka,
26th IUPAC International Symposium on Photochemistry(2016 IUPAC Photochem), April 4-8, 2016, Osaka, Japan“Photo-induced electron transfer between a reactant
molecule and semiconductor photocatalyst – “in situ
doping””, T. Shishido, 8th Singapore Catalysis Forum,
May 14-15, 2016, Singapore, Singapore“Selective molecular transformations by supported alloy
nanoparticle catalysts; Hydrosilylation by supported PdAu
catalysts as an example.” Tetsuya Shishido, Aug 24, 2016,
Oita University.
“Solid acid-base catalysts” Tetsuya Shishido, Catalysts
seminar, Aug 30-31, 2016, Fukui.
“Sutructure and catalysis of supported alloy nanoparticles;
Dehydrogenation over Pt-Sn alloy catalysts” Tetsuya
Shishido, 9th ESICB symposium, Oct 31, 2016, Kyoto
University.
“Supported platinum/gold alloy nanoparticles catalyst for
selective hydrosilylation of α,β-unsaturated ketones andalkynes” T. Shishido, K. Endo, R. Ogawa, H. Miura,
International Symposium on Catalysis and Fine Chemicals
2016 (C&FC2016), November 10-14, 2016, Taipei,
Taiwan“Development of oxide-supported Ru catalysts directed
toward synthesis of useful chemicals” Hiroki Miura, JPIJS
meeting in east division, Dec 9, 2016, Seikei University.
“Structure and catalysis of supported alloy nanoparticles;
selective molecular transformation and hydrogen
evolusion” Tetsuya Shishido, 2016 3th lectureship on
research centre for artificial synthesis, Feb 2, 2016, Osaka
City University.

7.

8.

9.

PdAu catalysts, K. Endo, R. Ogawa, H. Miura, T. Shishido,
6th IUPAC International Conference on Green Chemistry(ICGC-6), September 4-8, 2016, Venezia, Italy
Intermolecular [2+2+1] Carbonylative Cycloaddition of
Aldehydes with Alkynes by CeO2-supported ruthenium
catalysts, H. Miura, K. Takeuchi T. Shishido, International
Symposium on Catalysis and Fine Chemicals 2016
(C&FC2016), November 10-14, 2016, Taipei, Taiwan
Photocatalytic synthesis of heterocyclic compounds overlayered niobium oxides, S. Shimada, H. Miura, T. Shishido,International Symposium on Catalysis and Fine Chemicals
2016 (C&FC2016), November 10-14, 2016, Taipei,
TaiwanHydrogenolysis of tetrahydrofurfuryl alcohol by
Pt/WO3/Al2O3, Aiko Nagao, Hiroki Miura, Tetsuya
Shishido, International Symposium on Catalysis and Fine
Chemicals 2016 (C&FC2016), November 10-14, 2016,
Taipei, Taiwan
Ru-catalyzed [4+1] cycloaddition of aromatic amides withinternal alkynes, S. Terajima, H. Miura, T. Shishido,International Symposium on Catalysis and Fine Chemicals
2016 (C&FC2016), November 10-14, 2016, Taipei,
TaiwanDehydrogenative coupling of alcohols over supported Cu
catalysts, K. Nakahara, H. Miura, T. Shishido,International Symposium on Catalysis and Fine Chemicals
2016 (C&FC2016), November 10-14, 2016, Taipei,
Taiwan＊Domestic
See the annual report in Japanese (32 articles)■Awards
1. Poster Award ‘‘Hydrosilylation of alkynes by supported
PdAu alloy catalysts” Ryoichi Ogawa, Keisuke Endo, Hiroki
Miura, Tetsuya Shishido ， 14th Catalyst workshop in
Fujisawa, August 1, 2016, Fujisawa.
2. Poster Award ‘‘Dehydrogenative coupling of alcohols by
supported Cu catalysts” Karin Nakahara, Hiroki Miura,
Tetsuya Shishido ， 14th Catalyst workshop in Fujisawa,
August 1, 2016, Fujisawa.
3. Excellent Poster Award ‘‘Hydrosilylation of internal alkynes
by supported PdAu alloy catalysts” Ryoichi Ogawa, Keisuke
Endo, Hiroki Miura, Tetsuya Shishido， 6th CSJ chemistry
festa 2016, Novenber 11, 2016, Funabori.
4. Best
C&FC
2016
PosterPresentation
Award“Hydrogenolysis of tetrahydrofurfuryl alcohol by
Pt/WO3/Al2O3”Aiko Nagao, Hiroki Miura, and Tetsuya
Shishido, The International Symposium on Catalysis andFine Chemicals 2016 (C&FC2016), November. 10-14, 2016,
Taipei, Taiwan■Academic Meeting＊International
1.
Pt/WO3/Al2O3 catalysts for selective hydrogenolysis ofglycerol to 1,3-propanediol, Hayato Kobayashi, Takeshi
Aihara, Hiroki Miura, Tetsuya Shishido, The International
Symposium on Catalytic Conversions of Biomass(ISCCB-2016), June 27-30, 2016, Taipei, Taiwan
2.
Hydrogenation of ammonium bicarbonate over supported
Pd catalysts, K. Nakajima, H. Miura, T. Shishido, The 1st
International Symposium on Hydrogen Energy-based
Society, August 26- 27, 2016, Tokyo, Japan
3.
Development of the Cu-based catalysts efficient for steam
reforming of methanol, Y. Kubo, H. Miura, T. Shishido,
The 1st International Symposium on Hydrogen Energybased Society, August 26-27, 2016, Tokyo, Japan4.
1,4-hydrosilylation of unsaturated ketones over supported

35

Annual Report 2016
Published by
Tokyo Metropolitan University
Faculty of Environmental Sciences
Department of Applied Chemistry
April, 2017