サイズ：A4（210×297mm） 背幅：6.5mm

京
都
大
学
化
学
研
究
所
国
際
共
同
利
用
・
共
同
研
究
拠
点

令
和
2
年
度
成
果
報
告
書

京都大学化学研究所 令和 2 年度

国際共同利用・共同研究拠点 成果報告書
化学関連分野の深化・連携を基軸とする
先端・学際グローバル研究拠点

京都大学化学研究所

国際共同利用・共同研究拠点

化学関連分野の深化・連携を基軸とする
先端・学際グローバル研究拠点

令和 2 年度

成果報告書

まえがき京都大学化学研究所は、平成２２年度から「化学関連分野の深化・連携を基軸とす
る先端・学際研究拠点」（平成２８年度から第二期）として国内外の共同利用・共同研究を推し進め、それを新たな糧としてより多様でグローバルな化学研究の展開と若手研究者の育成・輩出を図って参りました。特に本拠点では、化学関連コミュニティの研究者の皆様からの要請を踏まえながら、化学研究所の研究分野の広がりと深さに加えて、これまでの様々な連携実績を活かし、国内外の研究機関の相互協力を担保す
るハブ環境も提供しています。先端・学際的分野深耕にあたっては、関連コミュニテ
ィの研究者の皆様と化学研究所の教員が推進する分野選択型、課題提案型、施設・機器利用型、連携・融合促進型等の多彩な共同研究と、拠点として主催・共催する各種
国際会議、シンポジウム、研究会等を通じて、多様性と先進性を担保し、さらに、国際的視点に基づいて次代の化学関連分野を担う若手研究者の育成にも注力しています。また、拠点運営では、所外、学外の関連分野有識者と化学研究所の教員を委員とする共同研究委員会および運営評議会を核として、共同研究課題の公募・採択などを戦略的に遂行しております。
このようなグローバルな拠点活動が評価され、化学研究所は、平成３０年１１月１３日文部科学大臣から国際共同利用・共同研究拠点に認定され、「化学関連分野の深化・連携を基軸とする先端・学際グローバル研究拠点」として活動を強化しています。
国際拠点活動の三年目にあたる令和２年度には、化学研究所教員が一丸となって、２０３件の応募の中から採択された１３２件の共同研究を遂行しました。そのうち、グ
ローバルな化学研究の展開と人材育成のため、国際共同研究枠を令和元年度の５５件
から６２件（若手国際枠３件を含む）に増やしました。しかし、世界的な新型コロナ
ウィルス感染症拡大のため、従来のように国際・国内共同研究を推進できない状況が未だ続いております。まだ終息が見通せないコロナ禍での拠点活動を支援するため、拠点ではリモート実験環境整備やハイブリッド会議システム導入など、研究・教育環
境整備に取り組んで参りました。今後とも、国際的ハブ機能を活用し、国際共同利用・共同研究の一層の促進、国際学術ネットワークの充実、国際的・先進的視野をもつ若手研究者の育成に取り組むことで、化学を中心とする研究分野の深化と境界学術分野の新規開拓を一層推進して参ります。皆様にはさらなるご支援・ご協力のほどよろし
くお願い申し上げます。
本報告書は、令和２年度の本拠点における研究成果をとりまとめたものです。本
報告書をご一読頂き、今後の本拠点の目指すべき方向や活動の推進方法などに関する忌憚のないご意見・ご提案などをお聞かせ下されば幸甚に存じます。
化学研究所所長 辻井 敬亘令和2年度 共同利用・共同研究報告書 目次
１．共同研究成果報告
分野選択型共同研究
ビーム科学分野
化学的手法に基づくキラルプラズモニックナノ構造体の作製および設計技術
2020-1
大阪産業技術研究所
中川 充
中赤外レーザーを用いた振動強結合による反応性変化の解明
2020-2
北海道大学 平井 健二
2020-3
X-ray structural studies on ligand complexes of maleylacetate reductase
Kansai University Tadao Oikawa
レーザープラズマ密度制御による金属表面機能性付与加工
2020-4大阪産業大学 草場 光博
2020-52色パルス誘起微細周期構造形成過程の研究
摂南大学
長島 健
2020-6ナノ構造を持つ ISOL 用標的の開発
理化学研究所 大西 哲哉
電子散乱による短寿命不安定核の奇妙な構造の解明
2020-7
東北大学 須田 利美
元素科学分野2020-8※ Gas sensing properties research of transition-metal oxides
Chinese Academy of Sciences Haichuan Guo
2020-9※ Separation and evaluation of thiolate protected metal clusters with atomic
precision by using LC/MS
Tokyo University of Science Yuichi Negishi
2020-10※ Small molecule activation using anionic crypto-FLPs
University of Bonn Rainer Streubel
2020-11※ Design and tailoring advanced functional materials: Symmetry operation andhigh pressure synthesis
National Taiwan University Wei-tin Chen
2020-12※ Development of unsymmetrical π-electron systems of heavier main groupelements and elucidation of their property
Tohoku University Takeaki Iwamoto
2020-13※ Optical control of high-order harmonic generation from solids
University of Tsukuba Shunsuke Sato
2020-14※ Iron-catalyzed C-H borylation
Visva-Bharati University Alakananda Hajra
2020-15※ Electrochemically engineered peptide based organic-inorganic
nanohybrids for electrocatalytic conversion of biomass into value added
chemicalsIndian Institute of Technology Indore Apurba K. Das
2020-16※ Iron-catalyzed enantioselective carbometalation and ring-opening
reactions of oxabicycloalkenes and other related substrates andmechanistic consideration
Indian Institute of Engineering Science and Technology Laksmikanta Adak
Study on the stability of novel ternary nanoparticles by doping 3rd elements
2020-17
Meio University Yasutomi Tatetsu※ 国際共同利用・共同研究

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体にお る2020-18
2020-19

マル

形光学のた の

ック
起

ノ

にお る

短中赤外光 の開発
子科学技術研究開発機構
強度 ラ ル パルスを用いたマ ノ
東

2020-20
2020-212020-22

工業大学

18

井

哉

19

研究機構 中Development of dinuclear nickel complexes based on a monoanionictridentate pincer-type ligand
Yokohama Nationa University Yoshitaka Yamaguchi

20

ラ

ル

性微

合

反応機構の

子を用いた ルール

的な理解 モ

ル化

21

の機能発

産業技術研究所
2020-23
Creation of effective oxidation scavenger for efficient perovskite-based solar cells
University of Tsukuba Takahiro Sasamori
学分野
2020-24※ A study on statistical machine learning for efficient graph structured data
analysis
Nagoya Institute of Technology Masayuki Karasuyama
2020-25※ Integrating omics data and module-based network with deep learning todevelop cancer type predictive models
National Chiao Tung University Jinn-Moon Yang
2020-26※ Next-generation bioinformatics approaches for the accurate identification ofprotease-specific substrate cleavage sites
Monash University Jiangning Song
2020-27※ Revealing associations between giant viruses and eukaryotes in the global ocean
through community networks inference and mining
CNRS UMR6004 Samuel Chaffron
2020-28※ Unveiling the genomic contents of ecologically important marine giant viruses
CNRS UMR8030 Tom O. Delmont
2020-29Development of predictive methods for marine microbial communities
based on remote sensing data
National Institute of Advanced Industrial Science and Technology Kentaro Tomii
2020-30
Control and analysis of complex networks via probabilistic minimum
dominating sets
Toho University Jose C. Nacher
2020-31
Genomics and transcriptomics of giant viruses
Tokyo University of Science Masaharu Takemura
2020-32
Whole genome analyses of marine bacterivorous heterotrophic
nanoflagellates
Fukui Prefectural University Takafumi Kataoka
2020-33
Comparative genome analysis of Parmales and diatoms: Looking for theancestral genomic feature
Fukui Prefectural University Shinya Sato
分子 ッ ーク解 の 計的機 学 による解法 応用
2020-34
産大学
野光
合成分野
2020-35※ Light emission from halide perovskites and related materials
National Taiwan University Ru-Shi Liu※ 国際共同利用・共同研究

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2020-36※ Exploration of cycloaddition properties of guanidine functionalized anthracenes
Rudjer Boskovic Institute Davor Margetic
2020-37※ Development of new blue TADF emitters with horizontal molecular orientations
University of St Andrews Eli Zysman-Colman
oupling of nanographenes an curve π-systems an eluci ation of their2020-38※
electronic and optical interactions
Okinawa Institute of Science and Technology Graduate University Akimitsu Narita
2020-39※ Development of hole transport materials for tin-perovskite and device characterization
Osaka University Akinori Saeki
Development of π-con ugate nic el comple es for high performance n-type2020-40
thermoelectric materials
Osaka Institute of Technology Michihisa Murata
ズレ の 性をた
機能性色素の 製
2020-41
工業学
2020-42
Preparation of chiral silica via chiral transfer
Osaka Institute of Technology Tomoyasu Hirai
マクにた反応中 体の化学
2020-43
島大学
安 学
機分子を用いるN-N 不 化合 の 度 的光学分 法の開発
2020-44
大学
田解 分野
2020-45※ Molecular understanding on the structures and dynamics of ionic end-aggregation
polymers
Suraneree University of Technology Visit Vao-soongnern
2020-46※ Observation of orbital Hall effect in ferromagnet/nonmagnet bilayers
University of Ulsan Sanghoon Kim
2020-47※ High frequency response of polymeric liquids: Rheology and dielectricrelaxation
Yamagata University Sathish K. Sukumaran
2020-48※ Dissolved and particulate Fe isotopic composition in the North Pacific
Ocean: Sources and internal cycling
Academia Sinica Tung-Yuan Ho
2020-49※ Revealing exciton quenching mechanisms in thermally activated delayed
fluorescent devices
University of St. Andrews Ifor D. W. Samuel2020-50※ Fabrication of low bandgap semiconductor films and their light induced
interfacial charge transfer and charge transport dynamics
RMIT University Yasuhiro Tachibana
2020-51※ Dynamics of shear-induced concentration fluctuation in polymer solutions
Stony Brook University Maya Endoh
2020-52
GISAXS-CT法による
分子
にお る
元素の不
分
西学 大学
明
基
ニ
にお る 性型
レ の同定
2020-53
大学
Origin analysis of atmospheric aerosol of mountainous areas by trace
2020-54
metal analysis
Kindai University Yuzuru Nakaguchi
分 ッ素化
性分子の
性 構造に
るRf 長
性の解
2020-55
大学※ 国際共同利用・共同研究

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2020-56

Dynamic viscoelasticity and tensile properties of thermoplastic elastomers
Nagoya University Atsushi Noro
プラズモニック合金ナノ 子を設計 るた の理 的の構
2020-57
北海道大学
田 健二
2020-58
Study on transportation of metal ions through a polymer membrane
containing ionic liquid
Kyoto University of Education Hiroshi Mukai
2020-59
Exploration of hierarchical dynamics of amorphous polymers by broadband
dielectric spectroscopy
Osaka University Osamu Urakawa
型共同研究2020-60※ Dielectric relaxation of type-A rouse chain under end-adsorption/desorption
equilibrium: Effect of motional coupling
Sungkyunkwan University Youngdon Kwon
2020-61※ Molecular mechanisms for the inactivation of a growth hormone in rice
Chinese Academy of Science Zuhua He
2020-62※ Well-defined AIE-based polymer brush for the application of theelectrochemical luminescence biosensors
South China University Ying Ma
2020-63※ Role of phosphoinositide signaling in pollen development
Peking University Sheng Zhong
2020-64※ Role of PX-PH-type phospholipase Ds in plant intracellular membrane traffic
MRC Yohei Ohashi
2020-65※ Proteomic approach to discovering specific inhibitors for bile-acidinteracting enzymes
Peking University Xiaoguang Lei
2020-66※ Transfer of redox sensitive elements across the sediment-water interface in a
hypoxia area near the East Chia Sea
Xiamen University Pinghe Cai
2020-67※ Application of artificial viral capsid to intracellular delivery
Tottori University Kazunori Matsuura
2020-68※ Structural and functional analysis of curvature-inducing peptides and application
Karlsruhe Institute of Technology Anne S. Ulrich2020-69※ Site-selective protein acetylation by a small molecule
Fudan University Lu Zhou
2020-70※ Modulation of ferrimagnetic spin waves by electric field
KAIST Kab-Jin Kim
2020-71※ Novel strategy for intracellular delivery of nanomedicines
IBEC Silvia Pujals
2020-72※ Revealing exciton quenching mechanisms in thermally activated delayed
fluorescent devices
Tsinghua University Lian Duan
2020-73※ Fabrication of nanotopographical polymer surfaces for bactericidal
properties-II
Stony Brook University Maya Endoh
2020-74※ Synthesis of polyether nanocomposite solid polymer electrolytes forlithium ion batteriesMichigan State University Robert C. Ferrier, Jr.

※ 国際共同利用・共同研究

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2020-75※ Structural and functional analysis of the surface glycolipids of outermembrane vesicles released by bacteria
University of Naples Federico
Maria Michela Corsaro
2020-76※ Construction of heterologous protein secretion system at low
temperatures by using cold-adapted microorganisms
Southwest University Xianzhu Dai
2020-77※ Molecular mechanisms governing gene expression regulation in plant plasticity
National Center of Biotechnology Rubio Vicente
2020-78※ Formation of supramolecular complexes through a host-guest interaction
between cycloparaphenylene and azacorannulenes
Nanyang Technological University Shingo Ito
2020-79※ Research of multi-qubit diamond quantum processors
Australian National University Marcus W. Doherty
2020-80※ Research toward stable NV centers at shallow region in diamond
Leibniz institute for surface engineering Gopalakrishnan Balasubramanian
2020-81※ Advanced iodine–mediated stereoselective flow electrochemistry
Cardiff University Thomas Wirth2020-82※
ation-π interaction in enolate chemistry
University of Bristol Jonathan Clayden
2020-83※ Interdisciplinary approach to nanostructured materials for applications
Universite de Strasbourg Jean-Pierre Bucher
2020-84※ Relationship between chain orientation, amount of defects, and toughness ofglassy polystyrene materials
Changchun Institute of Applied Chemistry Quan Chen
2020-85※ Search for four-wave-mixing in the vacuum - Unveiling dark components in
the Universe Hiroshima University Kensuke Homma
2020-86
Fine synthesis of polymer brash on ferromagnetic nano-platelet formagnetophotonic LC
Osaka University Yoshiaki Uchida
型
体の
化
の機能解
2020-87大阪
大学
子
2020-88
Study on the regulatory network of plant epidermal cell differentiation
Hiroshima University Rumi Tominaga
化 るナノ 合体2020-89大阪大学
2020-90
Functional analysis of non-canonical strigolactones as plant hormones androot-derived signals
Meiji University Yoshiya Seto
2020-91
Analysis of phase equilibrium and molecular dynamics in mixture ofnematic liquid crystal and solvent
Japan Women's University Ryoko Shimada
2020-92のス
ラク
合成にお るCYP711A
ーの機能解
東 大学
井
2020-93
Analysis of the physiological functions of extracellular vesicles produced by intestinalbacteria and fermented food-derived bacteria and their application
Kindai University Atsushi Kurata
合性分子による細の化
2020-94
大学※ 国際共同利用・共同研究

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2020-97

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2020-99
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2020-102

2020-103
2020-104
2020-105
2020-106

2020-107
2020-108
2020-109
2020-110
2020-111
2020-1122020-113

2020-114

Observation of spin wave propagation in polycrystalline YIG thin films
prepared by coprecipitation method
Gifu University Keisuke Yamada 95
性
過 プ
による
応
大学 大
96
Giant exchange reaction from H to D terminating on nanocrystalline
silicon surface and their use
Nagoya City University Takahiro Matsumoto 97
面 性 を用いた
による金属
の
大阪
大学
健
98
Anomalous Hall effect of ultrathin Pt films grown on magnetic oxide
Hokkaido University Taro Nagahama 99
子
を機能性 化 合成の構造 性研究
ル ー加
研究機構
100
ビ ス
ーを
る
パラ
ニレ の
性の
大阪大学
101
Study on electronic and magnetic behavior of perpendicularly magnetizedcobalt ferrite films
Nagoya Institute of Technology Masaaki Tanaka 102
マル ス ールレーによる p型 機
体
の電
動度
形大学
二 103
DArP法を用いた
π共
マーの開発
機
電
の応用
島大学
104
Au25ス
強 性 電子 ラス
東 工業大学島
105
強度レーザー 構造性の作用による
ル ー密度プラズ
マの 成
持に
る
研究
大学
明 106
の外的ス レス 性にお る
の機能解
命 大学
107
ル ースの 形成 動の解明 表面による制御産業技術 合研究所
108
モの ナノレ ルにお る表面のNV中 作製
金 大学
109
田
モ
中のNV中 スの電 的制御 電 的産業技術 合研究所
野
110
4型分子
による化学選択的
ル化反応の理 的解
大学
中111
動的不 の発 を基る不性型 素素結合形成反応の開発
大学
112
Studies on enantioselective total syntheses of marine natural productbohemamines and their derivatives
Kanazawa University Tomoyuki Yoshimura 113
能
マスの
化学
の
的変 法の開発科大学
114
野※ 国際共同利用・共同研究

−vi−

合

型共同研究
13

2020-115※ Determine the three-dimensional structure ofla ele -synuclein in the Langmuir-Blodgett film and supported phospholipids bilayers by
p-MAIRS FT-IR
Middle Tennessee State University Chengshan Wang 115

2020-116※ Hydrophilic dendrimers as additive for polyvinylidenedifluoride based membranes
University of Montpelier MonaSemsarilar 117
2020-117※ Resolving percolation dynamics responsible for mechanical reinforcement inpolymer nanocomposites under uniaxial stretching
Stony Brook University Tadanori Koga 119
2020-118※ The 16th International Workshop for East Asian Young Rheologists
Osaka University Tadashi Inoue 121
設 機 利用型共同研究
2020-119※ Study on the mechanism of the crystal structural evolution of polydimethylsiloxane
University of Science and Technology of China Liangbin Li 123
2020-120※ High-pressure synthesis of potential multiferroic oxides
University of Edinburgh Kunlang Ji 124
2020-121※ Micro- and nano-structural characterization by advanced transmission electron
microscopy of novel functional materials for battery development
Chiang Mai University Torranin Chairuangsri 125
2020-122※ Electron energy loss spectroscopy analysis of hexagonal multilayer graphene
National Taiwan University Cheng-Yen Wen 126
2020-123※ Electronic excitations in charge-density-wave systems
National Taiwan University Ming-Wen Chu 127
2020-124※ Synthesis and characterization of novel organoselenium and -tellurium compounds
Rikkyo University Mao Minoura 128
2020-125
結 X 構造解 を用いた
ッ素共 分子の結 構造にお る
ル ラス
作用の解明
大学
129
2020-126 Synthesis and structural characterization of low-valent species of heavier
group 14 elements
Kindai University Tsukasa Matsuo 130
2020-127 DNP-NMRを利用 た 素
表面 能基解 法の開発
大学
131
ナノ
の理 設計
い動作 理の 究
2020-128 平面
東北大学
132
中の 素
ム 動の
度 定
2020-129 核 合プラズマ
島 大学
光
133
2020-130 Synthesis and structures of cationic aromatics bearing thiopyrylium units
Fukuoka University Noriyoshi Nagahora 134
2020-131 FT-ICR-MSを用いたび
中機 の化学 性および起 解
工大学
135
2020-132 2 元の起子のSTEM-EELS解
大学
光 136

※ 国際共同利用・共同研究−vii−

２．国際学会、シンポジウム・研究報告会
新型コロナウィルス感染拡大防止のため、令和 2 年度は開催せず。

137

３．成果発表論文（令和 3 年 2 月までに刊行された論文で、平成 22－令和元年度の成果報告書に掲載されていないもの）

紙数の都合により、*を付けた論文のみについて、別刷りを本報告書に記載する。

1)* Highly Luminescent CsPbBr3@Cs4PbBr6 Nanocrystals and Their Application
Electroluminescent Emitters, J. Phys. Chem. Lett., 11, 10196–10202 (2020).

in2)* Effect of Head-to-Head Association/Dissociation on Viscoelastic and Dielectric Relaxation of
Entangled Linear Polyisoprene: An Experimental Test, Macromolecules, 53, 1070–1083 (2020).
3) Helicenes Fused with Hexafluorocyclopentene (HFCP): Synthesis, Structure, and Properties,
Eur. J. Org. Chem., 2020, 1871–1880 (2020).
4) Development of P- And N-Chirogenic Ligands Based on Chiral Induction from a Phosphorus
Donor to a Nitrogen Donor in Palladium Complexes, Organometallics, 39, 1672–1677 (2020).
5) Reaction of germabenzenylpotassium with TBDMSCl: Unusual trimerization
germabenzene skeletons, Phosphorus Sulfur Silicon Relat. Elem., 195, 936–939 (2020).

of6) Visible-Transparent Aromatic Polymers Obtained by the Polycondensation of aBis(trifluorovinyl)benzene with Bisphenols, Macromolecules, 53, 2942–2949(2020).
7) Insertion reaction of chalcogens into an Al-P bond, Heterocycles, 100, 1084–1093 (2020).
8) Facile preparation of , -diynes bearing a perfluoroalkylene linker –(CF2)n– (n = 4,6) andtheir application for Co- or Rh-catalyzed [2+2+2]cycloaddition reactions affording aromaticcompounds with perfluoroalkylene units, J. Fluorine Chem., 234, 109512 (2020).
9) Additive-Free Conversion of Internal Alkynes by Phosphanylalumanes: Production of
Phosphorus/Aluminum Frustrated Lewis Pairs, ChemPlusChem, 85, 933–942 (2020).
10) 1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene, Dalton Trans.,
49, 7189–7196 (2020).
11) Discovery of Self-Assembling Small Molecules as Vaccine Adjuvants, Angew. Chem. Int.
Ed., 60, 961–969 (2020).
12) A Single H2O Molecule inside Hydrophobic Carbon Nanocavities: Effect of Local
Electrostatic Potential, Chem. Lett., 49, 244–247 (2020).
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architecture, Polym. Chem., 11, 4417–4425 (2020).
14) Cation Recognition on a Fullerene-Based Macrocycle, Chem. Sci., 11, 12428–12435 (2020).
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−viii−

20) Enhanced antiferromagnetic resonance linewidth in NiO/Pt and NiO/Pd, Phys. Rev. B, 101,
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23) Observation of superconducting diode effect, Nature, 584, 373–376 (2020).
24) Tailoring THz antiferromagnetic resonance of NiO by cation substitution, Phys. Rev. Mater.,
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27) An Artificial Amphiphilic Peptide Promotes Endocytic Uptake by Inducing Membrane
Curvature, Bioconjug. Chem., 31, 1611–1615 (2020).
28) Enhancing the activity of membrane remodeling epsin-peptide by trimerization, Bioorganic
Med. Chem. Lett., 30, 127190 (2020).
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33) Discovery of a Small-Molecule-Dependent Photolytic Peptide, J. Am. Chem. Soc., 142,
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34) Tris(triazolo)triazine-based emitters for solution-processed blue thermally activated delayed
fluorescence organic light-emitting diodes, Mater. Adv., 1, 2862–2871 (2020).
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−ix−40) Rheo-Optical and Dielectric Study on Dynamics of Bottlebrush-like Polymacromonomer
Consisting of a Polyisoprene Main Chain and Polystyrene Side Chains, Macromolecules, 53,
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．
158
162

4-1.令和２年度公募要
4-2.令和２年度採択課題一−x−1．共同研究成果報告2020-1
化学的手法に基づく

ル
および設

モニックナ
術

の

中 充 大

[目的]

ルな

活性を す

を有する

ナ

ル

ナ

は、

モニックナ

は主に

リ グ

モン共

に基づく特

として んに研究されている。
ィーなどを用いた術研究所

加 によって成および設に られることから、より多様な術が められている。そこで、

モニック

されるが、

では化

ルな

した分

合 の存 下で 化 (III)

を

の合

を有する分

を 型とするらせん状 ナ ワイ ーの合成法を 展させることで本課題の
[実験]

能なナ

に 応できるナ々が報告した学

ル

学合成法に関する研究が特に注目を めている。しかしながら、化学合成によってのバリ ーシ ンは

な

合

を行った。

、L- スコル ン を 元 として、

ナ ワイ ーを合成した。このとき、 元 の 度を 化させることで、 なる 件のもと ナ
ワイ ーを合成した。 成された ナ ワイ ーについて 応後 14 日後の（TEM）によりし、ナ ワイ ーの 学特性評価および

を

による

型
ネル ー

ス クトル 定（EELS）を行った。
[ 果と

]

/

元

度 が 1 未 の 合、の ナ ワイ ー（NW-3, Fig. 1a）が 成し、 元の度をおよび長さに大きな 化は見られなかった。一方、~3 nm、長さが

から

nm

度

しても 成される ナ ワイ ー/

元

度 が 2 のとき、

~7 nm かつ、長さが 400 nm 未 のナ ワイ ー（NW-7, Fig. 1b）が多く 成した。NW-3 の分
は中外

外
に

内で長さおよびにブロードなを したのに し、NW-7 では 1350 nm（0.92 eV）

ークを し、それに い二 性ス クトルも 化した。また、同一の なる ナ ワイ ーについて EELS を 定したところ（Fig. 1c, d）、 いま

たは ス クト の さいワイ ーほど、

ネル ー に ネル ー

果から ナ ワイ ーの 状 化に う 学特性 化の主なス クト ののであることを らかにした。

−1−を した。これらのは、ナ ワイ ーの長さまたは2020-2
中

外

ー

ーを用いた

動強

合による

応性

化の

平井 二

の
を

動

や

す。

、

れている。

強

導

や

ブリ

と

が強く

学の分野で、共合すると新たに

ロー共

ティ）

と

が

に

づく

などのいくつかの

器、

トニック

深い

、

に関連する

ティの
に

強

ネル

合が化学

応

展している。

外

ー

を
の

における

に

し、この

本研究では、

ッ

、

を指し、

ド

では、分
ン）はテ

合が基

合が注目さ

用して、

えることが報告され、

動強

深い特性

強

ブバンド

の 動（

の

成し
の

器を

としてきた。
を

が

化学研究所

ス

が提案されている。これまで、

モン共く研究されてきた。これらの研究の多くは、
ど、

成状

器（

合とは、
増強相

大学

的、応用的な

強

、

ン

の

動

合が広
ウ

な
と

動強

合化学の分野がル（THz）から中

点から

が

たれ

ている。
LC 共

と

を 100nm に めたス リットリング共 器（SRR、図１）の

ロブス

イト

導

の

ンモードとの（O 300Pm）で 成できることを した。この さな
た。SRR

は、

ティングの

ッ

ことによって

べた。

た。

イ

ッ

ンの の

ームリ グ
イ
が

存性は、テ
ッ

内の

のより
つ

ル

の
ット

的な

じ

めが

ティによって

をシミュ

界増強
イ
強

した THzス

ッ

しの中に含まれる的な増加につながることが された。
存性がない の合状

ティとしている。このようなは、

リットリング共 器

−2−

定を行う

ートすることによってームとなる 能性がある。

図 1.

ス リッ

法による

の増加が

能なことを

られた

合 が 0.95 THz

ッ の 合強度は 0.24 であっ分を上 ることにより、 合強度のッ強した。強 合状 における界増強

さくなると、

この 果は、SRR が、 合強度の
ッ

ィで

の

学や化学

して、

ブミクロン
応の研究に

2020-3
X-ray structural studies on ligand complexes of maleylacetate reductase
Tadao Oikawa

Kansai University

Rhizobium is a genus of tubercle-forming bacteria. It grows in the root of a plant in symbiosis with otherbacteria to fix nitrogen from the air. Although considerable attention has been paid to Rhizobium genes andgene products, there is still little information available on the molecular structures, functions, and propertiesof the enzymes involved in the metabolic pathways. Rhizobium sp. strain MTP-10005 was isolated fromnatural river water during a screening experiment. Enzymological and genetic studies showed that thetranslational products of the graA, graB, graC, and graD genes (GraA, GraB, GraC, and GraD, respectively)
could be potentially involved in the resorcinol degradation pathway. To reveal the structure and function of allthese proteins, I have performed X-ray structural studies of the proteins in collaboration with Dr. Tomomi Fujii
and Prof. emeritus Dr. Yasuo Hata, Institute for Chemical Research, Kyoto University. In this study, we focusedon maleylacetate reductase (GraC), which catalyzes the NADH- or NADPH-dependent reduction of
maleylacetate to 3-oxoadipate and attempted to determine the structure of GraC-cofactor-ligand complex.
N-terminal His-tagged GraC was overexpressed in Escherichia coli BL21 (DE3), purified, and used forcrystallization. The GraC-NADH complex crystals were prepared using the sitting-drop vapor-diffusion
method with a protein solution containing NADH and a reservoir solution consisted of 20% (w/v) PEG1500
and 0.1 M Bis-Tris pH 6.5. The crystals were soaked in cryoprotectant solutions consisted of 30% (w/v)
PEG1500, 5 mM NADH, 0.1 M Bis-Tris pH 6.5, and each of several substrate analogs. Each soaked crystal
was picked up in a cryoloop and frozen immediately in liquid nitrogen. Diffraction experiments were
performed on beamline BL-5A, Photon Factory, KEK, Japan. Diffraction data for each crystal were collectedunder cryogenic conditions. The electron density maps were calculated using the data collected for each crystal
and the phases derived from the previously determined structural model of the GraC-NADH complex. The
electron density map of the crystal soaked in the cryoprotectant solution containing 10 mM adipic acid
dipotassium salt showed a blob of density at the active site. An adipate molecule was modeled in the blob, andthe structure was refined at 1.9 Å resolution.
In the present crystal, one homodimeric GraC molecule exists in the P1 unit cell, and each subunit binds an
NADH molecule and an adipate molecule. The subunit of GraC molecule consists of two domains: an Nterminal domain with an / structure formed by residues 1–159 and a C-terminal -helical domain formedby residues 160–351. The adipate molecule is located in the vicinity of NADH bound to the active site cleft
between the domains of the subunit. The superposition of subunit C atoms between GraC-NADH-adipate
and GraC-NADH complexes results in the root mean square deviations of 0.49 Å. No significant
conformational changes are observed in the protein backbone upon the binding of adipate to the GraC-NADH
complex. In the active site, one of the carboxyl groups of the adipate molecule forms hydrogen bonds with theside-chains of Asn170, His243, His253, and His257. These residues might be involved in substrate binding or
catalysis.
−3−2020-4
ー

ー

度

による

機能性

加
大

大学

1.

はじめに
ン(Ti)はインント材として広く用いられているが、材 であるが に長期的な 用 に題点を有している。この 題点をするために Tiに新機能を 加する 要がある。これまでの研究において、Ti 基 上にムトー ーをすることにより 成した 期的(LaserInduced Periodic Surface Structuring, LIPSS)が展に有 であることを報告されている 1)。特に、展を行なうにあたって LIPSS の 期が 要であることがされた。LIPSS の 状は材 特性、 ー ー 長、等の件によってることが かっており、
の
（
の なる
を
に設 ）を人 的に 化させることで LIPSS の 期をすることにも成 している 2)。しかしこれらの手法で られる LIPSS の 状は 定的であり、の 一な 期性を ることには成 していなかった。そこで 々は、
ムトー ーの基本 と二を用いた二 ーム 合により Ti 基 に い 期性の LIPSS 成をた。二 長の ルスの なる応 により LIPSS の 状を行い、また、 ルス のが LIPSS の 状（特に期性）に えるを べたので報告する。
2. 実験方法
Cyber Laserのムトー ー
からの ー ー ルス ( 長 800 nm
り し
1 kHz
ルス 150 fs) をハー ミ ーにより分 させ、一方は
(
)を
し、もう一
方は二
（
は基本 に して）にし 基本 と同軸にイ ントした後に Ti 基した。スポット はともに 25 m (FWe-1M) となるように 整した。二が先に基 にする 件を のと定 し
700 ps の で 化させ実験を行った。30 300 ルス
し、型(SEM)を用いて状をした。
3. 実験 果Fig. 1 (a)および(b)に基本 の を 60 ルス
したときおよびを 0ps に設定し、基本と二を 60したときの SEM
をそれ れに す。二 ーム 合の件（
、 ルー ンス）を化することで LIPSS の 期性が向上したことが分かった。

Fig.1 SEM images of Ti surface after (a) only fundamental wavelength pulse
irradiation and (b) two color double pulse beam irradiation.
参 文1) T. Shinonaga, M. Tsukamoto, T. Kagwa, P. Chen, A. Nagai, T. Hanawa, Appl. Phys. B. 119 (2015) 493.
2) K. Takenaka, M. Tsukamoto, Y. Sato, T. Ooga, S. Asai, K. Murai, Appl. Phys. A, 124 (2018)410.
成果報告[1] M. Hashida, Y. Furukawa, S. Inoue, S. Sakabe, S. Masuo, M. Kusaba, H. Sakagami, M. Tsukamoto, J.
Laser Applications 32(2020)022054.

−4−2020-5
2 色パルス誘起微細周期構造形成過程の研究
長

大学

1 つの
ムト
ー
ルスを
ン
に
した後に、
（
）をつけてもう 1 つのー
ルスをする「 ブル ルス」により られる
期について、1 つの ルスのを（シングル ルス
）した 合とした。特に、組 合 せる ルスの 長を えた「二 長ブル ルス」（図 1）を行い、 ブ ーシ ンの深さやナ
期
の 状が、
や ル ン
スの組 合 せによって 化することを らかにした。
の都合上ここでは べないが、二 長 ブル
ルス
を行うことで ブ ーシ ンの深さがシングル ルスの 1/3 にされ、 の1）や 入長の いが ブ ーシ ンのにしていることがされた 。 期の 一性は、
期

SEMの 2 次元 FFT から られる広がり GT（DOLA: dispersion in the LIPSS orientation

angle）を用いて評価した（図 2、 一性が いほどGTは さくなる）。二 長 ブル ルス
されたは い 期性を つことが分かった（図 3）。図 3 (a)は期整された 400 nm のムト

ルスで り出されるー

ルスを 60が nm

はルス

して 成された 期

ー ーで、 の向きはであった。 一性を す指 はGT= 26 であった。図 3 (b) に遅延
ルスに 800 nm

ルスを同軸状に 整し 60

ルスの ル ンスは

の 0.9

た 期

び の向きは 800 nmの

図 3 (a)の 400 nm
ーシ ン
に じる

であり、

の 1.5

の ル ンスにを す。400 nm

方向（ の

）に しほ

を 0 ps に設定し、先の 400 nm

したときに 成される 期
方向（ の

により 成

）は 400 nm

ルスとを す。800 nmさせた。 成されルスで まっていることが かった。GT= 12°となり、ルスの の 合より 一性が向上した。また、 ルスのを らかにするため ブと ー長の関 を べた。第 2 ルスの 長が いほどの 度が関 っている 能性がされた。

は くなり、

Femtosecond laser(800 nm)

800nm
400nm

Ti plate

Fig.1 Experimental setup for two color
double pulse beams.

Fig. 2 The uniformity of LIPSS were determined bydispersion in the LIPSS orientation angle (DLOA) for
obtaining 2D-FFT spectrum.

参 文1） Takenaka, K. Tsukamoto, M.

Hashida, M. Masuno, S. Sakagami, H.

Kusaba, M. Sakabe, S. Inoue, S. Furukawam, Y. Asai, S.: Ablation
suppression of a titanium surface interacting with a two-color double-pulse
femtosecond laser beam, Appl. Surf. Sci. 478, (2019) 882-886
2） Hashida, M. Furukawa, Y. Inoue, S. Sakabe, S. Masuno, S.

Kusaba, M.

Sakagami, H. Tsukamoto, M. : Uniform LIPSS on titanium irradiated by
two color double-pulse beam of femtosecond laser, J. Laser Appl. 32(2020)022054-1-022054-4.

−5−

Fig. 3 High periodicity LIPSS on titanium surface
irradiated by two-color double pulse beam2).

2020-6
ナ

を

つ

用

大

的の開
化学研究所 科加 器科学研究 ン ー

目的
定核 成法の一つである
法では、 的内で 成した定核を、 的をにすることで取り出している。そのため、でもが くかつ融点も い、 化 が 的として用いられることが多い。しかし、これまでの研究によって、 化
的の
が 一
度で
あることが分かっている。これは、環境下では 化 のが進むため、 的内部のが さくなり、定核が出てこなくなるためである。
として、 年 ー ンナ
ューブを用いた 化的が提案されるが、しやすく、取り いには 用の設備が 要である。本研究の目的は、 ー
ンナ
ューブやグ
ン等のナ
をもつ新たな 化 を用いて、取り いやすい用
的を開 することである。
実験手法とする元 の化合 ( 化 など)を
材 と 合し、をかけ、 さ 1 mm、20 mm 度の的を 成する。 成した 的はンバー内でに加 し、 化とする。 成した 化
的は、を用いて、そのナを べる。その後、
ーム
もしくは
ームを
し、
定核 成 の 化から 的や 成などを べる。本年度はグンを用いた
的 成 び 化行った。
所は核取り いの 要から、 化学研究所 科加 器研究 ン ーにて、 科 ン ー
進一 と共にを行った。手 としては、
ま
化ウ ンを
に
し
ウ ニル
を 成する。次に
ウ ニル
をグ
ンに含
後、
・ 化する。 化 に 要に応じてグンを 加後、
ス機を用いて的を 成する。 成した
的は、ンバー内でに することで、 化とする。
果化ウ ン(U3O8:4.15g)を
ウ ニル
に
後、グ
ンに含 し、・ 化
を て、
的(UO3+グ
ン、20mm,1mm)を 成した。このでは U:C モル が1:8 になるようにグン を 整し、 化
後に U:C モル が 1:4 度になることを目指した。
成した
的はンバー内で 1100
度までし、 化 応が終 するまで 10 日
状 をした。
中は、6UO3+C Æ 2U3O8+CO2, U3O8+CÆ3UO2+CO2, UO2+3CÆUC+2CO
といった一連の 応を て、 化ウ ン(UC)が 成されていると えられる。
化
終 後の 的を1-1)に した。従来ので 成した 的と同様にが見られた。しかしながら、中にに 化が まってしまい(
1-2)参 )、ものの 分ですべて 化ウンにされた。 化後は1-3)に すように層らしきものが見られたが、グンの特性によるものなのかは、さらなるが 要である。

1: 1)

化

後の 化ウ ン 的、 2)

的の 化中の様 、 3)化後の 的の様

グンを用いた的の 成には成 したが、 化後ここまです に 化 応が きてしまうのは、外であった。とはいえ、今 の 果は、 成した 的が定核の導出に 要なを備えていることもしており、 的の性 として期 が てるものである。今後はい 化 応に 応するべく、取り いの開 を進めていく 定である。
成果報告 特になし。

−6−

2020-7
電⼦散乱による短寿命不安定核の奇妙な構造の解明
利

大学

学研究

ン

ー

ーム科学研究の若ととも目的と研究方法
本研究は、化学研究所・先端
に

科学

定核の内部

の

により

ームナ

核に

し

は

の

核と

をあ

相互

より

用が

定的な

を果たしてきた。実験

験

で研究

になり、

での

進化

の
に

ー・
を目

としている。

核内部

の

報を

き出す

学で

に

されているために存する

り出すことができる。したがって、

は

が

ン

れた

な

核の

には存

しない

識を

す

要であることから世界各

で

を
を

ームを

定方法であるが、定から定術の進展により

定核で

は、

さなく内部
では
な

定核が実

する研究やこれらのる研究が展開されている。

本研究と今年度の成果
定核

研究にも

保が

な

が

定核の

る SCRIT 法とよち
施設をであるが、 成かつ

えられてきた。 たちはこの

を

能と

用新

成法を

出し、世界

的

今年度の共同利用

申請書では

についての

ち合

せを実施することを提案していたが、

かった。

での議

大研究者が京都大学を 2

するため

の

定核研究用

し新規研究を含む今後の研究ながらコロナ禍のため実できなはできなかったが、リモート会議システムを利用し定期的に会合を行い、共同研究を進めることと今後の研究
研研究者を含む１５

イドでは

分

の分

続した。この研究の

を議

の参加を

大

と中性

的

研究は

めている。

した

分な

による

設・運用を

行して、

で

することはできた。また関連した研究に関するもてリモートで実施した。
により提案された

報を

果を今年度

定する新しい
文として

性

で

方法の

定する

度分

ならびに実験

能性の

を利用
を

した。

The mean square radius of the neutron distribution and the skin thickness derived from electron scattering
H. Kurasawa, T. Suda and T. Suzuki, Progress in Experimental and Theoretical Physics, 2021 (in press).
今後の
年度

定
3 月には

大学

モート研究会を開催する
や

で

学研究

ン

ーの支援も

て、

国の研究者に定である。また、来年度も本研究についての

定できる分

報

度について京都大学の共同研究者と

る。

−7−

を

をかけたリ

続し、実験

めて行く

能性

定としてい

2020-8（国際）Gas sensing properties research of transition-metal oxides
Haichuan Guo

Ningbo Institute of Industrial Technology

Introduction
The perovskite-type oxides are widely used to detect poisonous and harmful gases
because of high sensitivity and excellent selectivity, which demonstrates excellent
application potential in the field of gas sensors. Herein, a new design of sensor array (Fig.
1) was realized by integrating a series of transition-metal oxides LnFeO3 (Ln = La, Pr,
Nd, Sm), which revealed excellent recognition ability for various VSCs (H2S, CS2, DMS,
and DMDS), showing promise for real time monitoring [1].
Experiments and results
LnFeO3 materials were synthesized by the citrate sol-gel method. As-prepared oxide
powders were dispersed in deionized water and drop-coated on alumina ceramic
substrates with comb-type Au electrodes. The ceramic chips were calcined at 300 oC for
1 h to strengthen the stability and repeatability. Gas sensing properties were measured
using an intelligent gas sensing analysis system by the static volumetric method. The
recognition abilities of the LnFeO3 sensors were investigated by the sensor array and theprincipal component analysis (PCA) were conducted to distinguish four typical VSCs.
The results (Fig. 1 inset) clearly show that different concentrations, the region ofplots and various shape for each kind of VSCs. It can be obviously seen that the data
points of sensor array could be clustered and four different VSCs can be obviously
distinguished. Therefore,
the result indicates that thefootprints of different
VSCs
gases
were
successfully determined,
which demonstrated thepossibility of detecting
and discriminating the
VSCs in air pollution by
the LnFeO3 sensor array.
Fig. 1 Schema of the sensor array and the result of PCA analysis[1] Z. Zhang, S. Zhang, C. Jiang, H. Guo, F. Qu, Y. Shimakawa, and M. Yang, Integrated sensing
array of the perovskite-type LnFeO3 (Ln = La, Pr, Nd, Sm) to discriminate detection of volatilesulfur compounds. Journal of Hazardous Materials, 2021, in press.

−8−

2020-9（国際）Separation and evaluation of thiolate protected metal clusters with atomic
precision by using LC/MS
Yuichi Negishi
Objectives

Tokyo University of Science

Thiolate-Protected gold nanoclusters (Aun(SR)m) have size-specific physicaland chemical properties. In these nanoclusters, ligand-exchange reaction is commonly used toinduce further functionality. In recent years, although it was reported that ligand-exchange
reaction proceed with size-conversion at the same time, mechanism of this reaction is notrevealed. For elucidation of size-conversion mechanism, it is necessary to obtain the informationof intermediate products in reaction.
Experimental methods

In our work, we tried to

track ligand-exchange reaction with the size-conversionof Au25(SR)18 cluster to Au28(SR)20 cluster byintroducing LC/MS which was directly connected thechromatograph with the mass spectrometer. We usedreversed-phasehigh-performanceliquidchromatography (RP-HPLC) and electrospray ionization
mass spectrometry (ESI-MS) under guidance by ICR
partner researchers. The ligand-exchange reaction started
at addition of 4-tert-butylbenzenethiol (HSPhtBu) toFigure 1. UV chromatograms of[Au25(SC2H4Ph)18]– clusters (a) before
and after reaction at (b) 10 min, (c) 30
min, (d) 60 min and (e) 120 min.

[Au25(SC2H4Ph)18]– dissolved in toluene. The products ateach reaction time were evaluated by LC/MS.
Results and discussion

Figure 1 shows the UV

chromatograms of the crude product at each reaction
time. In these chromatograms, multiple peaks wereobserved. The reaction time of peaks were longer thanthat of Au25 (Figure 1a) with the progress of the reaction
time (Figure 1b–e). It is considered that polarity of the Figure 2. (a) UV chromatograms at 380
nm of the crude product after reaction forcluster change to lower as the number of ligand- 30 min and (b) UV-vis absorbanceexchange

increased.

Figure

2a

shows

the

spectra of the products at typical peaks

UV in (a).
chromatogram of the crude product after 30 minutes of reaction at 80 qC. Figure 2b shows theUV-visible absorption spectra of the separated products at typical peaks in Figure 2a. In spectra
i iv, the disappeared and the new specific peak of Au28 clusters was observed at 365 nm. Fromthese results, it was revealed that products of ligand-exchange reaction could be separated andthe electronic structure change could be tracked by our method.
Publications[1] Y. Negishi et al., Nanoscale, 12, 8017-8039 (2020).
[2] K. Isozaki, Y. Negishi, T. Hasegawa, M. Nakamura, K. Miki et al., Catalysts, 10, 908 (2020).
−9−

2020-10（国際）−10−2020-11（国際）Design and tailoring advanced functional materials:
Symmetry operation and high pressure synthesis
Wei-tin Chen National Taiwan University[Introduction] The exploration of fascinating functionalities and phenomena of novel materials
is essential in modern condensed matter sciences which is motivated much by the succession
needs of novel technology applications. High pressure synthesis techniques are one of mostimportant methods in preparation of such novel materials. The previous supported project has
successfully demonstrated the unique ability to prepare novel materials with high-pressure
synthesis, and this project proposes to continue the utilization of such unique techniques fornovel materials exploration. It is targeted to design and investigate, for instance, compounds
containing unusual high valence state or showing exotic structural/charge/orbital/spin phasetransitions. With the 6-8 two-stage Kawai-type 111 geometry and cubic anvil DIA-type highpressure apparatus equipped at Advanced Solid State Chemistry Laboratory (Shimakawa lab),extreme pressure and temperature synthesis conditions were realized for novel materials
synthesis.
[Results and discussion] The joint research became difficult under the situation of pandemic inyear 2020. Nevertheless, various projects were carried out with utilizing the unique high-pressure
apparatus at Prof. Shimakawa’s lab, and high resolution synchrotron x-ray powder diffraction
experiment were performed at Taiwan Photon Source, NSRRC (Taiwan) with beamline joint
research proposal. For compounds containing unusual high valence state, successive complex
site-selective charge-redistribution transitions were revealed in hexagonal 12-layered BaFeO3
perovskite.[1] Li-hydroxide halides with antiperovskite structure LiBr(Li2OHBr)2 was preparedwith solid state reaction, and it was shown that the Li+ ions primarily contribute in twodimensional ion conduction.[2] In order to further understand the intriguing structural phasetransitions observed in HgMn7O12 quadruple perovskite,[3] e-/h+ doping effect and chemicalpressure effect were investigated with introducing
various cation into A site (Fig. 1). Apparent changeof the LT structure and transition temperature wereobserved and detailed structure analysis is ongoing
to understand the origin of the modification.
Fig. 1 T-dependent SXRD patterns of the doped
quadruple perovskite (HgxA1-x)Mn7O12.

[References]
1. Z. Tan et. al., Phys. Rev. B, 102, 054404 (2020)
2. A. Koedtruad et. al., RSC Adv., 10, 41816 (2020)
3. W.-T. Chen et. al., Phys. Rev. B, 97, 144102 (2018)−11−

2020-12（国際）Development of unsymmetrical -electron systems of heavier main groupelements and elucidation of their property
Takeaki Iwamoto

Tohoku University

Objectives: -Electron systems containing multiple bonds of heavier main group elements havebeen studied as prospects for advanced materials and reagents for small molecule activation. We
aimed at developing unsymmetrical -electron systems containing a double bond between group14 and group-13 elements, which remain scarce compared to other heavier -electron systems.
Experimental methods: To synthesize the unsymmetrical -electron systems R2Si=AlR', weinvestigated the preparation of the corresponding precursor containing an Si–Al bond using thereaction of cyclic (alkyl)(amino) silylene 1 with halogenated alanes.
Experimental Results and Discussion: We prepared a series of trihaloalanes coordinated bysilylene 1 (2a-2c), all of which were fully characterized by a combination of NMR spectroscopy,
elemental analysis, and X-ray single-crystal diffraction (XRD) analysis. Notably, in the presenceof an excess amount of 1 for the reaction of AlI3, we obtained a 2:1 adduct 3c as colorless crystals.
Compound 3 is a product resulting from the formal insertion of silylene 1 into the Al-I bond of
2c. 3 is stable only in the solid state and dissociates into 2c and 1 in solution, indicating that thereaction of 1 and 2c is reversible. During the investigation of the reactions of 2a-2c with various
bulky nucleophiles to introduce a protecting group for an Si=Al bond, we obtained
diphenylamino-substituted silylalanes 4b and 4c. Although the reductive dehalogenation of 4band 4c by the reducing agent such as KC8, Na, etc. provided essentially a complex mixture, thereaction of 4c with unsolvated (Me3Si)3SiK provided a product assignable to 5c. Although themechanism for the formation of 5c remains unclear at this time, unsolvated silyl anion may be asuitable reagent for the dehalogenation reaction of the silylhaloalane precursors to provide thedesired Si=Al species.

This project was done in collaboration with Professor Norihiro Tokitoh (ICR Partner
Researcher) and Professor Shigeyoshi Inoue (International Collaborating Researcher, Technical
University of München, Germany).

−12−

2020-13（国際）Optical control of high-order harmonic generation from solids
Shunsuke Sato

University of Tsukuba

Objectives
High-order harmonic generation (HHG) is an extreme photon-up-conversion process via
extremely-nonlinear light-matter interactions. Thanks to the high coherence of the HHG process
in gas-phase targets, a technology of ultra-short laser generation has been established. Recently,
HHG from solid-state materials has been observed, and it has been gathering much interest as apromising candidate for novel light sources beyond the gas-phase HHG. However, themicroscopic mechanism of the solid-state HHG is still highly controversial. In this research, weaim (i) to clarify the microscopic mechanism of the solid-state HHG and (ii) to establish aprocedure to optimally-control HHG through optimization of driving laser fields, together withthe partner ICR researchers Prof. Kanemitsu and Dr. Hirori.
Theoretical results
To obtain microscopic insight into the HHG, we
simulated the electron dynamics in graphene underelliptically-polarized light with the quantum masterequation. Figure 1 shows the computed intensity of the
7th order harmonics from graphene as a function of theellipticity of the driving laser fields. As seen from thefigure, the HHG can be enhanced by elliptically polarizedFig.

light. Based on the microscopic analysis, we clarified that

intensity from graphene as a function

the enhancement of the HHG with elliptically-polarizedof light ellipticity.

1The

7th-order

harmonic

light originates from the complex interplay among thefield-induced intraband and interband transitions.
Discussion
Having clarified the microscopic mechanism of the HHG in solids based on the interplay of
intraband and interband transitions, we further developed a way to control the HHG bymanipulating the interplay through the laser parameter optimization, e.g., the relative phase
control of two-color lasers. The experiment-theory joint project along these lines is already undera way.
OutcomeShunsuke A. Sato, Hideki Hirori, Yasuyuki Sanari, Yoshihiko Kanemitsu, Angel Rubio, "Highorder harmonic generation in graphene: Nonlinear coupling of intraband and interband
transitions", Phys. Rev. B 103, L041408 (2021).

−13−

2020-14（国際）Iron-catalyzed C-H borylation
Alakananda Hajra

Objective:

Fe-catalyzed

sp2-C_H

Borylation

Visva-Bharati UniversityofalkenesandImidazo[1,2-a]pyridines
Imidazopyridine, an important class of nitrogen containing heterocycles,shows a wide range of biological activities such as antitumor, antiparasitic, antiviral,
antimicrobial, fungicidal, anti-inflammatory, hypnotic etc. In addition, this motif isthe core structure of some marketed drugs such as necopidem, zolpidem, olprinone,
saripidem, zolimidine, alpidem, etc. Furthermore, few of them exhibit excited-state
intramolecular proton transfer. Organoboron reagents are important synthetic
intermediates that have a key role in the construction of natural products,
pharmaceuticals and organic materials. The development of simpler approaches toorganoborons can open additional routes to diverse substances.
An efficient and practical borylation protocol has been developed for thesynthesis of borylated imidazo[1,2-a]pyridines via cost-effective and environmentallybenignFe-catalyzed

C-H

functionalization.

A libraryof

C3-borylated

imidazo[1,2-a]pyridines were synthesized.

Presently we are focusing on the precise role of FeCl3 and visible light, and latestage modification of the compound. To the best of our knowledge this is the firstreport for the synthesis of borylated imidazo[1,2-a]pyridines. Easy availability ofbasic chemicals as starting materials, less expensive metal catalyst tolerance of awide range of functional groups, operational simplicity and practical applicability
on a gram-scale are the notable advantages of this present protocol.

−14−

2020-15（国際）Electrochemically engineered peptide based organic-inorganic nanohybridsfor electrocatalytic conversion of biomass into value added chemicals
Apurba K. Das

Indian Institute of Technology Indore

The large-scale use of urea in the environment as a key ingredient of fertilizers and bio-waste
results in environmental pollution. The urea oxidation reaction (UOR) is an effective way toclean urea rich wastewater with the production of hydrogen.
Objectives: The main aims of this project proposal are:(a) Design and develop electrochemically engineered peptide-anchored electrocatalyst(b) Experimental validation of electrocatalytic biomass conversion to value added chemicals(c) To study the mechanistic insights for electrocatalytic biomass conversion
Experimental Methods: An aromatic benzo[2,1,3]selenadiazole-5-carbonyl protected
dipeptide BSeFL (BSe = benzoselenadiazole) suitable for electrodeposition method has beensynthesized, purified and characterized. The electrochemical deposition of the BSeFL/Ni(OH)2electrocatalyst on carbon paper (CP) was carried out by the pulse-electrodeposition technique.
Experimental Results: In this study, simultaneous pulses of oxidation potential and reduction
potential were applied to prepare the electrocatalyst. The BSeFL/Ni(OH)2 was pulse
electrodeposited at different reduction potentials. The SAED and XRD pattern confirmed theamorphous nature of nanosheets. The EDS and XPS analysis revels uniform distribution of Ni,
C, O, Se and N over cross-linked nanosheets of organic-inorganic nanohybrids. The catalytic
urea electro-oxidation activity of the pulse electrodeposited BSeFL/Ni(OH)2 (-1.0 V)
electrocatalyst was evaluated using the three-electrode cell. The LSV curves were recorded in 1
M KOH solution containing 0.5 M urea at a scan rate of 2 mV s-1. Gas chromatography
analysis was employed to identify the gaseous product during the electrochemical UOR
process. The gas chromatogram of the UOR process shows the evolution of O2 and N2.
Discussion: The Ni2+ ions present in the deposition bath interact with OH- ions and carboxylate of
BSeFL present on the electrode substrate surface by coulombic interactions which results in thesimultaneous deposition of BSeFL/Ni(OH)2. At a lower pH gradient and low reduction potentialof -1.0 V, pulse-electrodeposition provides a denser film of electrically interconnectednanospheres with low charge transfer resistance for efficient electrocatalytic OER and UOR
activity.
Publications: Jadhav R. G., Das A. K., Pulsed electrodeposited, morphology controlledorganic-inorganic nanohybrids as bifunctional electrocatalyst for urea oxidation, Nanoscale,
2020, 12, 23596-23606.

−15−

2020-16（国際）Iron-catalyzed enantioselective carbometalation and ring-opening
reactions of oxabicycloalkenes and other related substrates andmechanistic consideration
Laksmikanta Adak

Indian Institute of Engineering Science and Technology:
The transition-metal-catalyzed carbometalation of alkenes has attracted considerable interest among
synthetic organic chemists, as it offers a useful pathway for the efficient and selective construction ofcarbon-carbon bonds. Because of the importance of asymmetric reaction for the synthesis ofpharmaceuticals and natural products, significant efforts have been made to develop catalytic
enantioselective carbometalation reactions of olefins. Palladium, rhodium, copper, and iridiumcatalyzed (Acc. Chem. Res. 2003, 36, 48; Angew. Chem. Int. Ed. 2012, 51, 5400; Org. Lett. 2002, 4, 2703;
Chem. Commun. 2013, 49, 9959) asymmetric transformations of oxa- and azabicyclic alkenes have been
extensively studied, where enantioposition-selective addition of oxygen, nitrogen, and carbon
nucleophiles brings about subsequent ring-opening reactions provide access to enantioenrichedcompounds bearing multiple stereocenters. Only one example was found for the catalytic asymmetricaddition of terminal alkynes to oxabenzonorbornadienes without the ring opening, which wasachieved by use of a chiral phosphine-cobalt catalyst system (Chem. Commun. 2012, 48, 6106).
Although the use of iron catalysts in organic synthesis are attracting increased attention due to its
economic and ecological points, but there application in enantioselective carbometalation has been
limited to only highly strained cyclopropene derivatives (J. Am. Chem. Soc. 2000, 122, 978). Nakamuraand his group previously reported the iron-catalyzed diastereoselective ring opening of oxabicyclic
alkenes with Grignard reagents (Org. Lett. 2003, 5, 1373) and also the highly diastereoselective
carbometalation of oxa- and azabicyclic alkenes with arylzinc reagents in which zinc reagents areused to trap carbometallated products prior to ring opening (Angew. Chem. Int. Ed. 2011, 50, 454). With
collaboration of Prof. Nakamura’s group we developed iron-catalyzed enantioselective
carbometalation and asymmetric ring opening reactions of oxabicyclic alkenes using a single catalyst
system (Scheme 1).
Scheme 1. Iron-Catalyzed Enantioselective Carbometalation and Ring-opening of Oxabicyclic
Alkenes

The screening of reaction conditions for iron-catalyzed enantioselective carbozincation ofoxabicyclic alkene with phenylzinc reagent were performed. Various chiral ligands and metal salts
were used for the screening and optimization of reaction condition. Finally, it was found that 2 mol%
FeCl3 and 4 mol% (S,S)-Chiraphos provided the best result for the enantioselective carbometalation
reaction.
(1) Based on the optimization of reaction conditions, the substrates scope for enantioselective
carbometalation reactions will be performed(2) Substrates scope for the ring opening products will be done
(1) Adak, L.; Hatakeyama, T.; Nakamura, M. Iron-Catalyzed Cross-Coupling Reactions Tunedby Bulky ortho-Phenylene Bisphosphine Ligands, Bull. Chem. Soc. Jpn. 2021, 94, 1125-1141.

−16−

2020-17
Study on the stability of novel ternary nanoparticles by doping 3rd elements
Yasutomi Tatetsu

Meio University

Many scientists have been investigating the possibility of creating novel materials by introducing third
elements into stable binary nanoparticles with advanced chemical synthesis techniques that might increase thesystem’s magnetic properties due to the change of its crystal structure. Recently, a new Z3-type Fe(Pd,In)3
crystal structure was discovered by Teranishi’s group in Kyoto University [1]. The new structure wassynthesized by introducing a third element of In into L12-FePd3, which is the thermodynamically stable phaseof binary Fe–Pd systems. Although the addition of In might be the key behind this new finding, the physicalaspects of In in stabilizing the new structure is unclear and cannot be understood deeply only throughexperiments.
In this report, we conducted theoretical analyses for the stability of an In-doped novel Fe–Pd phase. We
calculated formation energies of In-doped L12- and Z3-Fe–Pd systems using first-principles calculation code,
OpenMX [2], and compared the obtained energies in order to check the systems’ stability against theconcentration of In. The model structures for the calculations were based on the chemical composition ratioof Z3-FePd3 obtained from experiments. The In sites were chosen by replacing Fe or Pd sites with a specialquasirandom-structure method implemented in the Alloy Theoretic Automate Toolkit [3]. We investigatedstable sites for In in the L12- and Z3-FePd3 structures by comparing formation energies and we found that an
In stably is substituted for Fe and Pd at the e sites respectively. One of the interesting findings is that the moststable structure changes from L12-(Fe, In)Pd3 to Z3-Fe(Pd, In)3 when the concentration of In is around 20 %which is illustrated in the figure below. Same tendency can be seen in the experimental results from XRD,
EXAFS, and STEM-EDS analyses. This indicates that the new nanoparticles with the Z3-type crystal structure,in which In atoms replace Pd atoms at the e sites, can0

Pd site in Z3
Fe site in L12

be stably synthesized in a narrow range of In‑0.005for deeper understanding of how the magnetic
properties are affected by the In concentration in Z3type Fe(Pd,In)3.

Eform (eV/atom)

concentrations. Further theoretical analyses are needed‑0.01‑0.015[1] K. Matsumoto, R. Sato, Y. Tatetsu, T. Teranishi, etal., submitted.

‑0.02[2] http://www.openmx-square.org

1

2

3

4

5

6

The number of In in a system[3] A. van de Walle et al., Calphad Journal 42, 13

Figure: Formation energies for L12-(Fe, In)Pd3 and(2013).

Z3-Fe(Pd, In)3 depending on the concentration of In.

−17−

2020-18
における

端

学のための
井

1

中

外

の開

科学 術研究開 機Purpose of research

In this research program, we develop an ultrafast intense light source in the middle-infrared region of thespectrum for researches on the generation of efficient high harmonics in metal-halide perovskites supplied
from the host laboratory of Prof. Kanemitsu.
2. Experimental method
The middle-infrared light source has been developed based on frequency-down-conversion in opticalparametric amplification using the output pulses (center wavelength: 1030 nm, pulse energy: 2 mJ, pulse
duration: 190 fs, pulse repetition rate: 10 kHz) from an ultrafast ytterbium-doped Potassium-Gadolinium
Tungstate (Yb KGW) regenerative amplifier as pump pulses. The system layout is depicted in Fig. 1. A partof the output pulses from the Yb KGW laser is spectrally broadened to generate intra-pulse difference
frequency pulses as seed pulses for successive parametric amplifiers. The generated seed pulses around a
wavelength of 3100 nm are amplified in the first optical parametric amplification stage that consists of a 4mm-thick KTiOAsO4 crystal pumped by 180-µJ pulses at 1030 nm. The amplified middle-infrared pulses in
the first optical parametric amplification stage is further amplified in the second optical parametricamplification stage up to 80 µJ per pulse around 3100 nm.

Figure 1. System layout of the middle infrared light source
3. Discussion
An output pulse energy of 80 µJ is limited up to approximately a repetition rate of 3

5 kHz. A further

upgrade of the repetition rate towards 10 kHz is under way with an expected completion until the end of thisfiscal year. The research results will be summarized as a publication in a scientific journal.

−18−

2020-19−19−

2020-20
ジ

ル

合

応機

の

的な

とモ

ル化

中

ジ

研究の目的
モ

ーの

により

応機

応を

や、 応機

成する基本
を

機

る

的な

定する要

、およびそれにかか

る

応や機

など

に関

を

ることに取り組んだ。

果とま、 年度（R1）共同研究より

機

について

合

応の一つである

ル

ジ

究により

ルの

C-N

応では

化と C-C合の合はindex（PI）は

合の 合は

の

性に

応の こる

度により

存することをクリロニトリルの選択性においても同様の度に合存し、C-N合はにおいては機

に二

あり、

とを

した。一方、これらを

では合

的なモ

ルを

性に

モ

ることはできておら

合の

存する

に関す

ジ

合 応が

こることを

合を

の

成

し、

合の

分
の

合と

ル
した

年度研
から

応に

定

する

の Polarity

さくなった。
化と C-C果は（的な合の選択性は） クリロニトリルの
度に

化学による
が

存する

が続くこ

を行ったが

点

要とされた。

CN
N

H

H

を行い、機

の

ルおよびそれを

に

C N

CN

合は

ルについて
、より多

ー

ジ

向が見られ、

CNH

端

定されるのに存した。これらの性にすると共同し、主要モ

らかにした。C-N

し、PI が大きいほど C-N

い相関を

合成長

年各種
々の研究

） クリロニトリルの合に加えて C-N

化、C-C

応について

についての

続して（

を用いてこれら 3

らかにした。各種したところ、する要研究機分であったものが教を行った。 クリロニトリルの合がらかになりつつある。本課題では化学研究所の

合

モ

ル 合

・材

- o
CN
CN

H

o arit t

NC H

H

H

H

t
t

i co it t

CN

CN

CN

H

H
i
CN

H

NC

CN

H

CN
- o

等

1) X. Li, T. Ogihara, T. Kato, Y. Nakamura, S. Yamago, Evidence for Polarity- and Viscosity-

Controlled Domains in the Termination Reaction in the Radical Polymerization of Acrylonitrile, submitted. 2)
X. Li, T. Kato, Y. Nakamura, S. Yamago, The Effect of Viscosity on the Coupling and Hydrogen-Abstraction
Reaction between Transient and Persistent Radicals, Bull. Chem. Soc. Jpn. in press.

−20−

2020-21
Development of dinuclear nickel complexes based on a monoanionictridentate pincer-type ligand
Yoshitaka Yamaguchi Yokohama National University

Tridentate pincer-type complexes have generated a lot of interest because the pincer-type ligand stabilizes
the metal complexes and its properties can be tuned to achieve the best reactivity of the complex. We haverecently reported the synthesis of a series of pincer-type nickel(II) complexes utilizing a combination of Eaminoketonato or E-diketiminato frameworks with a third donor such as a phosphino or amino group. Our
systematic study on these nickel(II) complexes revealed that the modification of the ligand framework has asignificant influence on the catalytic performance in the cross-coupling reaction of aryl halides or allylic etherswith arylmagnesium reagents (Dalton Trans. 2018, 47,
8003.; Eur. J. Inorg. Chem. 2019, 126.; Molecules 2019,24, 2296.). We have focused our attention on catalytictransformations promoted by well-defined these nickel(II)complexes.
Organoboronic acids and esters represent versatile synthetic intermediates in modern organic synthesis,
particularly in cross-coupling reactions. Therefore, synthetic routes to organoboron compounds have been
extensively explored. We were interested in developing the hydroboration reaction of vinylarenes using ournickel(II) complexes as catalysts. We found that E-aminoketonato-based O,N,P-coordinate tridentate pincertype nickel(II) complex, Ni-ONP, shows high catalytic activity for the hydroboration of vinylarenes withbis(pinacolate)diboron (B2Pin2) in the presenceof KOAc as a base. These reactions proceeded
in a regioselective manner under mild

Ar

+

O

Ni-ONP (5 mol%)
KOAc (2.5 equiv)OO

toluene/MeOH
25 °C, 24 h

Ar

B B
O

conditions and afforded the correspondingO(2.0 equiv)

Markovnikov products in high yield [1].

BO
H

up to 99% yieldt

Alkyl aryl ethers are fundamental structural units for natural products, medicinal compounds and so on.
Various synthetic methods have been developed for the preparation of alkyl aryl ethers. Transition-metalcatalyzed cross-coupling reactions of aryl halides with aliphatic alcohols are one of the most efficient approachfor the construction of C-O bonds. During the study on thehydroboration reaction as mentioned above, we found that the
O,N,N-coordinate nickel(II) complex, Ni-ONN, shows highcatalytic activity for the cross-coupling of aryl halides withAr

Ni-ONN (5 mol%)
B2Pin2 (2.0 equive)
KOtBu (3.0 equiv)

X + ROH
toluene, 60 °C, 24 h
X = I, Br
R = 1°, 2° alkyl

ArOR

up to 86%

primary and secondary aliphatic alcohols in the presence of B2Pin2 and KOtBu as a base [2].
Further investigations on the application to catalytic reactions and the modification of the ligand framework
to construct dinuclear complexes are currently underway in our laboratory.
[1] Hashimoto, T.; Shiota, K.; Yamaguchi Y. “Selective Synthesis of Secondary Alkylboronates: MarkovnikovSelective Hydroboration of Vinylarenes with Bis(pinacolato)diboron Catalyzed by a Nickel Pincer Complex”,
Org. Lett. 2020, 22, 4033.
[2] Hashimoto, T.; Shiota, K.; Funatsu, K.; Yamaguchi Y. “Cross-Coupling Reactions of Aryl Halides withPrimary and Secondary Aliphatic Alcohols Catalyzed by an O,N,N-Coordinated Nickel Complex”, Adv. Synth.
Catal. 2021, 10.1002/adsc.202001346.
−21−

2020-22
性を用いたウルシ

ール

の機能
一 京都

術研究所

してきた。これはの主成分であ

目的
来より

に

を 合し

るウルシ ール（長

化

することで

を有する テコール 導 ）と イ ンのれている 1)。 の 化 応に
れる

は

の を

本来の

する テコールは イ ンとの 応により一部
・の 合を 化させることで成によるものとさ感をられるした状 となる。そこでの評価を行い

れるが
を用い

イ ンの

について

ら

イ ン
した。

実験
めに

化 (II)を所定のの に し件下にて 3 分させすることでを た。さらにを 成させた。

定を行った。 られた（日本

合（0, 0.1, 0.25, 0.5, 0.75, 1.5, 3.0 wt%）で 合し

の

の

は

で 50 Pm とした。同 に

れ

の評価（ス

を 20 oC/80%の 件下で

られた

験機

） び

の

定により

の評価

）を行った。

果は 0.8

化 (II)を加えていないの 定を行った。
化 (II)のであった。
の と合を増加させていくと 0.75 wt%までは 0.8 1

して は見られなかった。一方 それ 上の 度ではれ 1.5 wt%では 0.5となり 3.0 wt%では増 により 定

けでなく分

成が

での
られた

（図 1）。

の度かにのように 度の増加に（L*） 定において L*の が さいほを す。図 1 の 果より

化 (II)の 加が ない 合（0.1, 0.25 wt%）では L*は 5
は化 (II)を加した 合では L*は 1

を 0.5

上となり

であった。一方 0.5 wt%

られた

成による

す

が 認された。本 果より0.75 wt% 加し化 (II)

成させることでとなった。これより 分 内だ30
gloss level
L*

20

60

15

40

10

20

5

0

0
0

1

2
3
Fe(OH)2 (wt%)

図 1.
度

化
び

(II)の 合に（L*） 定として実用に えうることが かった。

参 文
1)

その科学と実

大

−22−

25

80

上の

下となり

の 度の増加が見ら

100

度の
のない

となり

120

定を行った

終的に 3.0 wt%では くとなった。これはどび

化 (II)の増加に従い

が見られ

る。また

された。

gloss level (%)

次にの の 合 指見

1999, p87.

4

する

L*

めに

2020-23
Creation of effective oxidation scavenger for efficient perovskite-basedsolar cells
Takahiro Sasamori University of Tsukuba
The goal of our collaborative research with Prof. Dr. Atsushi Wakamiya (ICR, Kyoto
University) is development of an organic oxidation scavenger for the creation of efficientlead-free perovskite-based solar cells, and pioneering research achievements on the basis of thefusion of elemental science and functional physical chemistry. Challenges for lead-freeefficient perovskite-based solar cells such as Sn(II)-based ones compared with their Pb
counterparts predominantly include the facile oxidation of divalent Sn(II) into Sn(IV) whichleads to the increased nonradiative charge recombination in the perovskite films. Thus, wehave focused our research targets on the creation of low-coordinated main group element
species as effective oxidation scavengers, which exhibit redox-active property and considerable
solubility in organic solvents.
Silylenes, organosilicon compounds with an Si(II) center, are known to be easily
oxidized under ambient conditions, suggesting their possible ability of working as effecting
oxidation scavengers. Isolable stable silylenes remain scarce, and in most hitherto reported
examples, the silicon center is stabilized by electron-donating substituents (e.g., heteroatoms
such as nitrogen), which results in electronic perturbation. In order to avoid such electronic
perturbation, we have been interested in the chemistry of redox-active silylenes withcarbon-based substituents such as ferrocenyl groups. Due to the presence of a divalent silicon
center and the redox-active transition metal iron, ferrocenylsilylenes can be expected to work
as an active oxidation scavenger. In this research project, we have successfully synthesizedbis(ferrocenyl)siliranes as a precursor for a bis(ferrocenyl)silylene, which could be a bottleableprecursor for the bis(ferrocenyl)silylene under mild conditions. We are grateful to Prof.
t

Wakamiya (ICR, Kyoto Univ.), Prof.
Yoshida(NagoyaUniv.),

Mitsudo (Okayama Univ.), and Prof.
Tsuchiya (Kitasato Univ.) for theirsupport on the research, and fruitful
discussions.
1.

Fe

Prof.

Fe
Si

Dtp

Si:

Dtp
Dtp

Fe

Dtp

under mild conditionsFe–siliranes“bottleable precursor”
for a bis(ferrocenyl)silylenebis(ferrocenyl)silylene
Dtp = 3,5-di-t-butylphenyl

Nakamura, T.; Yakumaru, S.; Truong, M. A.; Kim, K.; Liu, J.; Hu, S.; Otsuka, K.;
Hashimoto, R.; Murdey, R.; Sasamori, T.; Kim, H. D.; Ohkita, H.; Handa, T.; Kanemitsu,
Y.; Wakamiya, A. Nature Communications 2020, 11, 3008.

2.

Pan, Y.; Morisako, S.; Aoyagi, S.; Sasamori, T. Molecules 2020, 25, 5917.
−23−

2020-24（国際）A study on statistical machine learningfor efficient graph structured data analysis
Masayuki Karasuyama Nagoya Institute of Technology
For a variety of scientific fields such as biology, chemistry, and materials science, effective
methodologies for analyzing their complicated data are strongly demanded. In particular, we
focus on a graph-based representation, which enables us to handle data with interactions
among each one of objects [1]. For example, a chemical compound is often represented as agraph in which an atom is a graph-vertex and a chemical bond is a graph-edge. Although graphis a versatile tool for data representation, analyzing its statistical property is usually difficult
because of its combinatorial nature. In this study, we consider developing statistical machinelearning methods for efficiently analyzing graph structured data by combining several
techniques from data-mining, machine learning, and numerical optimization. For thisinter-disciplinary topic, we have worked with the researchers including prof. Mamitsuka in the
bio-knowledge engineering research laboratory of ICR.
We mainly focus on a task that statistically predicts a property associated with a given graph.
For instance, predicting toxicity of a compound is a well-known example in this type ofproblems. We construct an algorithm that identifies sub-structures of the graph strongly
contributing to the target property [2], which can provide insight about the underlying
correlation structure. However, naive calculation is computationally infeasible because thenumber of possible sub-structures are usually extremely large. To overcome this difficulty, we
extend a feature selection algorithm called Least Absolute Shrinkage and Selection Operator(LASSO), which has been widely used in statistical data analysis. LASSO is a linear model inwhich a small number of important features can be automatically detected through sparsity
inducing penalty on the parameters. In our problem setting, the features are all the possible
sub-graphs, and thus, can be intractable even just to enumerate. We propose an optimization
algorithm that efficiently prunes unnecessary sub-graphs in the graph mining tree. Our pruning
criterion is based on the optimality conditions from the numerical optimization problem of the
LASSO penalty-based sub-graph selection model, by which the optimality of the result can be
guaranteed. Effectiveness of the proposed approach in terms of computational efficiency andprediction accuracy is demonstrated by using several graph benchmark datasets.
[1] M. Karasuyama, and H. Mamitsuka, Factor Analysis on a Graph, Proceedings of the 21th
International Conference on Artificial Intelligence and Statistics, vol.84, pp.1117-1126, 2018.
[2] T. Yoshida, I. Takeuchi, and M. Karasuyama, Distance Metric Learning for Graph
Structured Data, arXiv, 2002.00727, 2020.

−24−

2020-25（国際）Integrating omics data and module-based network with deep learning todevelop cancer type predictive models
Jinn-Moon Yang National Chiao Tung University
Objective: Classification of cancer types has been a major topic in biomedicine andbioinformatics. To classify cancer types, various machine learning approaches have beendeveloped to better analyze mRNA expression data and improve the classification accuracy.
However, current studies focus on dealing with unbalanced data, but not emphasize on
exploring mechanism across multiple cancer types. A crucial step toward understanding
cellular systems properties is to analyze the topology of biological networks and biochemical
progress in cells. To construct the protein-protein interaction (PPI) network as completely as
possible, genome-scale interaction discovery approaches, such as high-throughput yeast
two-hybrid screening and co-affinity purification, have been proposed. However, current
approaches are not satisfactory for the integrated analysis of mRNA expression data, PPI data,and other omics data. Therefore, we need to develop more flexible and accurate methods.
Results. In this year, we have done the following two studies as sub-projects. (1) Identificationof active sites for small molecules. Identifying active sites of ligands for kinase proteins mightlead to development of novel drugs for such difficult diseases as cancer. Therefore, we havebeen developing a novel method for the purpose, using graph convolutional networks.
Currently, we are evaluating our developed method using several data sets and trying to
improve it. (2) Prediction of human dicer cleavage sites. It is reported that miRNAs are related
to different types of cancers such as lung, breast, and thyroid cancers. Understanding how dicer(enzyme) specifically selects cleavage sites may be useful to interpret the effects of mutations
in miRNA coding genes. Therefore, several computational methods have been developed forpredicting dicer cleavage sites. In this study, we developed a novel method, ReCGBM, bycombining (i) new relational features to combine each sequence and its complementary strand,(ii) class features obtained via affinity propagation, and (iii) gradient boosting machine (amachine learning method). The results using benchmark data sets suggest that ReCGBM is an
accurate and interpretable predictor.
Publication.
P. Liu, J. Song, C-Y, Lin, T. Akutsu: ReCGBM: a gradient boosting based method forpredicting human dicer cleavage sites, BMC Bioinformatics, vol. 22, paper ID. 63, 2021.

−25−

2020-26（国際）
Next-generation bioinformatics approaches for the accurate identification ofprotease-specific substrate cleavage sites
Jiangning SongMonash University

In collaboration with Prof Tatsuya Akutsu and his research group at the Bioinformatics Center, wehave carried out research activities, which are briefly summarized as follows:
Objectives:
Understanding of the mechanisms of regulation of proteolysis by proteases is very important for
elucidation of cellular processes. The key to this understanding is to identify the complete
repertoire of specific substrates that each protease targets.
Experimental methods:
We design the Procleave methodology to enhance protease substrate cleavage site prediction byincorporating 3D structural features of substrate cleavage segments. Procleave uses the data
curated from the MEROPS database and maps substrate sequences to PDB structures byperforming BLAST search, thereby generating an extensive 3D structural substrate dataset. Multifaceted sequence and structural features are then extracted, which are further integrated into a
conditional random field algorithm with a data-smoothing strategy to train prediction models.
Experimental results and discussions:
We also assessed the performance of Procleave with several state-of-the-art approaches. The
comparison results demonstrate that Procleave outperforms these methods, and the LOWESS
smoothing optimization is critical to the performance of Procleave. A user-friendly webserver ofProcleave is available as an implementation of the proposed approach. All predicted cleavage sitesof the human proteome with structure data are provided for protease biology research. This work
was published in the top journal Genomics, Proteomics & Bioinformatics in February 2020.
Publications:[1] Li F, Leier A, Liu Q, Wang Y, Xiang D, Akutsu T, Webb GI, Smith AI, Marquez-Lago T, Li J,
Song J: Procleave: Predicting Protease-specific Substrate Cleavage Sites by Combining Sequenceand Structural Information. Genomics Proteomics Bioinformatics. 18(1):52-64 (2020)[2] Mei S, …, Akutsu T, …, Song J. A comprehensive review and performance evaluation of
bioinformatics tools for HLA class I peptide-binding prediction. Briefings in Bioinformatics
21(4):1119-1135 (2020)[3] Chen Z, …, Akutsu T, Webb GI, …, Song J. iLearn: an integrated platform and meta-learner forfeature engineering, machine-learning analysis and modeling of DNA, RNA and protein sequence
data. Briefings in Bioinformatics 21(3):1047-1057 (2020)[4] J Zhu Y, Li F, Xiang D, Akutsu T, Song J, Jia C. Computational identification of eukaryotic
promoters based on cascaded deep capsule neural networks. Briefings in Bioinformatics, doi:
10.1093/bib/bbaa299 (2020)−26−

2020-27（国際）Revealing associations between giant viruses and eukaryotes in the global
ocean through community networks inference and mining
Samuel Chaffron

CNRS UMR6004

Nucleocytoplasmic DNA viruses (NCLDVs) are a monophyletic group of eukaryotic viruses that arehighly diverse and abundant in marine environments. NCLDVs are known to infect a broad range ofeukaryotes, from unicellular eukaryotes to animals. However, the knowledge of their hosts is largely
unknown. The number of viruses and hosts isolated in the laboratory represents a very small fraction ofexisting interactions in the ocean. Therefore, more consideration should be put into cultivation-independent
approaches. In our collaborative project, taking advantage of the recent Tara Oceans large-scale marine
metagenomics census, we used in silico network-based host prediction approaches to fill the gap and further
expand our knowledge of the unknown viral world.
First, we built co-occurrence networks of NCLDVs and eukaryotic taxa to predict virus-hostinteractions using Tara Oceans sequencing data (1). In total, 47,978 NCLDV-eukaryote associations wereinferred using FlashWeave, an efficient probabilistic learning algorithm for network inference. Then, weapplied a LR+ (positive likelihood ratio) based strategy to assess the accuracy of NCLDV host prediction
from these co-occurrence networks. For the first time, we demonstrated that the prediction of
NCLDV-eukaryote relationships based on co-occurrence networks is four times better than random
expectation. To further improve the performance of co-occurrence-based predictions and extract meaningfulpairs from high-dimensional co-occurrence networks, we developed a phylogeny-informed filtering method,
Taxon Interaction Mapper (TIM). We showed it further improved the host prediction of NCLDVs, and leadto a more concise list of candidate host lineages for three NCLDV families, which can be used to generate
novel hypotheses to be tested in future experimental studies.
Moreover, using network-based host predictions combined with TIM-based refinement, wedemonstrated that viruses explaining a large fraction of the variation of CEE (carbon export efficiency) may
infect hosts that are important in marine ecosystems, such as chlorophytes, haptophytes, diatoms, andcopepods. These findings imply that viral shunt and shuttle processes could depend on viral host interactions(2). We also used the co-occurrence network approach to predict the associations between NCLDVs andvirophage, known as NCLDVs’ “parasites”. The virophage-NCLDV associations further supported ourprevious statement that co-occurrence networks inference and related analysis are appropriate forinvestigating NCLDVs involved interactions in marine metagenomic data.
Publications:[1] Meng L, Endo H, Blanc-Mathieu R, Chaffron S, Hernández-Velázquez R, Kaneko H, Ogata H. 2020. Quantitative
assessment of NCLDV–host interactions predicted by co-occurrence analyses. bioRxiv
doi.org/10.1101/2020.10.16.342030[2] Kaneko H, Blanc-Mathieu R, Endo H, Chaffron S, Delmont TO, Gaia M, Henry N, Hernández-Velázquez R,
Nguyen CH, Mamitsuka H, Forterre P, Jaillon O, De Vargas C, Sullivan MB, Suttle CA, Guidi L, Ogata H. 2021.
Eukaryotic virus composition can predict the efficiency of carbon export in the global ocean. iScience 29;24(1):102002.

−27−

2020-28（国際）Unveiling the genomic contents of ecologically importantmarine giant viruses
Tom O. Delmont

CNRS UMR8030

Objectives. Nucleocytplasmic large DNA viruses (NCLDVs) possess complex genomes andlarge particles. The PI has been constructing metagenome assembled genomes (MAGs) of
NCLDVs based on Tara Oceans metagenomic data. Using this new resource, PI’s group worked
with the ICR partner lab (Hiroyuki Ogata’s lab) to investigate various issues around uncultured
marine NCLDVs, including their phylogenetic diversity, genomic features, infection strategies,
biogeography, possible hosts and deep evolution.
Methods. NCLDV MAGs were generated from Tara Oceans metagenomes. MAGs were built
using CONCOCT, HUMMER and the bioinformatics platform anvi’o.
Results. 745 NCLDV MAGs (average size 283 kb, ranging 101 kb to 1.4Mb) were generated.
First, we identified 1038 protein domains in the NCLDV MAGs that have been previously
unidentified in isolated viruses. These included myosin domains. These myosin genes were
scattered in the phylogeny of NCLDVs but formed a monophyletic group when analyzed withhomologs from various eukaryotes. Second, we used the MAGs to predict the hosts for the
NCLDVs that were identified as important predictors of the biological carbon pump in the oceans(Kaneko et al., 2021). Third, we are currently performing a systematic study to investigate therelationships between NCLDV MAGs and their eukaryotic hosts using the co-occurrence based
the FlashWeave and Taxon Interaction Mapper (TIM) software.
Discussion
The MAG curation/cleaning is a time-consuming process, but it is nearly the final stage. The
NCLDV MAG resource that PI’s group generated is a valuable resource to address evolutionary
and ecological questions on uncultured marine NCLDVs. This was already in part demonstrated
by the above works that PI’s group performed in collaboration with ICR’s partner laboratory.
Publication
Kaneko H., Blanc-Mathieu R., Endo H., Chaffron S., Delmont T.O., Gaia M., Henry N.,
Hernández-Velázquez R., Nguyen C.H., Mamitsuka H., Forterre P., Jaillon O., de Vargas C.,
Sullivan M.B., Suttle C.A., Guidi L., Ogata H. Eukaryotic virus composition can predict theefficiency of carbon export in the global ocean. iScience, 24, 102002 (2021).

−28−

2020-29
Development of predictive methods for marine microbial communities basedon remote sensing data
Kentaro Tomii National Institute of Advanced Industrial Science and Technology
It is important to realize the real-time monitoring of the global dynamics of marine
microbiome for various aspects such as knowing the function of each species of microorganism,predicting the changes in the global climate and searching for novel industrial applicablemicroorganisms. The main problem to overcome is the low temporal and spatial resolution of
the sampling using research vessels due to the limitation with cost and labor power. Satellite
remote sensing is able to solve this problem because of its automatic, periodic and global sensing.
The information obtained from satellite is the spectrum of reflected light (i.e., ocean color data).
Though it has the information of the sunlight absorption by the pigments harbored inphytoplankton, a large gap exists between ocean color data and microbial composition. We aim
to fill this gap by developing a method for predicting microbial composition from ocean color
data using state-of-the-art bioinformatics and machine learning technologies.
In the development of the method for predicting microbial composition, global marine
metagenomes of Tara Oceans are used as a prediction target. We are using following procedure
considering the small number of Tara Oceans samples. 1) Make a regression model for predicting
microbial composition from pigment data, which has ten times greater number of samples than
Tara Oceans. 2) Pre-train a neural network using ocean color data as input and microbial
composition predicted from pigment data as target. 3) Fine-tune the higher-level layers of pretrained network with the target of real microbial composition data (transfer learning). We have
implemented the first step of the procedure and found only the small part of the microbialcommunity can be predicted from pigment data. This result suggests we will get a method forpredicting relative abundance of some special microorganisms not a whole community when we
finalize the procedure. To overcome this problem, we are exploring other ways to develop a
prediction method, for example by detecting the patterns of microbial composition throughout
the oceanic regions and seasons.
Research achievements
人,
井
から
を
する リモ ン ×ム
報科学若手の会 第 12 研究会（）
人,
井
深層学 を利用した人によるリモート ンシングに基づく組成法の開 第 9
報学連合大会−29−

2020-30
Control and analysis of complex networks via probabilistic minimum
dominating sets
Jose C. Nacher

Toho University

Objective. In recent years, we have been focusing on structural controllability of complex
networks and developing theory and methods based on the minimum dominating set (MDS),
which is a well-known concept in graph theory. In particular, we developed a new concept, theprobabilistic minimum dominating set (PMDS), by extending the MDS for handling weighted
networks in which edges have some weights. In the last year, we developed a novel method foranalyzing metabolic networks by combining PMDS with stoichiometric matrices andsuccessfully applied to analysis of several cancer-related networks. However, our previous
method for computing PMDS needs considerable computation time and some improvements
are needed. Another major graph theoretic approach to structural controllability is based on
maximum matching on bipartite graphs. In this model (MM model). it is assumed that a single
driver node can send signals to many other nodes (driven nodes). However, such assumption
may not be appropriate for certain kinds of biological networks. Therefore, it is needed todevelop methods for identifying and analyzing driven nodes.
Results. We got the following two results. (1) In order to improve the efficiency of ourprevious method for identifying critical/intermittent/redundant nodes in PMDS, we havedeveloped a novel method which combines some pre-processing procedure and integer linear
programming, where critical, intermittent, and redundant nodes are nodes appearing in every
PMDS, some PMDS, and no PMDS, respectively. In the pre-processing phase, many criticaland redundant nodes are identified using some propositions, and then all kinds of nodes are
identified using integer linear programming [1]. (2) As for the MM model, Pequito et al.
developed a method (IEEE Trans. Automatic Control, 2016) for identifying a set of driven
nodes, using maximum matching for bipartite graphs and strongly connected components ofdirected graphs. However, this method cannot identify critical/intermittent/redundant node
categories (under the MM model). Therefore, we developed a novel method to identify
critical/intermittent/redundant nodes using integer linear programming [2].
Presentations (talks only).
[1] E. Yamaguchi, T. Akutsu, J. C. Nacher: Analysis of human brain transcriptomics data acrossthe lifespan using probabilistic network controllability, 7th International Conference on
Biomedical and Bioinformatics Engineering, 2020.
[2] Y. Shinzawa, T. Akutsu, J. C. Nacher: Identification and analysis of driven nodes toefficiently control metabolic pathways, 7th International Conference on Biomedical andBioinformatics Engineering, 2020.
−30−

2020-31
Genomics and transcriptomics of giant viruses
Masaharu Takemura

Tokyo University of Science

The giant virus is known for its large genome and viral particle size. Based on isolated giant
viruses, I worked with the ICR partner lab (Hiroyuki Ogata’s lab) to investigate the genomic andtranscriptomics of isolated giant viruses.
Transcriptomic study of medusavirus. Meduavirus was isolated from a hot spring in Japan. A
48-hour time-course RNA-seq experiment was done to investigate the expression profile of viraland host genes. Viral expression profiles were clustered into 5 temporal clusters, which allowed
us to identify the temporal tendency of functional category and subcellular localization of viralgenes across time. Putative promoter motifs that may account for the regulation of viral gene
expression were also predicted. The host transcriptional profile was greatly altered. We identified
suppressed and activated groups during the infection course by doing K-means clustering-based
Gene Ontology analysis and KEGG pathway enrichment analysis. Our study provides an insight
into the transcriptional shift of both medusavirus and its host.
Genomic study of medusavirus stheno. Medusavirus steno, the 2nd member of the proposed
Medusaviridae, was isolated from freshwater sediment samples from the Tatakai River, Uji,Japan (Yoshida, et al., 2021). Medusavirus stheno has a 362,811 bp contig, which showed a highsimilarity with the original medusavirus genome. The isolation of medusavirus stheno infreshwater indicates a wider habitat of this virus.
Recombination. Recently, we have isolated and assembled 14 new members of theMarseilleviridae from Niigata and Kyoto prefectures, Japan. This presented the opportunity to
study important genomic interactions between related closely giant viruses. Using a
recombination detection tool, we have detected genome recombination events between these
newly isolated viruses, and with other existing Marseilleviruses with nearly complete tocomplete genomes. Several recombination events are found only between giant viruses isolated
in Japan. However, some of these signals are also shared with viruses not isolated in Japan,
suggesting an ancestral recombinant. Our study provides insights on how recombination may be
involved for the evolutionary stability of large genomes of giant viruses.
Publication
Yoshida K, Zhang R, Garcia KG, Endo H, Gotoh Y, Hayashi T, Takemura M, Ogata H. 2021.
Draft Genome Sequence of Medusavirus Stheno, Isolated from the Tatakai River of Uji, Japan.
Microbiol Resour Announc 10:10–12.

−31−2020-32
Whole genome analyses of marine bacterivorous heterotrophic
nanoflagellates
Takafumi Kataoka

Fukui Prefectural University

Heterotrophic nanoflagellates (HNFs) are known as the main consumers of bacteria in the aquatic
ecosystems. They constitute important members to the microbial food web, which transfers energy andmaterials from small organisms to higher trophic levels1. Thus, detailed studies on their diversity, ecology,
and physiological characteristics are needed to better understand the marine biogeochemical cycles.
However, there are only few studies that examined the genomic and ecophysiological aspect of marine
HNFs2.
Recently, I succeeded to isolate several environmental clones of HNFs from a saline lake, Lake Hiruga.
As a result of phylogenetic analysis using 18S rRNA gene, it was suggested that an isolated clone (named
HIYC8) represent a novel independent lineage within the subclass Bicosoecida, a member of heterokonts. To
further understand the detailed phylogeny and potential function of this clone, it is essential to determine thewhole genome sequence and to annotate genes from the genome. In this study, I and the ICR collaborator Dr.
Hisashi Endo made use of the state-of-art long fragment sequencing technology and associatedbioinformatics tools to make a high-quality draft genome of HIYC8.
Genomic DNA was extracted using a proteinase K/PCI method. The average fragment of the extracted
DNA was 48.3 kbp and the quality (DNA Integrity Number, DIN) score measured by the TapeStation
system (Agilent) was 7.6. To generate ultra-long reads from the extracted and purified genomic DNA, theOxford Nanopore Technologies MinION sequencer was used with the library preparation kit SQR-LSK109
and the flow cell R9.4. The raw sequence reads were quality filtered and then assembled using the program
Flye3. As a result, we obtained 221 contigs, which had an N50 of 2.0 Mbp, the total length of 76.8 Mbp, andthe mean coverage of 52.1. A total of 19,053 genes were predicted from these contigs, although theseincluded genes likely derived from prokaryotes. The genomes completeness was measured with BUSCO andthe result indicated that 87.5% of the single-copy orthologous genes of eukaryotes were recovered in theassembly. The similarity between known 18S rRNA gene sequence of this clone and the sequences in theassembly were consistently 99.94% (1,736/1,737 residues). These results indicates that our draft genome ishighly completed and accurate, although additional refinement is needed to exclude contaminations fromother organisms.
References
x Azam, F. et al. (1983) Mar. Ecol. Prog. Ser., 10, 257-263.
x Jürgens. K. and Massana, R. (2008) Chapter 11, In Microbial ecology of the oceans. Wiley.
x Kolmogorov, M. et al. (2019) Nat. Biotechnol., 37, 540–546.

−32−

2020-33
Comparative genome analysis of Parmales and diatoms:
Looking for the ancestral genomic feature
Shinya Sato

Fukui Prefectural University

Objectives. The order Parmales is a unicellular eukaryotic phytoplankton with a cell wall madeof silica. Recent studies revealed that palmales are a sister group of diatoms that also have silica
cell wall.
Diatoms are one of the most diverse and successful groups of microalgae sustaining the food
web in the ocean. On the other hand, although parmales are widely distributed in the world’s
oceans from polar to subtropic, their diversity and abundance are extremely low compared todiatoms. A comparative study of parmales anddiatoms has a potential to address several

important issues, such as the physiological characteristics that made differences in ecologicalroles between them in the current ocean, the origin of cell walls and their early evolution.
Methods. We newly generated 7 parmales genome assemblies and conducted comparative
genome analyses together with 8 parmales and 5 diatom genomes publicly available.
Results. A comparison of the genetic composition of the diatoms showed that the parmales arephagocytotic mixotrophs and there was a large gene loss event related to phagocytosis in theearly stages of the diatom lineage. Parmales possess more genes related to lipid-fatty acidmetabolism and storage than diatoms, suggesting the existence of physiological processes uniqueto Parmales. Furthermore, parmales have plastocyanin gene that functions in photosystems underpoor iron conditions. These genomic features suggest that parmales are tolerant to oligotrophic
conditions. On the other hand, a comparison of genes involved in nutrient uptake, such as
nitrogen compound transporters and silicate transporters, suggested that diatoms have efficientnutrient uptake ability. The genomic composition of the diatoms also suggested a high tolerance
to nitrogen depletion, highly regulated cell cycle control processes, and the existence of peculiar
stress response processes. Comparison of genes involved in the formation of silica structures
suggests that diatoms have more complex regulation of structure formation processes thanparmales. These results show that the evolution of these traits supports the adaptation of diatoms
to dynamic environments.
.

−33−

2020-34
分

ネットワーク

本研究では、機
ワーク

学

と

の

学を融合させた法を提案する。分

、実験 件（的機（図１ ）、 ての５
者）では、

法と応用
野

広

大学

点から、

的な分

ネット

・代 に 点を て、

スウ イ）の推定や、それらのネットワーク のするためのののうち２つのの 意の は互いに相関している（図１ の）。いくつかのしており、すな ち、これらのしている（図１ のでは、この相関

機能が、がんなどにより
を

図

（ えば、

）。

る。本研究では、このような相関 化をもつの）が、は互いに相関が く、 ン ムにが互いに相関している（ム

方法を提案する。

の ート ッ である。図１において、（ えば、がん 者）では、

な

の

ム・

は、５つの

の

による

学

者と 者等）による い等を

ま 、 題を らかにする。図が学ルとして、主に、ネットワークや代 ネットワーク（代の的機していることを意 す

的に 出するための機 学 ・的方法を提案する。
々は、これまで、手法の提案、実験による提案手法の評価、公共のから入手した べ
的に意 のある

文を

し、

の

教 、

ている。今後、提案手法をさらに 展させ、グ
）、

教 ）を

えられる。また、これらのにおける学を め め、これらの成果を元に研究代 者と共同研究者とを（ 見 教 、Nguyen（中）に提案手法を 用し、が 出出来ることを 認した。また、先行研究で報告されている、相関ネッ

トワークが 化する
の共

の

ー （

的な

科学

機

学（Wicker 教 ）、 ル リ ムや イニングした機 学 ・
法の、

ネットワーク

学的な分 ネットワーク

学分野（特に加の応用を研究）および

法の提案が

学分野（大

教

）

している。

/
図

により相関

が 化する

（ ）と、同様な相関の ート ッ （ 。 いほどと 図のような相関

が い）。

化を つ

の中から 意の をとるの 化が見られる。 Kayano M., Shiga M. and Mamitsuka H., IEEE/ACM Trans.

Comp. Biol. Bioinform., 11(1): 154-167, 2014 より−34−

2020-35（国際）Light emission from halide perovskites and related materials
Ru-Shi Liu National Taiwan University
Objectives: Recently, zero-dimensional perovskite nanocrystals (NCs), which have relatively
high thermal stability and narrow luminescence spectral width, are considered to be applied tolight-emitting diodes and displays. The emission mechanism of this new material is under debate,
and thus studying the photoluminescence (PL) properties is quite important in this kind ofresearch.
Experimental methods: The high-quality Cs4PbBr6 zero-dimensional perovskite NCs, whose
PL quantum yield (PLQY) reached up to 59%, were obtained by tuning the synthesis process ofthe hot-injection method. To further explore the emission mechanism of our samples, the timeresolved PL (TRPL) and transient absorption measurements were conducted by using a streak
camera system and a pump-probe method.
Experimental results: The TRPL decay curves depend on the excitation photon fluences. A fast
decay component appears under strong photoexcitation, and this signal corresponds to the trion
recombination. By analyzing the PL decay curves at long delay times, the exciton lifetime x of
4.4 ns and the absorption cross-section of 1.8 × 10 15 cm2 were obtained.
Discussion: The obtained values of x and are almost the same order as the reported values for
CsPbBr3 NCs. Taking these PL properties and XRD diffraction data into account, we conclude
that the emission of Cs4PbBr6 NCs originates from very small CsPbBr3 NCs embedded in
Cs4PbBr6 NCs. The photon fluence dependence of the TRPL spectra also suggests the reductionof trion formation comparing to the standard CsPbBr3 NCs. The surface passivation of CsPbBr3
NCs can be well improved by Cs4PbBr6 matrices, and the reduction of trion formation leads tothe enhancement of PLQY.
Publication: Z. Bao, H. D. Chiu, W. Wang, Q. Su, T. Yamada, Y. C. Chang, S. Chen, Y.
Kanemitsu, R. J. Chung, and R. S. Liu, “Highly Luminescent CsPbBr3@Cs4PbBr6 Nanocrystals
and Their Application in Electroluminescent Emitters” J. Phys. Chem. Lett. 2020, 11, 10196–
10202.

−35−

2020-36（国際）Exploration of cycloaddition properties of guanidine functionalized
anthracenes−36−

2020-37（国際）Development of new blue TADF emitters with horizontal molecularorientations
Eli Zysman-Colman

University of St Andrews

This project focused on a novel type of acceptor, [1,2,4]-triazolo-[1,3,5]-triazine core (TTT). 1,2,4Triazoles and 1,3,5-triazines have each been widely applied as acceptor motifs in thermally activateddelayed fluorescence (TADF) materials due to their relatively weak electron-withdrawing characterand the combination of both, namely the TTT core, has previously been employed within TADF
emitters. However, the previous TTT-based organic light-emitting diodes (OLEDs) showed relatively
poor performance with maximum external quantum efficiency (EQEMAX) of less than 10%. Here, we
designed two novel TADF emitters (3,4,5-3TCz-TTT and 3DMAC-TTT, Figure 1a). The
corresponding OLEDs successfully exhibited improved device performances.
Our group designed these emitters. Prof. Kaji’s group conducted photophysical characterizationand device fabrications. We identified CzSi as an appropriate host matrix for the TTT-based OLEDs
and a doping concentration of 15 wt% was chosen as photoluminescence (PL) quantum yield ( PL)was highest. Both compounds present sky-blue emission at 485 nm and 475 nm (Figure 1b), and highPL under N2 of 80% and 79%, for 3,4,5-3TCz-TTT and 3DMAC-TTT, respectively. Both emitterspresent prompt fluorescence, with similar lifetimes reflecting tri-exponential decay kinetics, of 14.5
ns [ 1 = 26.14 ns (12.35%), 2 = 12.97 ns (63.43%), 3 = 22.71 ns (24.22%)] for 3,4,5-3TCz-TTT andbi-exponential decay kinetics, of 11.9 ns [ 1 = 6.95 ns (34.7%), 2 = 14.6 ns (65.3%)] for 3-DMACTTT. Both compounds also show very long delayed PL (Figure 1c) with bi-exponential decay
kinetics and lifetimes of 3.1 ms [ 1 = 1.17 ms (54.27%), 2 = 5.30 ms (45.73%)] for 3,4,5-3TCz-TTT
and 4.7 ms [ 1 = 1.16 ms (46.84%), 2 = 7.84 ms (53.16%)] for 3-DMAC-TTT. 3,4,5-3TCz-TTT and
3DMAC-TTT
basedsolution-processed
OLEDs exhibited blue emission with
Commission Internationale de l’Éclairage
coordinates of (0.17, 0.28) and (0.16, 0.23), andEQEmax of 5.8% and 11.0%, respectively(Figure 1d).
[Published paper by this joint work]
The paper highlighting this work has now been
published: Hundemer, F.; Crovini, E.; Wada,Y.; Kaji, H.; Bräse, S.; Zysman-Colman, E.
Tris(Triazolo)-Triazine-Based Emitters for
Solution- Processed Blue Thermally Activated
Delayed Fluorescence Organic Light-Emitting: a) Molecular structures of 3,4,5-3TCz-TTT and
Diodes. Mater. Adv. 2020, 1 (8), 2862–2871.
3DMAC-TTT. b) Emission spectra of 3,4,5-3TCz-TTT
Other
collaborative
work
for and 3DMAC-TTT in CzSi doped film (15 wt%) ( exc = 340
diindorocarbazole-based TADF emitters is nm); c) Time-resolved PL decay of 3,4,5-3TCz-TTT and
3DMAC-TTT in spin-coated CzSi film (15 wt%) and; d)currently ongoing and a manuscript related to EQE-J curves of OLEDs containing 3,4,5-3TCz-TTT (red)and 3DMAC-TTT (blue) as emitters. Inset: EL spectra ofthis work will be submitted shortly.
OLEDs at the current density of 1 mA cm 2.

−37−

2020-38（国際）Coupling of nanographenes and curved -systems and elucidation of theirelectronic and optical interactions
Akimitsu Narita

Okinawa Institute of Science and Technology Graduate University

Objective: To achieve the coupling of nanographenes with the curved -systems developed by
the ICR partner researchers, Prof. Takashi Hirose and Prof. Yasujiro Murata, the initial
objective in this project has been to prepare adequately functionalized nanographenes. To thisend, we have worked on syntheses of nanographenes with halogen or triflate groups that can beused for the transition-metal-catalyzed coupling reactions for the further functionalizations.
Results and discussion: We have previously prepared 5-bromobenzo[rst]pentaphene (2)during our attempts to synthesized N = 8 armchair graphene nanoribbons on surface [BCSJ,
2021, doi:10.1246/bcsj.20200382], and considered benzo[rst]pentaphene as a model case to
study the coupling with curved -systems by the ICR partner researchers. To increase thesolubility, 5-bromo-8-mesitylbenzo[rst]pentaphene (4) was prepared through the Suzuki
coupling of 3 with mesitylboronic acid, followed by bromination (Figure). The possibility touse 4 for further coupling reactions could be verified by model reactions, namely Suzuki
coupling with mesitylboronic acid to giveBr

5,8-dimesitylbenzo[rst]pentaphene (5) in 82%

NBS, CH2Cl2

yield as well as homocoupling to provide

r. t. 12 h88%

dimer 6 in 76% yield. Interestingly, chiral

1

hand,

we

dibromo-substituted

have

also

prepared

Mes
NBS, THF
r. t. 12 h80%

procedure [Chem. Asian J. 2019, 14, 1703.],and is ready for the further fuctionalization.

Br4dibenzo[hi,st]ovalene(DBOV), following our previously reported

3
B(OH)2

presence of enantiomers, and attempts on theother

Pd2(dba)3, SPhos
K3PO4, toluene
105 oC, 12 h71%

2

HPLC analysis of dimer 6 revealed theoptical resolution is currently ongoing. On theMes

B(OH)2Mes

Pd(OAc)2, SPhos
K3PO4, toluene
105 oC, 12 h82 %Ni(COD), COD
2,2'-bipyridine
DMF, toluene
85 oC 12 h
76%

Mes

5

Mes

Mes

6

Figure: Synthesis of bromobenzo[rst]pentaphene 4
and its coupling towards 5 and 6.

Conclusion: Bromobenzo[rst]pentaphene 4 and dibromo-DBOV have been prepared and areready for the further coupling studies together with the ICR partner researchers. Although theplanning of the research visits and stays at ICR needed to be postponed due to the Covid-19,
the synthesis of novel bibenzo[rst]pentaphene 6 could achieved. Optical resolution of 6 as wellas investigation of its photophysical and electrochemical properties are currently ongoing.

−38−

2020-39（国際）Development of hole transport materials for tin-perovskite
and device characterization
Akinori Saeki Osaka University
Tin iodide perovskite (ASnI3) is one of the most feasible, less toxic alternatives to lead halide
perovskite (APbX3), owing to its readily formed three-dimensional (D) structure and moresuited bandgap (1.2–1.4 eV) of the solar cell application than
APbX3 (1.5–2.3 eV). Here, we report the effect of ternary
mixing organic A-site cations (GA, FA, and PEA) on thesolar cell performance and charge carrier dynamics that areevaluated using time-resolved microwave conductivity(TRMC) (Fig. 1).[1] (GAxFA1–x)0.9PEA0.1SnI3 exhibit the
maximum power conversion efficiency (PCE) of 7.90% at x
= 0.15 and a drastic decrease with increasing GA content.
Notably, our TRMC measurements of ASnI3 with/without ahole transport layer reveal the same trend with the devices.
From the analyses, we suggest that a variation of electron
mobility affected by the location of the GA cation in thegrains significantly impacts the PCE. Our work sheds light Fig. 1. A-site cation mixing effect on
the charge carrier dynamics ofon the role of mixed A-site cations and directs a route tin-based perovskites.
towards the further development of Sn perovskite solar cells.
Silver-bismuth-iodide (Ag-Bi-I) semiconductors have increasingly gathered much attention
as an alternative to lead halide perovskites. However, Ag-Bi-I has not been thoroughly
investigated owing to the complexity in its composition and solution process, and the PCE of
its solar cell devices has still stayed at a low level. We report a rigorous exploration of the
Ag-M-I composition and III-V elements (M = bismuth, antimony, indium, and gallium) via
effective guidance of TRMC measurements (Fig. 2).[2] Screening of Ag:Bi precursor ratio
reveals the superior TRMC transients at the low Bi content to that at the high Bi content, which
relates to the predominant Ag2BiI5 and AgBi2I7
phases, respectively and leads to the higher
PCE in the former. The addition of hydroiodic
acid (HI) and mixing of the III-V elements
show dramatic effects on the charge carrier
dynamics. We obtain an improved PCE of
1.82% in the Ag-(Bi/Sb)-I composite
compared to the initial 0.78% of Ag-Bi-I
without additive, which broadens the library ofFig. 2. Screening of Ag-(III-V)-I semiconductors for
Ag-M-I semiconductors for a further evolution solution-processed solar cell.
of lead-free solar cells.
[1] E. Nakanishi, R. Nishikubo, A. Wakamiya, A. Saeki, J. Phys. Chem. Lett. 2020, 11, 4043.
[2] F. Iyoda, R. Nishikubo, A. Wakamiya, A. Saeki, ACS Appl. Energy Mater. 2020, 3, 8224.

−39−

2020-40
Development of -conjugated nickel complexes for highperformance n-type thermoelectric materials
Michihisa Murata

Osaka Institute of Technology

Introduction
Flexible thermoelectric generators are convenient and low-cost energy-harvesting devices that have recently
received increasing attention. Especially organic and organometallic semiconducting materials are suited for thispurpose due to their very low thermal conductivity. Moreover, relatively large films can be fabricated easily using
low-cost solution-based processes. For the generation of flexible thermoelectric modules, p- and n-type organic
semiconducting materials are of vital importance. While solution-processable high-performance p-type organic
materials have been intensively studied, the development of the corresponding n-type materials has been hampered
partially due to their instability upon doping with an n-dopant under atmospheric conditions. One promisingexample of an n-type material that can be used as a thermoelectric generator are nickel-ethenetetrathiolate (Ni-ETT)complexes, albeit that they are virtually insoluble in common organic solvents.

Results and Discussion
In this work, we have developed anefficient

solution-based

processforthefabrication of air-stable n-type thermoelectricfilms. A Ni-ETT complex (2) was synthesized andused to generate an aqueous dispersion (Scheme1). A film fabricated via a simple drop-casting methodwith ethylene glycol (EG) as the key additive, exhibiteda remarkably high thermoelectric n-type power factor(PF = 33

W m–1 K–2), which remains largely

undiminished

after

10

days

under

atmosphericconditions. This environmentally benign process stands
in stark contrast to previously reported methods that use
organic solvents during the film-forming process. The information obtained in part through the collaboration with
Prof. Yasujiro Murata and co-workers should thus strongly contribute to the advancement of flexible thermoelectricmodules.

References:1) K. Ueda, Y. Yamada, T. Terao, K. Manabe, T. Hirai, Y. Asaumi, S. Fujii, S. Kawano, M. Muraoka, M. Murata,
J. Mater. Chem. A 2020, 8, 12319-12322.
2) M. Murata, 2020 27th International Workshop on Active-Matrix Flatpanel Displays and Devices (AM-FPD),
Kyoto, Japan, 2020, 48-49. (IEEE Xplore)−40−

2020-41
テロンの特性を活かした新規機能性

の

敬

等

学

見を

てい

目的
これまでに

々は

テロ

る。しかし、有

な

化

に

ン
応の

の

化

には

っていない。本研究では目して、新たな機能性

の方法

存の含

互

活性

環からなる

応について

の

化

しており、 つかの

化合

は、

材

の

なら

互

の

環に

テロ

ンを基本

認識を活用した向した分設を行い、 ン

的には 1-ン

合成といくつかの

性について

る。

等に

が

用し、 性材ンや分では見られない
イ

ーの

の

応

を第一の目的とする。

など、多種多様な機能性を有する。この
ニットに

ンの 2

テロ

、
ン

ン

した。1 はジ

を導入した

ーなど

の応用を指

を利用した機能性の1 および 1,3-ジ

導

や

ンの

ロ

テンの部分

ニットは 1-

ン

を
2の

ミ

を有しておりその

動

たれた。

実験方法
本研究に

用する

1,3-ジ

ン

ンとこれらのの 2, 4, 6
び

テロ

ミ

とし、

導

である。主な応を用いた分

による共

拡

応部

の

ッ

を行った。1-

による

応

した

件を

し報告している。本研究では

果、特に

ル

および三

について合成およびと 2- ード

ついては、2- ミ

の合成を

は

ン

リングおよ

ンとその

合させた 1 の合成法については、これまでに Stille
種

導

ッ
の

性の

び

を

リング
ル

ル

を有するものについてを行った。また、1,3-ジの Ullmann 型 ッ

リングによって、2

ンに

で

合した二

した。

果と
1 についてクロロ

ルムをは 650 nm に し、1ン

に

来する

化によって

各成分の

が

化が期
ンの

と

定したところ、長

ンに

な長

長シ

した。一方、

べ大とトをえられた。しかし、していることが推かった。しかし、したところ、 ル

クトルをがたところ、NMR および MS ス

1,3-ジ

ス

（Oem = 330 nm, Oex = 600 nm）がることによって、た。 によるに用いてのされた。そこで、1 と三
定

果より、

した

と

が

されることから、今後、

ッ化

下 120

性の

を進める

で、二

と三

定である。
−41−

され

ッ化

ウ

の

、

動について

合

との

を

成していることが
の

する

の

成による

ウ

した BODIPYの端

グネシウムを加え2 の合成については、NMP 中で Ullmann

ン

の

は

されたことから、

クトルの

ミ

長

応を

が

し

され

定である。また、を用いて種々

成を認した。今後、2020-42
Preparation of chiral silica via chiral transfer
Tomoyasu Hirai

Osaka Institute of Technology

Silica-based chiral materials such as helical mesoporous silica has been attracted considerable attention in
the fields such catalyst, template, chiral recognition. These materials are prepared by sol-gel transcription using
an organic chiral structure as template. However, preparation of preferred -handed helical silica derivatives
using an achiral polymer as a template has not been reported yet. Polyhedral oligomeric silsesquioxane (POSS)
is an organic–inorganic hybrid nanoparticle. Methacrylate-functionalized POSS (MAPOSS) is commerciallyavailable and its polymers (PMAPOSS) with a well-controlled primary structure were obtained by controlled
radical and living anionic polymerization. It is anticipated that ifcontrolling of the helical conformation in PMAPOSS domains
could keep the helical structure during the calcinating process,then it gives a simple and cost-effective preparation method forchiral silica materials.
isotactic PMAPOSS (it-PMAPOSS) was prepared on the basisof a living anionic polymerization using a Grignard initiator. To
control the secondary structure in it-PMAPOSS, it-PMAPOSS
and chiral dopant (R or S-BN) were mixed and subsequently the

Figure 1. VCD spectrum of it-PMAPOSS
with R and S-BN.

molecular aggregation state was elevated using vibration
circular dichroism (VCD) spectroscopy measurements (Figure1). Split-type Cotton effect could be observed at 1730,
1240~1000 cm-1, which can be assigned to carbonyl, ester, and
Si-O-Si stretching vibration, and they showed mirror image
between R and S-BN. This suggests that it-PMAPOSS formed
preferred-handed helical conformation by mixing of chiraldopant. The samples thus obtained were annealed at 620°C at aheating rate of 10°C / min under air, the residue evaluated using
VCD spectroscopy measurements (Figure 2). The peaks ranging

Figure 2. VCD spectrum of calcinatedsamples prepared using it-PMAPOSS
with R and S-BN.

from 1000 to 1240 cm-1, which can be assigned to Si-O-Si vibration, were dominant. The two bands centeredat 1131 and 1047 cm-1 due to the cage and network Si-O bond stretching, respectively, broadened to a single
unresolved band, showing a silica structure owing to cage crosslinking. Hence, it is clear that most of theorganic segments were removed from the it-PMAPOSS. Interestingly, the split-type Cotton effect could still
be observed in this region and was more striking than that of the unannealed sample, indicating that the
distance between Si-O-Si decreased. The VCD results suggest that the induced preferred helical structure in
the PMAPOSS and BN mixture can be used as a chiral template and maintained during the calcination process,leading to the formation of silica with exclusive optical activity.

−42−

2020-43
クロ環内に導入した

応中

の化学
学

年、環状
が

んに行

環

を

内に

れている。

した

えば、

成したシクロ

ニ

イド

の

ジ
に

ニ

果の

を

内での

がれた

が

が

さくなるという特
ン

が

MeO

ル

ジ

MeO

ル

イド

の

成や

環

での

性の

、

い

状とは

m

n

[m]AZ-[n+3]CPPンn[m]DR-[n+3]CPP

Ni(cod)2
cod, bpy
Toluene / DMF(v / v = 5 / 1)

OMe

Quinoidal

OMe

なる性

中でのジ

ジ

動にも

OMe

N N

OMe

Br

AZ-6CPP(11 steps, yield : 1 %)
4K

6
5
60 K

を有

4
3

ルに関

なく、そのスNa+Naph THF

N N

MeO

される。また、応[7]CPP
Large
HOMO-LUMO gap[6]CPP

m

h

MeO

なり、

する研究報告は[5]CPP
Small

n

Br

とは

した環状

的な

することに

N N m

N N

クロ環

動

を

ン環の

した。

のものの

と

ン(CPP)は、 ン

分

環状状

状

合し、

n

の

ける

することが

で

大学

した

は、

応性など

ン環が

来する。本研究では、[m]AZ-[n]CPP（m
）を設

ン

性は、 ン

ル性に

ンで環状に

ン環の

の研究

ッ

動が報告されている。この特じるジが広がった分てのなくなるにつれ、HOMO-LUMO

よって

共

広

2
1620

1640

1660

1680

1700

0

1720

10

20

30

40

50

60

Magnetic field / Gンがたれるため、そのス

ジ

ル

ン多

度と

に

する

の

果

した。
果と

1)

ル

内環化、 元的化をとなる環状て、AZ-6CPP の合成をた。2-MTHF 中、4 K で AZ-6CPP の
応によって

じたジ

化合

ジ

(Hg

ルの Triplet 種にになった。このシグナルをモニ

ーし、

度

の合成を

成し、X

来する特
EPR

を

認し

することが

らか

であることから、

ン多

度が

められた。

化していることがしていく様に定を行い、Bleaney Bowers のであることが々ににて、その的なシグナルが一のシグナルは、30 K を えるとによる分)を行うことにより、1650 G

ンィッティングを行うことにより、基
果によりス

た。Ni

が

分

を用いた

では、基

三

らかになった。また、こ認され、 応性にむことがされた。1) Miyazawa, Y.; Wang, Z.; Antol, E.; Kayahara, E.; Yamago, S.; Abe, M. J. Am. Chem. Soc. in minor revision.

−43−

2020-44を用いる N-N 軸

有機分

化合

の

度

的

学分

法の開
大学

[目的] BINOL、BINAP に代用方法もリ

ンド、有機分

合による軸

の研究は、

性

の

化合

次

ルバ

ある化合

を

用させると、が存

基に多様性をになるとえ、は、 多くの研究報告が存
化学など多

る

的方法

N-N 軸

化合

の

度

の

定性を見

的

導

に

し、CH3CN-tBuOH

合

上で

モ

ッ

に進行する

された N-Nする

たせることで様々な分野において利用価は皆学分である。そこで今
法の開

を

もるために

化合

を

による

した。また、 ルバ

ールか

ミ化

1

定

の

、有機分

および

1 の軸

の存

ル HPLC でをミ化認したのち、

ーを度、CD ス

クトルを用いてナンーを 110で加し、による ee の 化の様

期、

ミ化

ミ化

期を

めた。

の

ミ化

度

ムによって

にした。また本化合をの一方の定、 イリング

ロットか出し、27 日、34.6 kcal/mol という 果をな C-C 軸

を

つ化合

を

として

をそれ

めて実

定であることが分かったため、N-N 軸
し、次に

ル分取

れ

れは BINOL のように強

れると

未

中、

た。このような N-N

見を

ナン

件に

応が

合を有する

られた各

ル化合

リング

では三環

果]

に化合

ら

たる。一方、N-N

らかになっていない。 研究なる研究を進めているが、N-N 軸

として

に

し、その利

も

クリドン

し、N-N 軸上に軸

学活性

[実験

なくその性

大学で

は、

らなる N-N 軸が化合

認識化学、材

応を用いて

定にも成
化合

に

和

ことを見出た。さらに本軸、分

ールあるいはナトリウムのされる C-C 軸

的

学分

の基

に

する

果であり、N-N 軸からなるらかに出来た。本

化合

の

度

的

た。こ

学活性
学分

合成を行った。 ニリン化合

の

がある
応

度の

件には

7 を 応の基えらとするべく、その合成に取り組んだ。2 を出にモニトロた後、様々な
ッ

3を
化的

リングを

が 4 はほとんどたられなかった。また、5 を た後、であった。そこで
基
度

の
的

、2 のモ

を

ている。化合学分を[成果報告]日本

る

選択的なニトロ化を

ブロモ化の後、KMnO4 によって 6 を 、が合成出来次第、 端研究

で開

定である。

学会第 141 年会

たが、こちらも

28V03-am11

−44−

された

シル化

から

ミ

を用いて、

2020-45（国際）Molecular understanding on the structures and dynamics of ionic
end-aggregation polymers
Visit Vao-soongnern

Suranaree University of Technology

We collaborate with ICR faculties through an iJURC project to investigate structures and dynamics ofmonofunctional polymers undergoing head-to-head association and dissociation.
Objective: To study the effect of head-to-head association/dissociation on molecular dynamics bycomputational and experimental techniques
Methods
1. Monte Carlo (MC) simulation of coarse-grained monofunctional polymer model on a highcoordination lattice.
2. Molecular Dynamic (MD) simulation of the fully atomistic model of carboxylated poly(cis-1,4isoprene) and the neutralized form with cation (PICOOM).
3. Synchrotron X-Ray Absorption Spectroscopy (XAS) of carboxylated poly(cis-1,4-isoprene)
neutralized with cation (PICOOM) where M = K and Ca.
Results and Discussion
1. MC simulation: For the association/disassociation of monofunctional polymer as a function ofinteraction strength, slower dynamics was seen at the scale of molecular (the mean squaredisplacement for the center of mass and decorrelation of the end-to-end vectors), chain segment(head-to-mid vector and mid-to-end vector) and beads near the interacting group.
2. MD simulation: For fully atomistic model of carboxylated poly(cis-1,4-isoprene) and the neutralized
form with/without cation (PICOOH and PICOO- & Li+, K+, Ca++), we can obtain the information of
the local aggregated structures (distance and number of solvated atoms) and short time dynamics ofion, functional group and chain segment (up to 100 nanosecond).
3. XAS experiment: synchrotron XAS studies of carboxylated poly(cis-1,4-isoprene) neutralized withcation (K+ and Ca++) were performed to get results for the cation solvation structures.
Publication
1. Y. Matsumiya, H Watanabe*, N. Sukhonthamethirat, V. Vao-soongnern, Viscoelastic and Dielectric
Behavior of Polyisoprene Monofunctionally Head-modified with Associative Metal-Carboxylate
Group, NIHON REOROJI GAKKAISHI (2021, In Press)
2. Monte Carlo simulation of structures and dynamics of monofunctional polymer with head-to-headassociation/dissociation (In Preparation)
Activity
We have organized the first International Rheology Symposium at Thailand during February 23-26, 2021
(on-line due to Covid19) https://iumrs-ica2020.com/symposium-detail.php?id=23−45−

2020-46（国際）Observation of orbital Hall effect in ferromagnet/nonmagnet bilayers
Sanghoon Kim University of Ulsan
Recently proposed orbital-Hall-induced torque (OHT) can be a candidate to enhancemagnetization switching efficiency because the orbital current jorbital, as a result of the orbitalHall effect (OHE), has been expected to be quite larger than the jspin in some elements. The OHE
is originated from the orbital texture, which is ubiquitous in condensed maters. If the jcharge is
injected into NM, in other words, NM is in the non-equilibrium state with an introduction of anelectric field, the orbital angular momentum ±L can be accumulated at edges against orbital
quenching. As a result, the transverse jorbital, flows by diffusion of Ls. In order to observe such
effect, we have conducted research to find such large OHE collaborating prof. Teruo Ono’s groupin ICR of Kyoto University.

Figure 1. (left) Measurement Scheme to observe the orbital accumulation. (right) Current
dependence of the orbital and spin accumulation in terms of the field direction.

Previously, we observed much larger torque efficiency of 3.28 in the Gd/Cr bilayer systemthan SHA of 0.09 in the Co/Cr bilayer system by conducting the harmonic Hall measurement.
Here, we note that the torque efficiency in the Gd/Cr system is much higher than the Co/Cr
system. In other words, large orbital accumulation can occur in the Gd/Cr system. Through the
ICR international join research, we succeeded in observation of the current-driven orbital
modulations in the Gd/Cr bilayer from the XMCD study. Figure 1 shows the measurement setup
to observe the orbital accumulation at the Gd/Cr interface. The low incident angle of thepolarized X-ray can detect whether the spin or orbital angular momentum is parallel or
antiparallel in a system. Gd M5 and M4 edges of Gd/Cr films were scanned varying current
density with different current (±x) and magnetic field directions (±y) at 17K as shown in Fig. 1.
We could observe clear current-density-dependence of the orbital magnetic moment mo. This
result is now under preparation for submission to a physical journal. This will be the firstobservation of the current-driven orbital generation.
−46−

2020-47（国際）High frequency response of polymeric liquids:
Rheology and dielectric relaxation
Sathish K. Sukumaran Yamagata University
To investigate the dynamics of polymer chains and their response to imposed fields,
experiments are typically performed under isothermal (constant temperature) conditions. To
simplify the analysis, it is assumed, often implicitly, that the system temperature is not affectedby the imposed field and remains uniform throughout the system. Therefore, the theoreticalanalysis of polymer dynamics uses isothermal response functions. However, the constanttemperature assumption might not be valid for the high frequency response due to theinsufficient time for the thermal equilibration of the relevant dynamical processes. Under these
conditions, the adiabatic response functions might even be more appropriate. Therefore,
combining the experimental and theoretical expertise of ICR (Hiroshi Watanabe, Yumi
Matsumiya), and the computational, modelling and theoretical expertise of international (Jorge
Ramierz, Madrid; Manlio Tassieri, Glasgow) and domestic (Yuichi Masubuchi, Nagoya)
researchers, we have initiated a collaboration between ICR and several international anddomestic research partners.
We began our investigations by studying the effect of imposing isothermal and adiabatic
conditions on the linear rheology of an unentangled (short chain) polymer melt. We used a
simple bead-spring model for the polymer and simulated it at high densities using molecular
dynamics simulations (the so called Kremer-Grest model). The isothermal simulations were
performed by controlling the temperature using a Langevin thermostat. The adiabatic
simulations were performed at constant energy, i.e., without using a thermostat. Oscillatory
shear deformation was imposed at several frequencies while ensuring that the amplitude of thedeformation was small enough for the response to remain in the linear regime. Our results
indicated that the storage modulus, G’, and the loss modulus, G’’, under both the isothermal
and the adiabatic conditions were rather close to each other. This also indicated that therelaxation times of the polymer chains were not significantly affected. Therefore, at least in thelinear regime, preliminary results suggest that the imposed conditions did not substantiallymodify the dynamics. However, under adiabatic conditions, as expected, the temperature of thesystem progressively increased with time. In addition, the temperature increase under highfrequency oscillatory shear deformation was significantly larger than under low frequencies.
The increase in temperature under adiabatic conditions cannot be sustained indefinitely without
any effect on the system response. If nothing else, eventually the system is likely to undergo achange in state due to the heat generated by the imposed oscillatory shear deformation. We are
currently further exploring this regime both to confirm our preliminary results and also to
elucidate the response when the oscillatory shear is applied for longer times.
−47−

2020-48（国際）Dissolved and particulate Fe isotopic composition in the North Pacific
Ocean: Sources and internal cycling
Tung-Yuan Ho

Academia Sinica

Objectives:
The major objective of this joint study is to investigate the sources and internal cycling of
dissolved and particulate Fe in the water column of the Northwestern and subarctic Pacific Ocean
and to evaluate the impact of anthropogenic aerosols originating from East Asia on the processes.
My host at ICR, Kyoto University, is Prof. Yoshiki Sohrin.
Methods:
Seawater samples were taken on Japanese GEOTRACES cruises, KH11-7 and KH15-3 with Prof.
Yoshiki Sohrin’s and other Japanese PIs’ research groups in the subarctic North Pacific Ocean.
Both dissolved and suspended particulate samples were collected for trace metal elemental andisotopic composition analysis. Elemental and isotopic composition of trace metals were
determined by HR-ICPMS and MC-ICPMS, respectively. The detailed information of thesampling and pretreatment are described in the following papers.
Result and Discussions:
The details of the results and discussions are described in the following two papers. Chih-Chiang
Hsieh, my Ph.D. student, has measured Fe isotopic composition in the samples and is preparing
the other manuscript. In brief, we have observed lighter Fe isotopic composition in the suspended
particles, indicating the important roles of anthropogenic aerosol Fe input in the oceanic region.
Publications:Due to the impact of Covid-19, it was pity that I could not visit ICR, Kyoto University in 2020.
However, Sohrin-san and my laboratory have still kept close interaction in the research topics.
During the past year, we have submitted the following two papers. Both of them have received
positive review comments and are currently under final revision. Another paper about the
proposed research topic is under preparation.
Liao, W.-H., S. Takano, H.-A. Tian, H.-Y. Chen, Y. Sohrin, and T.-Y. Ho* (in revision) Znelemental and isotopic features in the sinking particles of the South China Sea: the implications
to its sources and sinks Geochimica et Cosmochimica Acta
Zheng, L.*, T. Minami, S. Takano, T.-Y. Ho, and Y. Sohrin. (final revision) Sectional distribution
patterns of Cd, Ni, Zn, and Cu in the North Pacific Ocean: systematic importance of scavenging.
Global Biogeochemical Cycles−48−

2020-49（国際）Revealing exciton quenching mechanisms in thermally activated delayed
fluorescent devices
Ifor D. W. Samuel University of St. Andrews
Highly efficient organic light-emitting diodes (OLEDs) especially at high brightness aredesired for outdoor display and lighting application. As emitter materials, thermally activateddelayed fluorescence (TADF) materials can theoretically achieve 100% of exciton conversion
into light and it has been expected to use TADF materials in place of conventional emitters in
OLEDs. However, TADF materials suffer from efficiency roll-off at high brightness mainly
because of singlet-triplet annihilation (STA) and triplet-triplet annihilation (TTA). Therefore,
we have tried to establish quantitative analysis method for STA and TTA by ultra-fast transient
photo luminescence (Tr-PL) and transient electroluminescence (Tr-EL) measurements.
In our collaborating researchers, Yoshimasa Wada and Hironori Kaji have prepared neat films
and host-free OLEDs using a highly efficient blue TADF material, MA-TA. The OLEDs
exhibited high efficiency at low brightness and severe efficiency roll-off at high brightness,
which is suitable for our research. To analyze STA of MA-TA, transient singlet exciton
densities were estimated by Tr-PL measurement for neat MA-TA film using streak camera with
pico-second time resolution and frequency adjustable laser (Figure 1). The laser frequencies
were modulated from 2 kHz to 10, 50, and 200 kHz, where STA was expected to occur only athigh frequency. From the following equations (1) and (2), we have determined Förster radii, R0,
which will be used for the calculation of rate constant for STA ( STA). Here, NS1X kHz, A, t, NT1
and are singlet exciton density at X kHz, perfector, time, triplet exciton density, andfluorescent decay lifetime, respectively.
೉ ೖಹ೥
ேೄభ

మ ೖಹ೥
ேೄభ
ସ

ൌ ‫ି ݁ ܣ‬ఉξ௧(1)యߚ ൌ ߨ మ ܴ଴ଷ ்ܰଵ ߬ ି଴.ହଷ

(2)

Slopes of the figure tell , from which we
calculated R0 = 4.7–6.3 nm. For the determinationof STA, we need further investigation of otherparameters, a and enc, which are the distance
between singlet and triplet excitons and theirencounter rate constant, respectively as shown in
eqs. (3) and (4).
ோ݇ிோா் ൌ ߬ ିଵ ቀ బ ቁఊ௞௔ߛௌ்஺ ൌ ೐೙೎ ಷೃಶ೅௞೏ ା௞ಷೃಶ೅

଺

(3)
(4)

We will continue this analysis as well as Tr-EL
experiments for TTA analysis.

−49−

௑ ௞ு௭
ଶ ௞ு௭
Figure 1. Normalized intensity of ܰௌଵ/ܰௌଵ
as a function of ξ‫ݐ‬.

2020-50（国際）Fabrication of low bandgap semiconductor films and their light induced
interfacial charge transfer and charge transport dynamics
Yasuhiro Tachibana

RMIT University

Introduction
Low bandgap semiconductors such as metal halide perovskite and metal chalcogenide
semiconductor quantum dots have been recognised as the most promising material for next generation
photovoltaic devices after the era of crystalline Si solar cells. They can be easily prepared with asolution processed method, and therefore applied for solar cells. However, the prepared solar cells
may not necessarily indicate optimal solar cell performance. In this project, we employ different typesof solution processed semiconductor films, and assess charge carrier mobilities and interfacial chargetransfer dynamics. We have conducted this project with Professor Teranishi at the ICR, characterising
low bandgap semiconductor films.
Experimental
Methylammonium lead iodide perovskite (MAPbI3) nanocrystals were synthesized with theinjection method. PbS quantum dots (PbS QDs) were synthesized using the method developed by us
previously.[1] PbS QD sensitized TiO2 films were prepared by first attaching mercaptopropionic acid
(MPA) on the TiO2 surface, and subsequently attached QD to MPA. Photo-induced charge carrier
dynamics were quantitatively assessed by state of the art transient absorption spectroscopies covering
femtoseconds to 10 seconds and 350~6,600 nm under modified experiment conditions.[2] The
quantitative charge carrier separation properties were correlated with interfacial nanostructures.
Results and Discussion
We could successfully synthesized MAPbI3 nanoplatelets, and moreover found that nanoplatelets
or nanocubes can be selectively synthesized by altering the ligand concentration.[3] We also foundthat the ligand concentration kinetically controls nanoplatelet and nanocube formation. We found that
exciton relaxation of PbS QDs are size dependent, and interestingly smaller QD shows fasterrelaxation compared to a large size.[4] Hot electron injection from PbS QD to TiO2 was observed.
Charge recombination rates are size dependent, that is, the larger QD is, the slower change
recombination is.
References[1] S. Chan, M. Liu, K. Latham, M. Haruta, H. Kurata, T. Teranishi, Y. Tachibana, J. Mater. Chem. C, 5, 2182 2187 (2017).

Outcomes[2] Tachibana et al, submitted.
[3] Tachibana et al, manuscript in preparation.
[4] Tachibana et al, manuscript in preparation.

−50−

2020-51（国際）Dynamics of shear-induced concentration fluctuation in polymer solutions−51−

2020-52
法による

材

におけるナ

の

一分
関

法は、

材

ことで、

を

強された

を

の

なナ

に

をすれすれに入

、

との

ール

手

として

かしながら、

報をット

ームを用いた開が進んでいる。各度りられた二次元イージを上のナられる。特に、二次元イ
各

における

強度から

た

の

から

なったナ

状、

ク

の

がら、

本研究では、 に
るナ

ス

ールの分

で
シ

ン

定によ

法により

成する

ール

状

が

ールを

す

の分

成するため、

ール

報

ス

状

いた

を

がある。 定をくにす

くなってしまう。そこでのFig.1 Reconstructed CT images as a function of οT : (a)οT= 1.0°; (b) οT= 3.0°; (c) οT= 6.0°; (d) οT= 12.0°;(e) ο T= 24.0°; and (f) ο T= 48.0°. Recovered CT
images using TV regularization for downsampling CT
images (g) οT= 3.0°; (h) οT= 6.0°; (i) οT= 12.0°;(j) οT= 24.0°; and (k) οT= 48.0°

におけ

を

度が

をトー

ルバリ

した 図

ー
。各

いた
と

した 果、

化による

は、

のシグナル

ことが

る

要がある。しかしな

による

ーティ

能である。

は長くなってしまう。ま

能は

ーンした

なっ

えば、相関、成することが

定

化により
度に

で

を

度を
の分

に

ス

ルの

で

法の

度において

の

られる

定が

合 せる

ス

ージの

るためには、

に強

ージ内の

成には、各

た、

内部

リントが大きくな
所

び

ルなど を

要があるため、トー

増

するため、

法を組

法では、基

大学

んに研究・利用が進んでいる。しある。そこ でこれらの 課題を

の

によって

ることができ、上におけるることから、 イクロ

学するる手法である。これにより、

ス

力な

して

評価

クトの

かった 図

イ
。

の

が

び

能である

Fig.2 MSE values as a function of οT at (a) the circular patterned and(b) background areas obtained from Figures 1. Filled circles were
estimated from the line profiles of FBP-CT images with various
οTanglesFilled squares were estimated from the line profiles of the
TV-CT images using TV regularization

−52−

2020-53
基部

上

・

ニ

における活性型ジ

リンの

と同定
内

これまで

ルモン「ジ

用いて、 合成やリン(GA)」に関して、主にシロイ
など多くの

したのかは

である。GA のて的にするため、 ニ

的

により

上

報や

定し、

の

し、 年

モ

の分

ム

ム

ルである。また、 備的な実験から

ニ

上

から

のバイ

ッ

機能が分
進化に

進化の軸に

とした。 ニ
し、

が

る

を

され、

進化について、読が先的な GA 分 （GAx）の実

長、基部

こされる

性がどのようにすることを見出し、GA の進化的進化におけるからき(Marchantia polymorpha L.) を上が部分的に存究では、 上とそのシグナル

進化の基部に術を備えた基部ナやイネといった

され GA によってがされてきた。しかし、このような多様な GA 応

ルで

ナ

京都大学

っ

は、

術が

学

され基
の GA

には

能性を見出していた。本研とその機能をするため、GAx を特の進化といった多様な

層性

の

を目指

した。
GAx を特定するため、 ニ
器

成期が

器

的な GA

することから、一

成期を指

イを

にしたバイ

ッ

法である二相分

イを

器

分に、GA

成

期を指

合成

の

にしたバイ
器

分

ことで GAx の

定を行う

年、モ

ル

の

ル・ モ

成

イン

ー
GA

ッ

（共同研究者）、増

つ

性

ン

性

する

が含まれていることがの有機化学合成を組を元にした共らか合せる

報を利用してーをから新たな代
の GA

ニ
し、共

合成

ー

した。 ニ

の GA

合成

合成

が

共

を見出した。

・・を成した。その果、この P450

成

期の

が

された。

(研究協力者) は分の推定を進め、にの長的に機能する能性をイによりで活性をした動から GA化合の P450がいとえられた。バイイン部

上の GA の同定を進める

ティクスにより

−53−

ー

を

との共

(研究協力者・大学
は

は、その

となった

定である。 、今年度は関連したていない。

の RNA-seq

すすることを見出した。さらに、共

が
出

・

ースを

ースを

器

ルを

が

ニ

についてその

とバイ

を用いた

される

したところ、 の分

した分) は、公開・ネットワーク

づいて GA 合成

は法に従って分果、

化合ーの公開 RNA-seq

し、共型と同様に、

果を

要に応じて

ティクス

(研究協力者・大学のするの RNA-seqをするため、 ニとして機能未から二相分イを行った。その果をることを進めた。

を

出

次

合成

である。

見が相次いでいる。バイ

の同定を加

ッ

や NMR、またになった。今後、法に従ってした。化学研究所の（研究協力者）との共同研究により、 ニ
成し、

の GA

ち上げた。 ニ

) は、上

の GA

合成

P450

合成
学的

の

に基

した。
である

と合

文公開および学会

能性

せて、基
には

っ

2020-54
Origin analysis of atmospheric aerosol of mountainous areas bytrace metal analysis
Yuzuru Nakaguchi

Kindai University

Purpose) The authors have been studying about cross-border pollution of the Asian Dust in Higashiosaka cityfrom 2017 to 2020. The concentration of Al and Fe in the coarse particles which was supplied from soil increased
during Asian Dust event. However, the concentration of Zn, V, and Pb in the coarse particles which was supplied
from anthropogenic origin did no increase during Asian Dust event. On the other hand, the concentration of V
and Pb in the fine particles increased during Asian Dust. The origin of Al in the atmosphere is the crust, and its
dry deposition velocity is used as an index to indicate the scale of Asian Dust. The dry deposition velocity of Al
decreased from 2017 to 2020. It is difficult to understand the origin of cross-border pollution because there aremany sources of human pollutants since Higashi-Osaka City has many industrial areas and highways around thecity. In this study, atmospheric aerosols were collected and analyzed in mountainous areas where the effects oflocal pollution were small, and the effects of cross-border pollution of Asian Dust were investigated.
Experimental) Atmospheric aerosol samples were collected on the PTFE filter of air sampler (Kimoto-electric
co.Ltd, Type AS-9) at the rooftop of the Yamanashi University building during from March 16 to March 24,
2020. The PTFE filter paper was changed every 24 hours. After sampling, the filter is cut into a Fine part (particle
size < 2.5 m) and a Coarse part (particle size from 2.5 to 10.0 m). The cut filter was transferred to an HDPE
bottle, pure water was added, ultrasonic waves were irradiated for 15 minutes to elute, and it was filtered througha 0.45 m filter, and then the ionic components were analyzed.by ion chromatography system (Dionex, Type
ICS-1500). The cut filter was transferred to a reaction decomposition vessel for microwave ovens (San-ai
Kagaku, Type P-25), high-purity nitric acid, high-purity perchloric acid, and high-purity hydrofluoric acid wereadded and decomposed in the microwave oven, and after decomposition, Trace heavy metals were determinedwith an inductively coupled plasma emission spectrometer (Thermo Scientific co Ltd., Type iCAP7600). hePM2.5 and PM10 were analysed by the automatic fine particulate matter measuring instrument (Kimito-electric
co Ltd, Type SPM-613).
Results and discussions) The Asian Dust event was observed in Kofu city from March 21 to 22, 2020. The resultsof the backward trajectory analysis showed that this Asian Dust passed over the Mongolian desert and Shanghai,
China, and reached Kofu city. The dry deposition velocity of Al and Pb in the Coarse fraction during Asian Dust
(AD) event were 249 and 0.93 mg / m2 year, respectively, and the dry deposition velocity of these element
during non-Asian Dust (nAD) event were 89, 0.37 mg / m2 year, respectively. It was found that soil-derived(crust) Al during AD was 2.8 times higher than nAD, and Pb, of anthropogenic pollutant during AD was about
2.5 times higher than nAD.
Achievement report) Nakaguchi, Y., Ikeda, Y., Sakamoto, A., Zheng, L., Minami, T., Sohrin, Y., 2020,
Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the East China Sea, Journal of
Oceanography, https://doi.org/10.1007/s10872-020-00577-z−54−2020-55
部分

ッ

化

性分

の

性・

に

する

長

存性の
大学

目的

たちは

化学的な研究によりが Rf

ン ク 研究に する部分 ッ 化リンー ル

ロ ル ル基(Rf)をの設 指 を るための端に部分的に導入した

長 n=5お長 存的な際だった 性を すことを らかにして来た。本研究ではよび 7 の Rf 基を有する部分 ッ 化ミリス ン

Fn-MA とリン

Dimyristoylphosphatidylcholine（DMPC）の部分 ッ 化 ナログ分 である Fn-DMPC を新たに合成しをすることにより

方法

の Rf

性・

界

た。

Fn-MA およびリン

二分

の

性の

分

には日 ハ

DSC6100-Exstar6000 を用いた。

イテク イ ンス

F5-MA および F7-MA については グ ムス ールで 度の い

果と

性および分

長 存性を らかにすることを目的とした。

これまでの方法に じて部分 ッ 化したミリス ン

Fn-DMPC のグ ムス ールでの合成を性分

それらを用いて Fn-DMPC の合成をたところ F7-DMPC は 度の いとに成 したが F5-DMPC については ス ールでの合成を終えが られた。
を大 合成するこグ ムス ールでの合成を行っているところである。
られた F7-DMPCル

相では 45.0の 19.9および 14.2（DSC） 定を行った。 果を下図に す。24.4
による 2 本ののにシ ー な 1 本のと F8-DMPC の 64.4

では DMPC に上ののークを す DMPC に して F7-DMPCークがされた。F7-DMPC の相度 Tm は F6-DMPCのほ 中 にした。したがって Rf長の い n=2 および 4

して Tm が大きく下する一方 さらに Rfを 長した Fn-DMPC では Tm が向に じることが らかになった。F7-DMPC のン ル ー'H は 11.6 kJ/mol と 出され n = 6 とほ 同じであった。 上のように Rf

が n = 6 よりも長い Fn-DMPC では'H は DMPC（18.9 kJ/mol）よりもさい を し Tm は上
れた。今後
分

の

するという 向が合成中の F5-DMPC を含めて

上

一分

外

有

等

ス クトルの 定により Fn-DMPC
長 存性の

に見ら

化学的

および
の Rf

を らかにする 定である。

図

および

の

成果報告
Masashi Sonoyama, “Partially Fluorinated Phospholipid Membrane”, Symposium 2S-9 "New lipid
membrane technologies for reconstitution, analysis, and utilization of 'living' membrane proteins", 58th
Annual Meeting of Biophysical Society of Japan (Sep. 16, 2020, online).

−55−

2020-56
Dynamic viscoelasticity and tensile properties ofthermoplastic elastomers
Atsushi Noro Nagoya University

Background and objectives: To develop elastomers with excellent toughness and processability, block
copolymer-based thermoplastic elastomers (TPEs) with dynamic noncovalent cross-links have been actively
studied in recent years; for instance, we developed an ABA triblock copolymer with hydrogen-bonding groupsof amide on the B middle block with a glass transition temperature lower than room temperature, and we also
evaluated the effects of hydrogen bonds formed in the ABA triblock copolymer-based TPE on the mechanicalproperties. However, most of the previous studies on noncovalent-bonded TPEs, including our previous reports,
mainly focused on the incorporation of hydrogen bonding groups into the rubber-component blocks. Therefore,
in this study, an ionically functionalized thermoplastic elastomer (iSIS) was synthesized by incorporating ionicgroups into the polyisoprene block of a polystyrene-b-polyisoprene-b-polystyrene (SIS) triblock copolymer.
Mechanical properties of SIS and iSIS were also compared by performing tensile tests.
Experimental methods: Film samples of neat SIS (Fig. 1a) and ionically functionalized iSIS (Fig. 1b) wereprepared by using a solution-casting method. Uniaxial tensile tests were performed at room temperature toevaluate the tensile properties, where an initial distance between jigs is ~10 mm.
Results and discussion: Fig. 1c shows the stress-strain curves of neat SIS
and iSIS. The tensile strength and the toughness of neat SIS were 9.1 MPaand 112 MJ m 3, respectively, where toughness can be estimated from theinner area under the stress-strain curve. On the other hand, iSIS exhibitedmuch higher tensile strength (43.1 MPa) and toughness (480 MJ m 3).This
surprising result is attributed to formation of ionic multiplets from ionicgroups in iSIS, which serve as strongly associated but reversible, dynamic
cross-links. Since the elastomers can be produced at industry scale, they
have great market potential for becoming next-generation elastomericmaterials.

Publication: “Extremely Tough Block Polymer-Based Thermoplastic
Elastomers with Strongly Associated but Dynamically Responsive
Noncovalent Cross-Links” Kajita, Takato; Tanaka, Haruka; Noro,Fig 1. (a) Chemical structure of

Atsushi*; Matsushita, Yushu; Nozawa, Atsushi; Isobe, Kousuke; Oda,

SIS. (b) Chemical structure of

Ryoji;

iSIS. (c) Stress-strain curves ofHashimoto,

Sadaharu,

Polymer

2021,

217,

123419,SIS and iSIS.

https://doi.org/10.1016/j.polymer.2021.123419−56−

2020-57−57−

2020-58
Study on transportation of metal ions through a polymer membrane
containing ionic liquid
Hiroshi Mukai

Introduction

Kyoto University of Education

Transportation of metal ions using a liquid membrane (LM) of a thin layer is an alternative

method of liquid-liquid extraction which use a large amount of harmful organic solvents and valuable carrier
molecules, and expected to reduce these risks and costs. However, the thin layer of LM is often mechanicallyunstable. Therefore, polymer membranes containing liquids have been applied to the LM in order to improve
its strength. In our previous work, the active transportation of copper (II) ions using polyvinyl chloride(PVC) membrane containing ionic liquid (IL) was achieved and its almost quantitative transportation for 24hours was observed. For the purpose of separation of metal ions, the transportation of metal ions through apolymer membrane was studied under the various different experimental conditions in this study.
Experimental (1) Preparation of PVC membrane: 1-Phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP) or
1,10-phenanthoroline hydrochloride monohydrate (phen HCl H2O) were dissolved in 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C6mim][Tf2N]) or dioctyl phthalate (DOP) at theconcentration of 0.005 mol kg-1. This solution of 1.25 g and PVC of 0.1 g for [C6mim][Tf2N] or 0.3 g for
DOP were dissolved in tetrahydrofuran of 5 g in the glass petri dish of 49 mm inner diameter and were dried.
(2) LM transportation: The membrane was fixed at the center of the U-shaped reaction cell. The 30 or 40
cm3 of aqueous supplying phase ([Fe(NH2)2(SO4)2] = 5.0 10-5 mol dm-3, [CH3COONa] = 0.01 mol dm-3,[CH3COOH] = 0.01 mol dm-3, pH 4.70) and the 30 or 40 cm3 of aqueous receiving phase ([HCl] = 1 M, pH0) were poured into each part of the reaction cell separated by the membrane. After 24 hours, the pH values,
the volumes and the Fe concentrations of the supplying and receiving aqueous phases were measured.
Results and discussion The membrane worked stably as a separator of two aqueous phases when themembrane left 6 mm margin around the center hole with a diameter of 25 mm in the reaction cell. Table
shows the results of LM transportation of Fe2+ ions for the different membrane composition. Compared with
the LM transportation of Cu2+ ions, Fe2+ ions were much less transportable due to less stable complex
formation according to Irving-Williums rule. It suggests the possibility of metal separation by the LM
transportation due to the different stability of metal complex formations. Compared between Nos. 2 and 3, it
was found that the transportation rate can be controlled by the choice of carrier molecules. Fe2+ ions seem tosuit N coordination atoms of phen rather than O atoms of PMBP according to HSAB theory.
Table Results of liquid membrane transportation of Fe2+ under the different experimental conditions.
No.

PVC

[C6mim][Tf2N]

DOP

PMBP

phen HCl H2O

TimeTransportation Rate

[g]

[g]

[mol/kg][mol/kg][mol/kg]

[h]

[–]

1

0.1

1.25

–

–

0.05

24

0.10

2

0.3

–

1.25

–

0.05

24

0.10

3

0.3

–

1.25

0.05

–

24

0.02

−58−

2020-59
Exploration of hierarchical dynamics of amorphous polymers by broadband dielectric
spectroscopy
Osamu Urakawa

Osaka University

We examined the hierarchical dynamics of a topological network formed by rotaxane-type movablecrosslinks consisting of a poly(ethyl acrylate) backbone threaded through peracetylated - or -cyclodextrins(CD) connected to other chains. Figure 1 schematically shows the structure of the movable crosslinking
network. These network materials were synthesized by bulk radical copolymerization of ethyl acrylate andperacetylated - or

-CD monomers: PEA- -CD, or PEA- -CD. The rotaxane structure was naturally

introduced through this synthesis even though the amount of rotaxane type CD moieties is small (22 mol% of
the feed CD content, determined from the dielectric
intensities). The obtained materials were rubber-like andDipole moment

highly stretchable. We conducted rheological and broadband
dielectric

spectroscopy

measurements toanalyzethehierarchical dynamics governing the material properties.
Figure 2 shows the storage modulus G (composite curves) as
functions of frequency

for PEA- -CD with

Figure 1. Rotayane-type movablecrosslink network

various CD contents at temperatures 50°C above
each glass transition temperature. By increasing
the molar fractions of CD (x), the G ( ) spectra at
lowchange: the terminal slopes change from 2

to 0, suggesting the formation of rotaxane typecrosslinks. In the glass to rubber transition region(atFigure 2. G ( ) for PEA- -CD with x=0~1.5mol%.

= 10~105 s-1), where network strand dynamics is

responsible, a new relaxation process called “slowmode” was detected. Figure 3 shows the corresponding
dielectric data ( -derivative of dielectric permittivity),clearly exhibiting the slow mode indicated by the blackarrow. We ascribed this dielectric relaxation mode to therotational motion of the rotaxane type cyclodextrin
moieties via sliding on the polymer backbone

Figure 3. dependence of the derivative of dielectric
permittivity for PEA- -CD with x = 0 ~ 1.5 mol %.

accompanied by the chain conformational change. The temperature dependence of this mode relaxation timeobeyed the Arrhenius type equation with the activation energy Ea = 140 kJ mol-1. From this Ea value, we
concluded that CD’s sliding motion occurs through a distance of about or longer than the Khun length.
Reference) Kashiwagi, Y.; Urakawa, O.; Zhao, S.; Takashima, Y.; Harada, A.; Inoue, T. Macromolecules 2021,
accepted.
−59−

2020-60（国際）Dielectric relaxation of type-A rouse chain under endadsorption/desorption equilibrium: Effect of motional coupling
Youngdon Kwon

Sungkyunkwan University

Properties of polymer nanocomposites reflect not only those of polymer matrix and nanoparticles but also
the behavior of the interface therein.1) The structure and dynamics of interfacial layers between the bulk
polymer phase and the particle surface have been studied with the aid of various experimental techniques, forexample, small angle x-ray scattering2) and broadband dielectric spectroscopy.3) However, those studies mainly
considered very strong adsorption of the segments, which is equivalent to an assumption of the chains attachedto the particle surface through strong bonds. Obviously, this assumption should fail for the adsorption
occurring through moderate bonding (for example, hydrogen bonding).4) This work is devoted for this caseof moderate adsorption, and a mathematical formulation of the unentangled dynamics (Rouse dynamics) forthe end-adsorbing type-A chains (Figure 1) has demonstrated a significant effect of adsorption/desorption
equilibrium on the end-to-end fluctuation of the chains (detected with a dielectric method).

ng= 0ug(ng)

ng = N1k ( W des)1
k ' ( W ads)

nf = 0uf(nf)

nf = N

Fig. 1. Illustration of a type-A linear Rouse chain undergoing end-adsorption and desorption. The adsorption
occurs on a fixed point in space. Nevertheless, a hypothetical, permeable surface is also illustrated forconvenience of distinguishing the desorbed (free) and adsorbed (grafted) chains.

log W / W olog < j>n/< f>on

This formulation considered a conformational exchange between the adsorbed and desorbed chains that
results in strong a motional coupling between those chains. Eigenmode analysis for those motionally coupledchains5) enabled analytical characterization of the time evolution of the chain conformation and thecorresponding changes of the end-to-end fluctuation time W with the adsorption and desorption time constants,
Wads and Wdes shown in Figure 1.
0.6
A typical result, obtained for a case of Wads = Wdes, is shown in
Figure 2. On enhancement of adsorption/desorption (i.e., on aadsorbeddecrease of Wdes), the conformational exchange is accelerated so
0.4
Grafted chainthat the fluctuation time W normalized by W o in the absence of theadsorption decreases and increases, respectively, for the chains
0.2
desorbedFree
chain
in the adsorbed and desorbed states. In an extreme of fastoadsorption/desorption (Wdes 0), W /W of the chains in those states
0.0
merge with each other and the two states become-2 -1 01
2
3
4
indistinguishable. These results demonstrate a new aspect inloglogW or/d,f
W desthe dynamics of adsorbed/desorbed chains, a strong effect of
Fig. 2. Changes of fluctuation time of
their conformational exchange.
adsorbed and desorbed chains with Wdes.


Acknowledgement:This work has been published in J. Soc. Rheol. Japan, 48, 27 (2020).

references: 1) Cheng et al, J. Chem. Phys., 146, 203201 (2017). 2) Jouault et al, ACS Macro Lett., 5, 523(2016). 3) Klonos PA, J. Phys. Chem. C, 122, 50 (2018). 4) Srivastava et al, Curr. Opin. Chem. Eng., 16,
92 (2017). 5) Kwon et al, Macromolecules, 52, 8484 (2019).

−60−

2020-61（国際）Molecular mechanisms for the inactivation of a growth hormone in rice
Zuhua He Chinese Academy of Sciences
Objectives: Gibberellins (GAs) are a group of diterpenoid carboxylic acids. They act as plant
hormones that play critical roles in promoting growth, including internode (stem) elongation ofrice. The elongated uppermost internode 2 (eui2) mutant of rice shows a tall phenotype due toits elongated uppermost internode. Because of this reason, this mutant has been used in hybrid
rice breeding in order to eliminate panicle enclosure in male sterile parents. We havepreviously identified the EUI2 gene by map-based cloning, and found that EUI2 is afunctionally-uncharacterized protein that belongs to the D,E-fold hydrolase superfamily. In
collaboration with Shinjiro Yamaguchi’s group, we have previously characterized the rice euimutant and found that EUI encodes a cytochrome P450 enzyme that deactivates GAs via
epoxidation. Interestingly, the eui eui2 double mutant plants are phenotypicallyindistinguishable from the eui single mutant, supporting the idea that EUI and EUI2 act in thesame pathway. Based on this notion, we speculated that EUI2 might act as an epoxy hydrolase
and further deactivate epoxidated GAs in the uppermost internode of rice. Our objective of thiscollaborative research is to prove this hypothesis. First, we need to examine whether EUI2
protein can hydrolyze epoxy GAs. Second, we determine the levels of endogenous epoxy GAs
in wild type and the eui2 mutant. We would also need to examine the biological activities of
epoxy GAs. Because of his expertise in plant hormone biochemistry, especially GAs, we
collaborated with Prof. Shinjiro Yamaguchi at ICR in Kyoto University on this project.
Experimental methods: EUI2 recombinant protein was prepared in bacteria. Epoxy GAs inrice plants were analyzed by LC-MS/MS after derivatization as ethyl esters. Biological activityof epoxy GAs was determined by a micro-drop method using GA-deficient rice seedlings. The
physical interaction between the GA receptor GID1 and epoxy GAs was analyzed bydifferential scanning fluorimetry (DSF).
Experimental results: We found that the recombinant EUI protein is able to hydrolyze epoxy
GAs to produce diols in vitro. To analyze endogenous epoxy GAs in rice, we could not simply
follow the normal method for GA purification because epoxy GAs are not stable under weakacidic conditions during the purification steps. We therefore derivatized epoxy GAs as ethyl
esters and purified them as neutral compounds. This method was successful in finding that theeui2 mutant accumulated epoxy GA4 at higher levels than did wild type plants. Our biologicalactivity test showed that epoxy GA4 was weakly active. We chemically synthesized epoxy GA4.
DSF analysis indicated that epoxy GA4 can physically interact with the GA receptor GID1,
consistent with its weak biological activity. These results suggest that the accumulation of
epoxy GA4, which is weakly bioactive, is the cause of the tall phenotype of eui2.
Publications: In preparation.
−61−

2020-62（国際）Well-defined AIE-based polymer brush for the application of theelectrochemical luminescence biosensors
Ying MaSouth China University

Electrochemical luminescence (ECL) sensors have demonstrated broad applications inbiomedical analysis with high sensitivity, and been applied in clinical diagnosis for avariety of biomarkers. However, the development of new ECL agents with high quantum
yields and good stability is the key issue to improve the sensitivity of sensors.
Fluorophores with aggregation-induced emission (AIE) property are good candidates tosatisfy this requirement owing to their high ECL performance, while their fixation onelectrode surface with controlled thickness and density is still a challenge.
In this project, we are working with Prof. Kohji Ohno (ICR partner researcher) to focus
on the fixation of AIE dyes on a gold (Au) electrode surface based on the surface-initiatedatom transfer radical polymerization (SI-ATRP), and achieved the good ECL signals interms of high intensity and good stability. The experiment involves in four key sections:(1) synthesis of ATRP initiator with disulfide group to allow its fixation on Au electrodesurface; (2) synthesis of tetraphenylethylene (TPE)-carrying monomer and its subsequent
graft on electrode surface via SI-ATRP; (3) the ECL behavior of TPE-carrying polymer
brush; (4) the ECL detection of alkaline phosphatase (ALP).
The results show that AIE-carrying monomer can be successfully grafted on Au surface
via SI-ATRP, and its thickness can be well tuned by the polymerization conditions. The
polymer brush has been characterized by the fluorescence and infrared spectra. More
importantly, the resulting polymer brush exhibited good ECL behavior in the presence oftriethylamine, and its ECL intensity is very dependent on the thickness of polymer brush,which reached a maximal intensity with the polymer molecular weight of 15 kDa. In
addition, the ECL signal remained 95% of its intensity after 50 times of cyclic
voltammetry scanning, revealing its good ability as an excellent ECL agent for sensors.
Furthermore, we developed an ALP sensor based on a bipolar ECL sensing platform withthe polymer brush-modified electrode as an ECL reporting electrode and a bare Au
electrode as a sensing electrode. The ALP could catalyze its enzymatic substrate into
phenol to generate an electrochemical current, which induces the tunable ECL signals.
Therefore, the ALP concentration could be readout by ECL signals. Good linearity of thesignal in the ranges of 0.1-20 mU/L for ALP was obtained and the limit of detection canreach as low as 0.02 mU/L, which could be well applied in the clinical profiling of ALP.

−62−

2020-63（国際）Role of phosphoinositide signaling in pollen development−63−2020-64（国際）Role of PX-PH-type phospholipase Ds in plant intracellular
membrane traffic−64−2020-65（国際）Proteomic approach to discovering specific inhibitors for bile-acidinteracting enzymes
Xiaoguang Lei

Peking University

Bile acids (BAs) are important amphipathic molecules produced in the liver that improvelipids digestion by emulsification. Bile acid metabolism and signaling have been gaining
significance due to the relationship between bile acids and diseases such as cancer, type 2
diabetes, cardiovascular, cholestatic and fatty liver disorders (Thomas et al., 2008). While
endogenous receptors for bile acids, in particular the nuclear farnesoid X receptor (FXR) andthe plasma membrane bound G protein-coupled receptor (TGR5) have been widely
investigated (Thomas et al., 2008), the biological significance of other bile acid-binding
proteins remains unexplored.
Our group in Peking University recently discovered more than 600 novel bile
acid-interacting proteins (Zhuang et al., 2017). In this project, we collaborated with the Uesugigroup in ICR for analyzing those bile acid-interacting proteins and for discovering small
molecules that selectively block the interactions. The Uesugi group of ICR has recently
developed a chemical library of bile acid analogues. Bile acid analogues have shown toactivate or antagonize known bile-acid interacting proteins (Thomas et al. 2008).
In 2020, our collaboration identified an immune receptor X as an unprecedented bile-acidbinding protein in immune cells. Intriguingly this highly important protein is not listed in the
600 bile acid-interacting proteins that we previously found in non-immune cells. Uesugi groupin ICR experimentally tested its ability to interact with bile acids and found that bile acids
physically associate with protein X. The photo-affinity probe of bile acids that was synthesizedin our group in Paking University was exploited in ICR for the demonstration of theinteraction. Biological significance of the interaction remains unclear at this moment, andexperiments using immune cells are currently underway.
It has long been known that bile acids and their metabolites modulate immune responses;
however their modes of action remain incompletely understood. Our findings suggest an
exciting possibility that bile acids are hitherto unidentified endogenous modulators of protein
X for controlling immune responses.

−65−

2020-66（国際）Transfer of redox sensitive elements across the sediment-water interface in a
hypoxia area near the East China Sea
Pinghe Cai Xiamen University
Objectives: By working with Prof. Yoshiki Sohrin at ICR, this project aims to 1) quantifying
benthic fluxes of dissolved trace metals and 2) examining how these fluxes change with varying
redox potentials at the sediment-water interface in a seasonal hypoxia area near the Yangtze
River Estuary (China).
Experimental methods: Sediment and porewater samples were collected along a transect in the
East China Sea in summer 2020 (Figure 1). Exchangeable radium-224 (224Ra) and surface-boundthorium-228 (228Th) in sediments were
measured using a RaDeCC system. Porewater
profiles of dissolved iron (Fe) was analyzed
using an ICP-MS. Phosphate concentrations inporewater were determined as per the classic
colorimetric method. Oxygen concentrations
in bottom seawater was obtain using the
Winkler titration method.
Figure 1. Sampling stations in the East China Sea
Experimental results: Benthic fluxes of dissolved Fe estimated from 224Ra/228Th disequilibriumin the sediment show an increase with decreasing dissolved oxygen concentration (Figure 2). At
bottomseawaterdissolved

oxygenconcentrations lower than 63 µM, benthic fluxesof dissolved iron increased to a maximum of 10.8mmol m-2 d-1. When oxygen concentrations werehigher than 150 µM, benthic fluxes of dissolved
iron declined to a level of <1.0 mmol m-2 d-1. In
the meantime, benthic fluxes of phosphate
display a pattern similar to dissolved Fe.
Figure 2 Plot of benthic Fe flux vs. oxygen level
Discussion: Benthic fluxes of dissolved Fe are extremely sensitive to oxygen levels in the bottom
water. There is a tight coupling of dissolved Fe and phosphate, probably reflecting the dissolutionof poorly crystalline iron oxides in bottom sediments that releases dissolved Fe and phosphate
simultaneously into the overlying water column.
Outcome report : Not yet available.

−66−2020-67（国際）Application of artificial viral capsid to intracellular delivery
Kazunori Matsuura

Tottori University

There is increasing interest in the potential of functional proteins such as antibodies andpeptides that regulate protein-protein interaction (PPI) as biopharmaceuticals. However, whenthese are applied intracellularly, it is essential to develop a highly efficient introduction system
into cells. On the other hand, our research group reported a 24-residue artificial peptide(INHVGGTGGAIMAPVAVTRQLVGS) derived from the viral backbone forming E-annulus
structure [1]. We found that the peptide self-assembled in water, yielding virus-like nanocapsulesof 30-50 nm diameters. We also confirmed that the peptide assembly has a hollow structure bysmall-angle X-ray scattering, and the N-terminal (present inside the assembly) and the C-terminal(present on the surface of the assembly) of this peptide can be selectively modified with various
molecules [2]. The purpose of this study is to create a novel intracellular delivery carrier by
conjugating the E-annulus peptide with the intracellular delivery peptide HAad developed by
ICR partner researcher [3] and to evaluate their applicability to intracellular delivery.
As our first step toward this goal, a HAad-modified artificial viral capsid was preparedthat encapsulates the enhanced green fluorescence protein bearing a histidine tag (EGFP-His6).
NTA-E-annulus-C[HAad] which has a nickel-nitrilotriacetic acid (NTA) on the N-terminusof E-annulus peptide and the HAad peptide conjugated at the C-terminus was prepared. NTAE-annulus-C[HAad] formed a nanoparticle having diameter of ~30 nm. Moreover, efficient
encapsulation of EGFP-His6 was achieved in the presence of Ni 2+. Marked cytosolic
distribution of EGFP-His6 was also observed to 74% of cells when HeLa cells were treatedwith Ni-NTA-E-annulus-C[HAad] encapsulating EGFP-His6 for 1 h. The above results
suggested the promise of the use of E-annulus-based artificial viral capsids to intracellular
protein delivery.
Our original plan included the invitation of Professor M. Ryadnov, the National PhysicalLaboratory, UK to Japan. Unfortunately, due to the prevails of COVID-19, that was not possible.
However, we had a chance to have his lecture on web to discuss about the refinement of thestructure of virus-like nanocapsules and the possibility of collaboration in future.
[1] K. Matsuura et al. Angew. Chem. Int. Ed. 2010, 49, 9662–9665; [2] K. Matsuura et al. Org.
Biomol. Chem. 2016, 14, 7869–7874; [3] K. Sakamoto et al. Angew. Chem. Int. Ed. 2020, 59,
19990-19998.

−67−

2020-68（国際）Structural and functional analysis of curvature-inducing peptides andapplication
Anne S. Ulrich

Karlsruhe Institute of Technology

Epsin-1 is a representative protein which induces the positive curvature necessary for theformation of clathrin-coated pits during endocytosis. Modulating the structural dynamics ofbiomembranes by inducing bilayer curvature and lipid packing defects has been highlighted asa practical tool to modify membrane-dependent cellular processes. Collaborative research of
Ulrich research group at KIT with Futaki research group at ICR, Kyoto University has alreadyshown that the N-terminus 18-residue peptide of epsin-1 (EpN18) possess curvature inducing
abilities of the parent protein (ACS Chem. Biol. 2013, 8, 1894). We also reported that EpN18
also promotes membrane remodeling including lipid packing defects in cell membranes (Angew.
Chem. Int. Ed. 2017, 56, 7644). However, a high concentration is required to exhibit apronounced effect. In this study, we demonstrate a significant increase in themembrane-remodeling effect of EpN18 by constructing a branched EpN18 homotrimer. Bothmonomer and trimer could enhance cell internalization of octaarginine (R8), a cell-penetrating
peptide. The EpN18 trimer, however, promoted the uptake of R8 at an 80-fold lower
concentration than the monomer. Analysis of the generalized polarization of a polarity-sensitivedye (di-4-ANEPPDHQ) revealed a higher efficacy of trimeric EpN18 in loosening the lipid
packing in the cell membrane. Circular dichroism measurements in the presence of lipid
vesicles showed that the EpN18 trimer has a higher-helix content compared with themonomer. The stronger ability of the EpN18 trimer to impede negative bilayer curvature is also
corroborated by solid-state 31P NMR spectroscopy. Hence, trimerizing peptides can beconsideredapromisingapproachforanmembrane-remodeling performance.

−68−

exponential

enhancement

of

their

2020-69（国際）Site-selective protein acetylation by a small molecule
Lu Zhou

Fudan University

Post-translational modifications (PTMs) play essential roles in regulating a myriad of cellular
processes in mammalian cells, including signal transduction, metabolism, and genetranscription.

Dysregulationofproteinmodifications

causesmetabolicdiseases,

neurodegenerative diseases and cancers. Among protein modifications, acetylation andphosphorylation represents the most critical PTM. In the present research with ICR, we
continued to collaborate with the Uesugi research group to design small molecules thatspecifically acetylate or phosphorylate cellular proteins.
Our collaboration has already led to the discovery of a small-molecule acetylase mimic thatspecifically acetylates Lys-100 of PGAM1. The molecule, referred to as KHAc, has an acetyl
ester group as an acetyl donor. Together with the Uesugi group, we have checked theselectivity of the molecule and found that KHAc is selective to PGAM1 at the proteome level.
We have summarized the data which were published in ACS Chemical Biology.
To discover more small-molecule acetylases selective for a number of different proteins,
we screened a chemical library of 280 acetyl ester compounds. Each of these molecules was
incubated with cell lysates or even live cells, and acetylated proteins were analysed by western
blots with a pan-antibody against acetylated lysine. Unfortunately, any of the screening hits
failed to exhibited clear acetyl transfer reactions in multiple assays. We therefore decided todesign acetylation compounds for protein X, which has recently been shown as an important
immune regulatory protein that is controlled by acetylation. We have synthesized a number ofcompounds and subsequently discovered a compound that is capable of transferring an acetylgroup to protein X in a selective way.
In the phosphorylation project, collaboration with Uesugi group allowed us to identify anitro-benzyl phosphate group as a donor of UV-induced phosphate transfer reactions inaqueous solutions. We conjugated a nitro-benzyl phosphate group to drug A, a known inhibitorof Y kinase. Such hybrid molecules may transfer a phosphate group upon UV irradiation. In
other words, this approach converts inhibitors to UV-dependent kinase activators. We arelooking forward to continued collaborations with ICR.

−69−

2020-70（国際）Modulation of ferrimagnetic spin waves by electric field
Kab-Jin Kim

KAISTObjective:
The aim of the research is to study the spin wave of ferrimagnetic alloys.
Experimental methods:
For this study, we prepared ferrimagnetic films at prof. Teruo Ono’s group in ICR and measured
the electrical properties at KAIST. The longitudinal resistance as well as the transverse resistance
was measured by sweeping the magnetic field at various temperatures. To characterize the spinwave, we also used Brillouin light scattering measurement technique.
Experimental results:
We investigate the spin wave handedness and magnetoresistance of ferrimagnetic GdFeCo acrossthe magnetization compensation temperature, TM as well as the angular momentum
compensation temperature, TA. The spin wave handedness was found to reverse at TM and TA.
The magnetic field dependence of longitudinal resistivity ( xx) shows opposite trends below andabove TM, and the variation of xx with B becomes more significant as the temperature decreases.
The transverse resistivity ( xy) of GdFeCo shows negligible field dependence.
Discussion:
The observed distinct spin wave handedness is attributed to the gyromagnetic reversal of
ferrimagnetic alloy. As for the unconventional magnetoresistance, we ascribe it to thesperimagnetism of GdFeCo. We also reveal that, contrary to the recent reports that the transition
metal dominates transport of rare-earth transition-metal ferrimagnets, the Gd contribution tomagnetoresistance is comparable to the FeCo contribution, showing that the transport of GdFeCo
is antiferromagnetic. Our results therefore show that ferrimagnets are a convenient platform forstudying antiferromagnetic spin wave as well as antiferromagnetic spin transport.
Publication:
J. Park et al., Phys. Rev. B 103, 014421 (2021).

−70−

2020-71（国際）Novel strategy for intracellular delivery of nanomedicines
Sílvia PUJALSInstitute for Bioengineering of Catalonia

Nanomedicine arose 20 years ago with the promise of selectively delivering drugs totarget sites, thus increasing their effectivity while minimizing undesired side effects. However,despite the great promise behind nanomedicine for drug delivery, very few products have been
approved for patient use. This poor translation into clinic comes from different factors, some ofthem being a poor characterization of the nanomaterials or a simplistic model to evaluate them.
Poor cellular uptake efficacy of these nanomedicines is also a big obstacle. Our research group
has a speciality in preparation of nanoparticles being applied for nanomedicine. We also havestrong background of nanomaterials characterization and intracellular behavior using various
microscopic techniques (including electron microscopy and super resolution microscopy). On
the other hand, Professor Futaki at ICR, Kyoto University is an expert on intracellular deliveryof nanomedicines.
The successful cytosolic delivery of nanoparticles is hampered by their endosomal
entrapment and degradation. To push forward the smart development of nanoparticles we must
reliably detect and quantify their endosomal escape process. However, the current methods
employed are not quantitative enough at the nanoscale to achieve this. Nanoscopy is a rapidly
evolving field that has developed a diverse set of powerful techniques in the last two decades,
opening the door to explore nanomedicine with an unprecedented resolution and specificity.
The understanding of key steps in the drug delivery process – such as endosomal escape –would benefit greatly from the implementation of the most recent advances in microscopy.
Therefore, we have made discussions on the possible design of ideal nanoparticles based on our
understanding on the current status of the use of nanoscopy for endosomal escapequantification.1) Alternatively, Futaki and coworkers developed delivery peptides potentiallyapplicable to cytosolic delivery of nanoparticles.2,3) Studies are underway by merging the above
insights.
References
1) T. Andrian, R. Riera, S. Pujals, L. Albertazzi, Nanoscale Adv., 2021, 3, 10-23
2) K. Sakamoto, M. Akishiba, T. Iwata, K. Murata, S. Mizuno, K. Kawano, M. Imanishi, F.
Sugiyama, S. Futaki, Angew. Chem. Int. Ed. 2020, 59, 19990-19998.
3) J. V. V. Arafiles, H. Hirose, Y. Hirai, M. Kuriyama, M. M. Sakyiamah, W. Nomura, K. Sonomura, M.
Imanishi, A. Otaka, H. Tamamura, S. Futaki, Angew. Chem. Int. Ed. in press.

−71−2020-72（国際）Revealing exciton quenching mechanisms in thermally activated delayed
fluorescent devices
Lian Duan

Tsinghua University

Organic light-emitting diodes (OLEDs) have become popular in the commercial products suchas smart phones, flat-panel displays and solid-state lightings. For further practical applications,one of the challenges is to realize both high efficiency and excellent device lifetime for blue
OLEDs, especially at high brightness. Recently, thermally activated delayed fluorescence(TADF) emitters have been reported, showing high device efficiency comparable tophosphorescent OLEDs. This is because TADF emitters have small single-triplet energy gap( EST), and therefore can convert non-emissive triplet excitons to emissive singlet excitons via
reverse intersystem crossing (RISC) process. However, the lifetimes and efficiency at highbrightness of the blue OLEDs are still far from satisfaction from the point-view of practicalapplications and guidelines for efficient and stable blue TADF OLEDs are still rare.
To overcome the above problems, we have developed efficient and stable blue OLEDs using
a TADF compound to sensitize a fluorescent dopant, known as TADF-sensitized fluorescenceemission (TSF). In this process, the triplet excitons generated on the TADF sensitizer can be upconverted into the singlet ones through RISC process, from where the energy will be transferredto the conventional fluorescent emitters through the long-range Förster energy transfer. Ourgroup have successfully achieved TSF-OLEDs with the external quantum efficiency (EQE) over
20% even at high brightness by combining the sterically hindered fluorescent emitters to avoid
the unfavorable energy transfer from triplets of the host and TADF materials to that of thefluorescent emitters by short-range Dexter energy transfer (D. D. Zhang et al., Adv. Mater. 2018,30, 1705250).
It is well known that the major degradation mechanisms in OLEDs are triplet-triplet andtriplet-polaron annihilation. These processes originates from Dexter energy transfer from thetriplet to triplet and the triplet to the polaron. Thus, the use of TADF emitters with very fast RISC
rate constant as sensitizer is expected to suppress these processes and thus simultaneously
improve the efficiency roll-off and lifetime of OLEDs. On the basis of the above concepts, wehave conducted the collaboration work with Kaji group to develop highly efficient blue stable
OLEDs.
In this year, due to COVID-19 related difficulties, our group and Kaji group have
independently advanced researches: our group have developed efficient and stable deep blue
TSF OLEDs by using wide-energy-gap TADF materials as sensitizer (D. D. Zhang et al., Adv.
Mater. 2020, 32, 1908355) and Kaji group have reported a new TADF emitters exhibiting
ultrafast RISC rate constant around 107 s 1 (Y. Kusakabe, et al., Front. Chem., 2020, 8, [530-1][530-9]). We now plan to further improve the efficiency and stability of our blue TSF OLEDs byadopting the ultra-fast RISC TADF materials developed by Kaji group. We anticipate that abreakthrough in blue OLEDs can be achieved by our continuing collaborative work, which ishighly desired for both academical and industrial fields.

−72−

2020-73（国際）−73−2020-74（国際）Synthesis of polyether nanocomposite solid polymer electrolytes forlithium ion batteries
Robert C. Ferrier, Jr. Michigan State University
Objective. The objective of this work was to develop novel
polyether-based nanocomposite materials for lithium ion
batteries (LIBs) by combining the epoxide polymerization
techniques of the PI and the surface initiated polymerization
techniques developed by the ICR partner researcher, Prof.
Ohno from Kyoto University. Experimental Methods.
Aluminum-based initiators were characterized by 1H NMR
spectroscopy. Polymers were characterized by size-exclusion
chromatography (SEC), 1H and 13C NMR spectroscopy,
Figure 1. Molecular weight control

differential scanning calorimetry (DSC), broadband dielectric
spectroscopy (BDS), rheometry, and small angle X-ray

scattering (SAXS). Experimental Results. Homopolymers of poly(butylene oxide) (PBO),
poly(propylene oxide) (PPO), and polyepichlorohydrin (PECH) were characterized by BDS andfound to have room temperature conductivity of 10-7 S/cm at 50:1
lithium to oxygen ratio. To improve conductivity, copolymers of
the above polymers as well as polymers containing high dielectric
constant units have been synthesized. The thiol based initiator
developed in last year’s grant (2019-74) was used to polymerize
propylene sulfide (PS), which can be converted to poly(propylene
sulfone). Figure 1 shows the molecular weight control of PPS to
100 kg/mol with narrow polydispersity (Ð). Copolymers of PS
and epoxides PO and ECH were also synthesized. Block and

Figure 2. Architecture control

statistical architectures were produced and copolymer structure was confirmed via diffusion ordered
spectroscopy (DOSY). Finally, architecture was tuned through the development and utilization of abi-functional and four-armed initiator. Figure 2 shows the architecture control. In the future, we will
perform surface initiated polymerizations of these polymers from silica nanoparticles and investigate
conductivity properties. Publications. An article entitled “Aluminum-based Initiators from Thiols
for Epoxide Polymerizations” co-authored by the PI and his ICR partner researcher Prof. Ohno was
accepted to Macromolecules (doi.org/10.1021/acs.macromol.0c00464). Another publication based on
the work above is in preparation to be submitted in March. My student, Ms. Niloofar Safaie, will
present this work at the April meeting of ACS, held virtually, with a talk entitled: “Aluminum-based
initiators from thiols for epoxide polymerizations.”−74−

2020-75（国際）Structural and functional analysis of the surface glycolipids of outermembrane vesicles released by bacteria
Maria Michela Corsaro University of Naples Federico II
Objectives:
Outer membrane vesicles (OMVs) secreted by bacteria to the extracellular space play importantroles in intercellular communication, pathogenicity, defense, and so on. The group of the ICR
partner researcher (Prof. Tatsuo Kurihara) recently isolated a new bacterial strain named
Shewanella vesiculosa HM13, which produces OMVs carrying a single major cargo protein
named P49. Disruption of wzx, which is located in the vicinity of the P49 gene on the genome
and codes for a putative flippase involved in oligosaccharide translocation, caused
mislocalization of P49, suggesting that P49 interacts with the surface glycolipids of OMVs. The
objective of this work has been the isolation and the structural characterization oflipooligosaccharides obtained from the constructed wzx-mutant.
Experimental:
Dried cells and OMVs from the wzx-mutant (5.1 g and 81 mg, respectively) of S. vesiculosa
HM13 grown at 18 °C were extracted with phenol/chloroform/light petroleum (PCP) method torecover LOS with a yield 1.9% w/w from dried cells and 19% w/w from dried vesicles.
Polyacrylamide gel electrophoresis (PAGE) was performed with sodium deoxycholate (DOC) as
detergent, as reported (Casillo, 2019). All the chemical analyses and NMR spectra were obtained
as already reported (Casillo, 2019).
Results:
After PCP extraction of cells (wzx_c) and OMVs (wzx_OMV) from the wzx-mutant, both crude
extracts were analyzed by DOC-PAGE, and the results compared with those of cells (wt_c) andOMVs (wt_OMV) from S. vesiculosa HM13 wild-type (Di Guida, 2020). No differences related
to electrophoretic pattern appeared among the four samples. The samples were then treated withhydrazine and, after that, with 4M KOH, obtaining the corresponding phosphorylated
oligosaccharides (OS). The 1H NMR spectral analysis and a comparison with those obtained
from wild-type samples revealed slight differences in the anomeric and carbinolic regions
between the samples from the wzx mutant and the wild-type ones.
Casillo, A. et al. Marine Drugs (2019), 17, 34.
Di Guida et al. Marine Drugs (2020), 18, 231.

−75−

2020-76（国際）Construction of heterologous protein secretion system at low temperaturesby using cold-adapted microorganisms
Xianzhu Dai[Objectives]

Southwest University

Gram-negative and Gram-positive bacteria secrete membrane-enclosed

nanoparticles called extracellular membrane vesicles (EMVs). EMVs are involved in bacterial
survivability, such as intercellular communication, biofilm formation, infection, and defense
against bacteriophages. EMVs also have attracted the attention of biotechnological industries fortheir potential use as a platform for drug delivery system, vaccine development, and secretory
protein production. In this study, we used a hyper-vesiculating and cold-adapted bacterium,
Shewanella vesiculosa HM13. This bacterium isolated by the group of the ICR partner researcher(Prof. Tatsuo Kurihara) secretes an S-layer-like protein, P49, as a single major cargo of the EMVs.
This highly selective cargo transportation mechanism is expected to be useful for vesiculationmediated heterologous protein production and the development of surface engineered vesicles.
Here, to examine whether the P49-selective cargo transportation to EMVs is available forsecretory production of heterologous proteins, green fluorescence protein (GFP) fused to P49
was expressed in S. vesiculosa HM13.
[Experimental methods]

A gene coding for GFP was fused to the 3’-terminus of the P49 geneby homologous recombination using a suicide plasmid, pKNOCK-Km. The recombinant strain
was cultured at 18 °C, and distribution of the fusion protein in the insoluble fraction of the cells,
the soluble fraction of the cells, the culture supernatant after removal of EMVs (PVF), and EMVs
was analyzed by western blotting with an anti-GFP antibody. As a control, the recombinant strain
producing GFP without being fused to P49 was constructed.
[Experimental results and discussion] GFP without being fused to P49 was detected only fromthe cellular soluble fraction, whereas GFP fused to P49 was transported to EMVs, indicating thatP49 can function as a carrier to deliver the fusion partner to EMVs. On the other hand, P49-free
GFP was also detected from the EMVs of the recombinant strain expressing GFP fused to P49,
suggesting the occurrence of an unexpected proteolytic cleavage between P49 and GFP.
Regulation of this putative proteolytic cleavage is supposed to enable production of P49-freeforeign protein by facilitating the cleavage. In contrast, it may be possible to obtain the fusion
protein with higher purity by suppressing the cleavage. These findings facilitate the applicationof the EMV production and the vesiculation-mediated protein secretion of S. vesiculosa HM13.

−76−2020-77（国際）Molecular mechanisms governing gene expression regulation in plant
plasticity
Vicente RUBIO

National Center of Biotechnology

Objectives: We focus to understand molecular mechanisms bridging proteolysis to pre-mRNA
processing in environmental adaptation. Plant plasticity is obtained by orchestrating numerous
spatiotemporal gene expressions. CULLIN4 RING ligase complexes (CRL4) mediatedproteolysis has been associated to gene expression regulation. We at CNB-CSIC have revealed
that one of its subunit, DDB1, associate with DDB1, CUL4-Associated Factors (DCAFs) andothers, which directly bind specific targets to promote their ubiquitination and degradation. Dr.
Tsuge’s group at ICR works on another CRL-interacting complex, COP9 signalosome (CSN)
that binds mRNA processing factors. Here, we aim to reveal that, by maintaining accurate
levels of regulatory proteins through targeted degradation and transcription control, CRL4,
DCAFs, and CSN survey nuclear processes essential for gene expression regulation.
Experimental methods: Arabidopsis was chosen as a model to investigate CRLs, DCAFs, CSN
and their binding factors. CFI (cleavage factor I) is a complex that binds CSN in mammals andplants, and is involved in processing 3' UTR ends of pre-mRNAs. As a start, Tandem affinity
purification method and protein detection system, at CNB-CSIC was utilized to analyze
CFI-interacting proteins under different conditions.
Experimental results: CNB-CSIC revealed that Arabidopsis CFI 25a subunit interacts with CFI
25a, CFI 59, and CFI 68, suggesting, for the first time, that an intact CFI complex could beformed in plants. Furthermore, we identified FIP1, which is involved in pre-mRNA 3' end
processing, and CSN subunit, which is involved in signal transduction, as CFI 25 interacting
partners. Based on these novel findings, the ICR group established knock out plants for CFI 25,
CFI59, CFI 68, etc. to further analyze in planta gene expression regulation. This revealed that
CFI regulates gene expression through regulating not only the lengths of 3' UTR but also thediversity of the 3' ends in the isoforms of transcripts processed from the pre-mRNA. Further,analyses are being conducted to comprehend the molecular mechanisms of this regulation.
Discussion: These results were unique and were due to the fact that this collaboration was
utilizing the plant system as a model to comprehend the universal regulatory system. We favor
our hypothesis that diverse yet temporal-regulated transcript usages are key to respond to
specific environmental stimuli. Further collaboration will provide understanding for the generalplatform for gene expression regulation via proteolysis and transcriptional regulation.
Publications: in preparation, “CFI 25 subunit of Cleavage Factor I is essential forpolyadenylation site determination and its diversity in Arabidopsis thaliana (L.) Heynh.” X.
Zhang, M. Garcia-León, V. Rubio, T. Tsuge et al.

−77−

2020-78（国際）Formation of supramolecular complexes through a host-guest interaction
between cycloparaphenylene and azacorannulenes
Shingo Ito Nanyang Technological University
Objective
Supramolecular chemistry of polycyclic aromatic compounds has attracted much attention
because of the interesting structures and potential applications in material sciences. My
research group at NTU previously reported the synthesis of azapentabenzocorannulene (APC)
as the first example of nitrogen-containing buckybowls. In this collaboration, we aim atstudying supramolecular chemistry between APC and cycloparaphenylenes (CPP), which havebeen developed and investigated by Prof. Yamago at ICR.
Results and Discussion
First, we have established an efficient method for large-scale synthesis of hydrogen-substituted
APC (Scheme 1), because it is hardly soluble in common organic solvents. We could obtain asufficient amount of APC by optimizing recrystallization and HPLC separation. Next, the size
and ring number of CPPs suitable for hosting APC as a guest molecule were investigated bymolecular modeling and theoretical calculations, which suggested that [10] and [11] are themost suitable fit the core of APC. Therefore, hydrogen-substituted APC was mixed with [9],[10], and [11]CPP and analyzed by NMR, UV-vis absorption, and fluorescence spectroscopy(Scheme 1). The NMR spectra showed that there is no change in the chemical shifts of thesignals, which indicated that no intermolecular interaction occurred. Further investigation iscurrently ongoing.

N

APC

NMR
UV-visFluorescenceanalysis+n[9]CPP: n = 4[10]CPP: n = 5[11]CPP: n = 6

Scheme 1
Reference
1) T. Nagano, K. Nakamura, Y. Tokimaru, S. Ito, D. Miyajima, T. Aida, K. Nozaki, Chem. Eur.
J. 2018, 24, 14075–14078.

−78−

2020-79（国際）Research of multi-qubit diamond quantum processors
Marcus W. Doherty

Australian National University

Quantum communication and quantum computation are expected to establish a new paradigm
and advance our understanding of quantum mechanics. It is considered that they will provide
cryptography that can not be decoded and super parallel computation that is much faster than that ofordinary computers. Besides these, technical issues intriguing questions concerning quantum
mechanical phenomena can be addressed. NV centers in diamond are significantly interested as a
candidate of a resource for demonstration and the realization of them [1]. It is because that single
spins can be coherently controlled [2] and electrically driven single photon source are realized atroom temperature (RT) in the NV center. In other solid materials such as quantum dot orsuperconducting devices, those are realized only in extremely low temperature.
In this project, we would like to develop further this system with multi-nuclear spin qubits. We
discuss new architectures for enhancement of speed and fidelity of quantum processor by using multiqubits NV centers in diamond. We discuss the usage and production of isotopically engineered
diamonds for the enhancements of speed and fidelity of quantum processor. It is considered thatquantum communication and quantum computation will e.g. provide secure data encryption and superparallel computation that in certain cases outperforms classical computers. The realization of themhas strong impact not only to science but also to industry and society.
Recently, we proposed a full model of multi-qubit diamond quantum processors and develop asemi-analytical method for designing gate pulses [3]. This method optimises gate speed and delity
in the presence of random control errors and is readily compatible with feedback optimisation routines.
We theoretically demonstrate in delities approaching 10 5 for single-qubit gates and establishedevidence that this can also be achieved for a two-qubit CZ gate. Consequently, our method reduces
the effects of control errors below the errors introduced by hyper ne eld misalignment and theunavoidable decoherence that is intrinsic to the processors. Having developed this optimal control,
we simulated the performance of a diamond quantum processor by computing quantum Fouriertransforms. We nd that the simulated diamond quantum processor is able to achieve fast operations
with low error probability. We discuss the experimental demonstration of this method in this project.
References[1] M. W. Doherty, N. B. Manson, P. Delaney, F. Jelezko, J. Wrachtrup, L. C. L. Hollenberg, Physics
Reports 528 (1), 1-45 (2013).
[2] P. Neumann, N. Mizuochi, F. Rempp, P. Hemmer, H. Watanabe, S. Yamasaki, V. Jacques, T.
Gaebel, F. Jelezko, J. Wrachtrup. Science, 320, 1326 (2008).
[3] Y. Chen, S. Stearn, S. Vella, A. Horsley, M. W. Doherty, New J. Phys. 22, 093068 (2020).

−79−

2020-80（国際）Research toward stable NV centers at shallow region in diamond
Gopalakrishnan Balasubramanian

Leibniz institute for surface engineering

A negatively charged NV center in diamond is a versatile atomic-sized spin system forremarkable applications in quantum sensing and quantum-information science. The reason is that it
has excellent properties such as long coherence times [1,2] and high sensitivities with nanometerscale resolution. By utilizing nanoscale shallow NV centers, applications for nanoscale imaging [3]and nanoscale nuclear magnetic resonance were demonstrated. Furthermore, NV centers weresuccessfully integrated into photonic and mechanical structures, and in electronic devices, which
expands their versatility.
Toward these issues, Kyoto University groupdemonstrates the extension of the spin-coherencetime (T2), the stabilization of the charge state, and an
improvement of the creation yield of NV centersformed by the ion-implantation technique at a depthof ~15 nm in phosphorus-doped n-type diamond [4].
The longest T2 of about 580 s of a shallow NV
center approaches the one in bulk diamond limitedby the nuclear spins of natural abundant 13C asshown in figure. The averaged T2 in n-type diamond

Figure, Hahn-echo decays of NV centers in

is over 1.7 times longer than that in pure non-doped

undoped and Phosphorus (P) doped diamonddiamond. Moreover, the stabilization of the charge

sampels. Echo decays of the longest and an averagestate and the more than twofold improvement of thelength T2 in each sample are shown. The revivals

creation yield are confirmed. The enhancements forin echo decays are due to 13C nuclear spin

the shallow NV centers in an n-type diamond-precession, which rate matches the Larmor

semiconductor are significant for future integrated

precession frequency for the 13C nuclear spin.

quantum devices.
References[1] G. Balasubramanian, P. Neumann, D. Twitchen, M. Markham, R. Kolesov, N. Mizuochi, J. Isoya, J. Achard, J.
Beck, J. Tissler, V. Jacques, P. R. Hemmer, F. Jelezko, J. Wrachtrup, Nature Materials 8, 383 387 (2009).
[2] E. D. Herbschleb, H. Kato, Y. Maruyama, T. Danjo, T. Makino, S. Yamasaki, I. Ohki, K. Hayashi, H.
Morishita, M. Fujiwara, N. Mizuochi, Nature Communications, 10, 3766 (2019).
[3] Balasubramanian, G., et al. Nature 455, 648–651 (2008).
[4] A. Watanabe, T. Nishikawa, H. Kato, M. Fujie, M. Fujiwara, T. Makino, S. Yamasaki, E. D. Herbschleb, N.
Mizuochi, Carbon, 178, 294-300 (2021).

−80−

2020-81（国際）Advanced iodine – mediated stereoselective flow electrochemistryThomas Wirth

Cardiff University

Objectives: We want to explore the electrochemical generation of iodine(III) reagents in flow.
The key requirement for a successful reaction generating and using hypervalent iodine
compounds in only catalytic amounts is the ability of electrochemical process to make selectively
the hypervalent iodine compound in the presence of the substrate. We propose to use a biphasic
reaction system which should be able to provide an elegant solution since the iodine(III) reagent
can be formed in one phase while the oxidation of the substrate occurs in the other. For thisapproach we will develop iodine reagents with dual function as they will serve as the precursor
for iodine(III) but also as electrolyte.
Results and discussion: Due to the COVID-19 pandemic, Cardiff University was completely
closed for 4 months and then gradually re-opened. For the last 6 months (August 2020 – January2021) our lab could only be occupied with 40%. Therefore, research is very slow, and we were
not in a position to tackle the challenging objectives set out in the proposal. We did somepreliminary work on fluorination reactions outside this proposal as shown in Scheme 1. This
work is still under investigation and not yet published.
substrate(0.1 M)
CH2Cl2Tol-I (0.1 M)+
7HF•amine:CH2Cl2(1:1 v/v)

aq. NaOH

Tol-IF2

product
O

F

F

F F
Ph

Ph

F3C

O

F

N

O O
F

Scheme 1. Electrochemical fluorinations of different substrates in a flow electro-microreactor.

We hope that our laboratory work can fully resume in summer 2021.

−81−

OMe

2020-82（国際）Cation-Sinteraction in enolate chemistry
Jonathan Clayden University of Bristol
Objectives: Our group and Kawabata’s Scheme 1a)groups have developed unique methods for
OK
Me
CO2Et
EtO
K(NSiMe3)2
asymmetric synthesis of unnatural amino
CH2OMeNN
CO2t-BuMe
Boc
MOM
acids with tetrasubsituted carbon based on
1A
enolate chemistry.1,2) The strategy developed
t1/2 (racemization) = 1.1 h (–78 °C)
100 times racemization resistantby Kawabata is characteristic in the enolateb)intermediate with dynamic sp2 chirality
OK
M
CO2Bn
K(NSiMe3)2
PhCH2O(Scheme 1). Recent interesting finding is thatN CH2OMe
N
CO2t-Bu
Boc
Me
MOM
enolate B derived from benzyl ester 2 has a2
B~110 times longer half-life of racemaization
t1/2 (racemization) = 121 h (–78 °C)
compared with A derived from thecorresponding ethyl ester 1. The origin ofelongation of the racemization half-life of the t-BuO O K
MeOchiral enolate intermediate B was assumed to beNO
resulting from the enolate structure, in whichOaxial chirality along the chiral C-N axis isMecation-S interactionnstabilized by cation-S interaction (Figure 1).
Our Purpose of this joint research is to clarify
the origin of resistance of enolate B toward racemization.
1) Clayden, et. al., Nature, 2018, 562, 105. (2) Kawabata, et al., JACS, 2013, 136, 13294.
Results and discussions: Density functional theory (DFT) calculations were performed for the
racemization processes of enolates A and B. The activation energy for the C–N bond (shown in
red in Figure 2) rotation of the dimer of enolate A was estimated to be 14.9 kcal/mol at 78 °C,
whereas that of the dimer of enolate B was calculated to be 17.3 kcal/mol (Figure 2). The
racemization barriers were well compatible with the experimentally determined racemization
barriers at 78 °C (14.9 and 16.7 kcal/mol for enolate A and enolate B, respectively). The distance
between the potassium cation of the enolate moiety and the benzene ring of the benzyl ester moiety
was shown to be 3.31 Å (shorter than the sum of their Van der Waals radii:3.45 Å) in the groundstate of the dimer of enolate B, while that in the transition state of the C-N bond rotation(racemization process of axially chiral enolate B) was indicated to be 3.82 Å. These results suggestthat the stabilization by the cation-S interaction is more significant in the TS, indicating that theorigin of resistance of enolate B toward racemization is expected to be ground-state stabilizationby the cation-S interaction between the potassium cation and the phenyl ring.

−82−

2020-83（国際）Interdisciplinary approach to nanostructured materials for applications
Jean-Pierre Bucher Université de Strasbourg.
As the research activities were strictly limited in 2020, here we only include an ongoingcollaboration with the team of Prof. Jun Onoe (Nagoya University) which constitutes a firststep in the interdisciplinary project. For this project, Prof. T. Teranishi is our ICR contact.
The objective is to improve the energy conversion efficiency of organic solar cells bystudying the correlation between the photo-current elementary processes and thenano-structural properties. The Onoe team macroscopically examines the external quantum
efficiency of organic solar cells made of a hetero-junction of donor (phthalocyanine or
porphyrin) and acceptor (C60) films, using in situ electrical field modulated spectroscopy. The
Strasbourg team on the other hand is using bottom-up fabrication capabilities of model donor(D)/acceptor (A) interfaces and ultrahigh vacuum STM spectroscopy at cryogenic temperatures
to detect the spatial modification of electronic properties such as frontier-orbitals, ionizationenergy and electron affinity in relation to the nano-structural properties such as crystallinity,
molecular orientation and environment.
Experimental results show that the local HOMO and LUMO features as detected atinterfaces by STM spectroscopy are very different from the ensemble averaging frontier
orbitals obtained by optical absorption spectroscopy. In particular, the proximity of an interface
or electrode has dramatic effects on the very first interface monolayers. Experiments(Strasbourg) and DFT calculations (Nagoya) show strong hybridization of C60 with ZnPc in thebuffer layer upon adsorption on Ag(111) thus highlighting the importance of boundary layers
where the A-D character is strongly perturbed. The anomalous behavior at the interface isaccompanied by a significant charge transfer from the Ag to the molecular complex. Two
papers have been published and one submitted prior to the iJURC project. Due to the epidemic
situation, no workshops or meetings could be organized.

−83−

2020-84（国際）Relationship between chain orientation, amount of defect, and toughness ofglassy polystyrene materials
Quan Chen Changchun Institute of Applied Chemistry
Objectives: Polystyrene (PS) is a widely used thermoplastic polymer. Since its glass transition
temperature is much higher than the room temperature, it is usually used in the glassy state in ourdaily life. Nevertheless, its brittleness has limited the potential applications on more occasions.
How to improve the toughness of brittle glassy materials is one of the most challenging subjects
in polymer science. In this study, we prepare the telechelic PS samples, and examine whether the“anchoring effect” of the end groups would increase the chain orientation during flow, so as toenhance the ductility of the samples thatare quenched directly after the flow.
Experimental methods:
The telechelic PS vitrimer samples
were obtained from reaction of two
precursors, Precursor T and Precursor
C, in THF, where Precursor T was
prepared via the two-step RAFT
polymerization, and Precursor C was
prepared via the click reaction, as
shown in Scheme 1.
Scheme 1. The synthesis route of telechelic PS vitrimer samples

Experimental results and Discussion:
Figure 1 shows the (pseudo-) master curves of storage and loss moduli, G' and G", plottedagainst frequency, ZaT, for the PS-T-9.1-C-x system, where T-9.1 means that Precursor T contains
9.1 functional end groups per chain on average, and x means a molar ratio between Precursor C
and Precursor T. The precursor chain (x = 0) shows atypical Rouse behavior characterized by a Rouse powerlaw region followed by the terminal relaxation,
indicating that this sample is unentangled. Increasing x
leads to the sol-to-gel transition, PS-T-9.1-C-x (x = 0.3,
0.4, 0.9, 2, 3, 4) show clear plateau, where the amplitudeof the plateau increases with increasing x for x 4,
meaning that they are above the gel point and the
network is densifies with increasing the Precursor
C/Precursor T ratio. The plateau modulus decreases withincreasing x from 4 to 6, indicating a reverse gel-to-sol
transition when the Precursor C is in great excess.
In the future, nonlinear elongational rheologicaland mechanical measurements will be coducted in Figure 1: Comparison of the linear viscoelasticof the PS-T-9.1-C-x samples, where panel
collaboration with Prof. Yumi Matsumiya in ICR, Kyoto behavior(a) and (b) shows the storage and loss moduli, G'
and G", respectively for x ൑ 6 reduced at 180ºC.
University.

−84−

2020-85（国際）Search for four-wave-mixing in the vacuum– Unveiling dark components in the Universe –Kensuke Homma

Hiroshima University

Purpose and Method
The purpose of this study is to search for Four-Wave-Mixing (FWM) phenomena in the vacuum inorder to understand dark components in the Universe. So far, we have constructed and improved anultra-high vacuum chamber in ICR toward the search. In this vacuum chamber, two-color laser pulses
are collinearly combined and focused into the vacuum along the same optical axis. If photon-photon
interactions occur in the vacuum environment, generation of intrinsic FMW photons via thestimulated interaction
laser pulse and u

+

(2-u)

+u

is enhanced, whereis the energy of the creationis the energy of the inducing laser pulse with 0<u<1. The signal photon energy

in this scattering process corresponds to (2-u).

Progress and Achievements
We have extended the search by increasing laser intensity by one order of magnitude. Accordingly,
quantification of background signal photon yields from the known atomic processes has beenfurther required, because we must subtract them from the signal yield in order to discuss the dark
components in the vacuum. We then have established a way to quantify background yields fromthe surface origin in addition to the residual gas origin.
As the present status, we have succeeded to publish a paper on one of the search results to ajournal and we are now preparing for the next submission on the rest of the results. In addition, we
have developed an idea to extend the same method to the GHz-band and invented a concept ofstimulated radar collider. On this concept we have called a press conference in Hiroshima
University and the article has been published in Chugoku Shinbun. We summarize publishedpapers, a relevant invited talk and the press release during FY2020 as follows.
Published papers:[1] Extended search for sub-eV axion-like resonances via four-wave mixing with a quasi-parallel laser collider in a high-quality vacuum system,
Akihide Nobuhiro, Yusuke Hirahara , Kensuke Homma*, Yuri Kirita, Takaya Ozaki, Yoshihide Nakamiya, Masaki Hashida, Shunsuke Inoue, Shuji
Sakabe, Prog. Thoer. Exp. Phys. 20120(2020) 7, 073C01.
[2] Stimulated radar collider for probing gravitationally weak coupling pseudo Nambu-Goldstone bosons,Kensuke Homma* and Yuri Kirita, Journal of High Energy Physics volume 2020, Article number: 95 (2020).

Invited talk:
[1]

の
,

ELPH

(2021.2.25)

Press release:[1] https://www.hiroshima-u.ac.jp/research/news/60232−85−

2020-86
Fine synthesis of polymer brash on ferromagnetic nano-platelet formagnetophotonic LC
Yoshiaki Uchida

Osaka University

In response to the rapid spread of automated systems everywhere like factories and vehicles, short-range
communication systems using visible light with optical fibers made of inexpensive polymers have recently
attracted attention. However, as the communication speed and the number of nodes incorporated in the systems
increase, problems arise with the interference between cables, complicated wiring, and the limit of flexibility
for bending. To solve these problems, fiber-free short-distance optical transmission systems are promising.
We have focused on the photonic structures of liquid crystalline (LC) phases: cholesteric LC (CLC)
materials with flexible one-dimensional periodic structures, nematic LC (NLC) materials showing strong lightscattering as random laser resonators, and whispering gallery mode (WGM) in an LC microsphere, where lightis trapped inside the sphere by repeated total reflection on the sphere surface. We expect that opticaltransmission devices using these materials allow the remote control of light using magnetic fields. We havealready fabricated CLC capsules that work as three-dimensional laser resonators with three modes: WGM,
distributed feedback (DFB) mode and distributed Bragg reflection (DBR) mode [1]. Besides, we havesucceeded in switching the random laser action in NLC materials doped with ferromagnetic nanoplates byusing a weak magnetic field [2]. To synthesize such nanoplates, we have developed a synthesis method of
nanoplate dispersions using the LC phases as templates [3].
We focus on the stable dispersion of the ferromagnetic nanoplates in CLC phases to obtain ferromagnetic
CLC materials and the magnetic switching of optical elements that emit lights or receive lights. We have been
investigating the dispersion of solid magnet particles with polymer brushes into various liquid crystals. In theprevious year, we succeeded in dispersing the nanoplates in NLC materials, and we have been optimizing thecondition of the polymer brushes to disperse the nanoplates in CLC materials. Meanwhile, we investigated the
NLC droplets in aqueous surfactant solutions as laser resonators that could exhibit laser action at two different
wavelengths derived from their random mode and WGM. The two modes have been found to switch dependingon the excitation light irradiation position; it is the first example of the coexistence and tunability of the twomodes. The origin of the controllability is likely to be attributed to the correlation between the droplet diameterand the lasing threshold.

References
1. Y. Uchida, Y. Takanishi, J. Yamamoto, Adv. Mater., 25, 3234-3237 (2013).
2. T. Naruta, T. Akita, Y. Uchida, D. Lisjak, A. Mertelj, N. Nishiyama, Opt. Express, 27, 24426-24433 (2019).
3. Y. Uchida, T. Nishizawa, T. Omiya, Y. Hirota, N. Nishiyama, J. Am. Chem. Soc., 138, 1103–1105 (2016).

−86−2020-87
型の化とその機能
三

大

大学

・目的
イ ンは、
バイ

度、長

など有機

にはない

ン ーなどに応用されている。 々のグルー では

リ ミン部 からなる
クル状の合

ニ ン応 をををによる化学的・
ミ

ル

ン

ー開

が

中で シ

性

EuL.

中における

を分

認識

として活用し、的環境の化を視化する機能をを目指すため、まは状

での(EuL, Fig.1) の・ 性を らかにする。今 、Eu
化と 外分 法によるをもつ Eu性のポできることを見出した 1)。

による出力として

本研究課題では、

有する

を有し、

や

性のコ ステリル基とに開 し、特に、 視成する性特性を すことから、

Fig.1

評価を行った。

実験方法
L および

EuL について、Langmuir-Blodgett（LB）法により

した LB

および

) 法を用いた分を Si 基 に外分手法であり、
基 に平行/
中の分について MAIRS (した。L、EuL の

、

多 入 分

教

な方向に する IR ス クトルを分 し同 にすることが 能で、が開した分で定 的に評価することができる。

層 の 外 MAIRS ス クトルを す。Fig.2 (a) より、L は 1651 cm-1 に ミが 内方向に強く出ており、1547 cm-1 に ミド の NH

ド の C=Oの定を行った。MAIRS 法は共同研究者の長向を 能基

Fig.2 に L、EuL

上 分

向性があり C=O

強く出ていることが分かる。これより、 内に分が 外 (OP) 方向に
合は基 に して平行に動していると えられる。一(a) L方、EuL (Fig.2b) は 1627 cm-1、1574
される

ミド基

強度に がなく、分来の向性はAbsorbance

cm-1 に

L 3ML op
L 3ML ip見られなかった。このように、
型

およびその

内でどのようにC=O(b) EuLが向しているか

4000

3600

3200

2800

2400

2000

1600

1200

800

-1
Wavenumber s (cm)

Fig. 2Si 基

上 LBの IR-MAIRS ス

を めて らかにした。
文N-H

EuL 3 ML op
EuL 3 ML ip

1) T. Sagami et al., Chem. Commun., 2017, 53, 3967.

−87−

クトル (a) L, (b) EuL, OP

, IP

----

2020-88
Study on the regulatory network of plant epidermal cell differentiation
Rumi Tominaga

Hiroshima University

Introduction:
Plant epidermal cell development including root hair and trichome cells represent well-studied model systems
for cell-fate specification in Arabidopsis thaliana. Some regulatory factors have been shown to contribute tothis regulatory network. The CLAVATA3/ESR (CLE) plant polypeptides act as peptide hormones in various
physiological and developmental aspects in a diverse array of land plants. One of the CLE family of genes,
CLE14, is reported to induce root hair formation in Arabidopsis roots. Previously, we demonstrated that theapplication of CLE14 polypeptide induced excess root hairs, and reduced the expression level of the non-haircell fate determinant gene, GLABRA2 (GL2) in Arabidopsis roots. In this study, we investigated the functionof CLE14 polypeptide in rice (Oryza sativa) and tomato (Solanum lycopersicum) roots.

Methods:
Root phenotypes of CLE14-treated 10-day-old rice and tomato seedlings were observed.
Real-time PCR was performed to analyze the expression levels of the OsGL2 and SlGL2 genes, i.e., homologsof the Arabidopsis GL2 gene, in rice and tomato seedlings, respectively.

Results and Discussion:
CLE14 polypeptide treatment clearly induced excess root hair formation in rice roots. Unlike the result seen
in rice, the CLE14 treatment did not have a substantial effect on tomato root hair induction. Consistent withthe findings of Arabidopsis, we detected a significantly lower accumulation of OsGL2 transcripts in the riceroots treated with the CLE14 compared with those of the control plants. These results suggested that CLE14
is functional in rice roots as well as in Arabidopsis roots, where it inhibits the expression of the GL2 homolog
gene OsGL2 and promotes root hair formation. Unlike the results seen in Arabidopsis and rice, CLE14 did not
induce root hair formation in tomato seedlings. However, consistent with the results from Arabidopsis and rice,a significantly lower accumulation level of the GL2 homolog gene (SlGL2) transcripts was detected in the
CLE14 treated tomato roots compared with those of the control plants. These results suggested that regardlessof the root hair phenotype, CLE14 polypeptide can suppress the GL2 homolog gene expression in rice, tomato,and Arabidopsis seedlings. Although further investigations of the effects of CLE14 polypeptide on crop plants
are required, the present study offers new insights into the molecular basis of CLE peptide signaling in riceand tomato root epidermal cell differentiation.

N. Hayashi, et al., Plant Biotech., 36, 205-208 (2019)−88−

2020-89
活化するナ

合
大

ワク

ンは感染症を

めた

化ワク

果的なワク

するための

ン（

ワク

ンとして

ルスであるため取り出した

ジュバントと
や

中

型

ルスに

入である。

と
化ワク

ンが開

の
ンは

され、ワク

ンは

ルシ

学的

方の

ンなどが

応を

との

き

の手

を

するため、

だが、 きたウイのとなる部分を的に広く用いられている。し

、 分な

用が

こす

続的に

するために

ンの主力として性を有しておら
活性化を

果的な感染症題がある。この課題を

ばれる

応して

が

用する。

活性化ワク

れた

ン）は、

において

かし、 活性化ワク

もす

応要。これまでにを導するためにはム（

ルミニウム

験的に利用されているが、 実上この二つだけである。新

果的なワク

ンを

大学

備するためには、 ジュバントの）ウイートリーを増やすことである。
これまでの上

コリ

グルー

イドと

イルス

より、

が

５

合性と

な
のジ

に

ミンによって活性化能にポストコロナのに、その都度ワク
ジュバントが開
る。

展

れた

ー部

の化合
代でも、新たな新

ンが開

合した

とコリ

な

化化合

シコール

つことが分かった。リン験したところ、グルーををされれば、新にイドの上国を含めたグローバル

会に

かつ
すると期

−89−

というウ

イドの様々な

を化学

イドは

えた化合

ウイルスが次々と出

ウイルスに

見し、

は

見した。

を

され、 ジュバントが組

合

を

（

シコー

である。さらなる有機合成展開に

に き

２がコリ

ジュバント材イドのジュバントを見つけ出した。コリの活性化を評価したところ、
の活性を

ン

）。コリ

に認識される。本共同研究では、上

）２分

合性ワク

けた（

合成し、より強力かつルとの共同研究によって、

を指

にして

１がコリ

イド

き えた化合の活性をするだろう。今状を合成して同様っていた。
のコロナ禍のようまれる。本研究成果が先導して、様々な価なジュバントを選択できるようになできる。

2020-90
Functional analysis of non-canonical strigolactones as plant
hormones and root-derived signals−90−

2020-91
Analysis of phase equilibrium and molecular dynamics
in mixture of nematic liquid crystal and solvent
Ryoko ShimadaJapan Women's University

Liquid crystalline (LC) molecules exhibit rich behavior when mixed with non-LC molecules, because thefree energy of the mixture is contributed not only from the LC free energy determined by the order parameterQ but also from the mixing free energy not directly related to Q.1,2) This free energy has been utilized to
discuss complicated phase evolution in LC/solvent mixtures.1,2) A characteristic feature of these mixtures isthe coupling between the LC free energy and the mixing free energy that allows the LC transition to trigger
the phase separation. This coupling is expected to affect properties of the mixtures even in the isotropic onephase state, but details of this effect have not been well elucidated. This study attempts to resolve the effect on
the static and kinetic properties in the isotropic one-phase state for a mixture of 4-cyano-4'-pentylbiphenyl(5CB) with dimethyl phthalate (DMP; wDMP = 3.1 wt%). Pure 5CB forms nematic LC at TIN = 35 C.
The DMP/5CB mixture separated into LC and isotropic phases at a transition temperature TIN* = 27 C.
This TIN* is lower than TIN of pure 5CB because of the mixing free energy contribution explained above. The
mixture and pure 5CB commonly exhibited simple thermal expansion and the Andrade-type behavior of theirmass density Uand kinematic viscosity Q at temperatures T well above TIN* and/or TIN. However, at T justmoderately above TIN* and/or TIN (still in the isotropic one phase regime), non-trivial deviations from thishigh-T asymptote were observed.
This observation is demonstrated in Figures 1 and 2 where the deviations 'U and 'Q are normalized by thehigh-T asymptotes Uiso-high T and Qiso-high T and plotted against T. Filled and unfilled symbols show that thematerials were in the LC and isotropic one-phase state, respectively, and the circles with inner dot indicate thatthe DMP/5CB mixture was phase separated into LC and isotropic phases. For pure 5CB, the positive
deviations 'U/Uiso-high T and 'Q/Qiso-high T in the isotropic state emerge only at T in a close vicinity of TIN becauseof the first-order nature of its isotropic-nematic transition. In contrast, for the 5CB/DMP mixture, the deviation
emerges in a considerably wide range of T spanning almost 10K. This remarkable deviation is attributable tothe concentration fluctuation not existing in pure 5CB. Namely, the fluctuation of the 5CB concentration due
to a small amount of DMP (3.1 wt%) induces correlation between 5CB molecules locates at distant points inthe mixture thereby enhancing the density and viscosity, as deduced from the statistical theory of Helfand.3)
0.4

0.006

(a) 5CB

0.005

0.003

(a) 5CB

TIN

0.2

0.004

0

0.002

-0.2

0.001
0

TIN

-0.0010.005 15

20

25

30

35

-0.4
0.4 10404550(b) DMP/5CB

0.004

20

55

30

40

0.2

50

60

(b) DMP/5CB

TIN*

0.003

0

0.002
0.001

-0.2

0
-0.001

TIN*
15

20

25

-0.4
30

35

40

45

50

55

T/ C

20

30

40

50

60

T/ C

Fig. 1. Density change of 5CB and DMP/5CB mixture with T.

Acknowledgement:

10

Fig. 2. Viscosity change of 5CB and DMP/5CB
mixture with T.

This work has been published in J. Soc. Rheol. Japan, 48, 199 (2020).

References: 1) Araki and Tanaka, Phys. Rev. Lett., 93, 015702 (2004). 2) Reyes et al, Soft Matter, 15, 6044
(2019). 3) Helfand, Phys. Rev., 119, 1 (1960).

−91−2020-92
イネのストリクトン

合成におけるミリーの機能井ストリ

クトン（SL）はロ

ミの分かれなどをルとしても機能しており、 ーバスなどで甚大なをもたらす成に関する研究は的に進展し、その

用を

も

する上で、

の

学的および

を

要な「

ルモンである。また、SL は

ー

の

ュ

導

合成に

化学的な機能

分

導

用や、

リ

用を有している。

年、SL合

らかになりつつある。しかし、SL のルモンとしての活性本として、活性型 SL の

イネを材

する

の種
が

京大学

要な

」は未

を果たすと

ルモン

である。本研究では、えられる CYP711A

ミリー

ルモンとしての活性型 SL 分の共同研究を行い、種らかにすることを目的とする。
本年度、井

イネの施

グルー

に応

では、

する

として同定した CYP711A
ミリーに

する

につい

て、CRISPR-Cas9 システムを用
いて、

や二

を

型

出した。

果、二

の
分かれ）が増加したことから、これらの CYP711A

において分げつ（型 SL 分種の合成に

CYP711A
あるー

要な機能を有することがミリーは、リコン

クトン（CL）から

ー

ナント

ン

環性 SL である 4-

はなく
も関

次

シ

の

を、

が

が主要な

合成中

機能であるとクロ

分

し、CL がえられロバンコール（ORO）の合成に点が多い（図 1）。そこで、化学研究所

機能には

トグ

で

が 5 つ存 し、CLA だけでする（共同研究者）との共同研究により、二上部において CLA がことから、これらの CYP711Aを用いた実験などから、SL

ロバンコール（4DO）や（共同研究者）、増

ける CL や CLA の内

ク

ミリーに

することが報告されており、それら

の

された。

クトン （CLA） のている（図 1）。しかし、イネには CYP711A

が活性

に

を用いて定

していることが

した。その

にお
果、二

らかとなった。このは、イネ

内でも CL から CLA

分かれ用を有する活性型 SL は CLAのを担っていることされた。
上のことから、イネにおいてとがされた。今後、CYP711A の二性 SL の
なる

ー

見を

クトン
たいと

における、

ル（MeCLA）の内を定環性 SL である 4DO や ORO、
し、SL の「活性本えている。なお、今年度は本研究課題に関する行っていない。

−92−

に存

文

するこ
環

」についてのさらおよび学会は

2020-93
Analysis of the physiological functions of extracellular vesicles produced byintestinal bacteria and fermented food-derived bacteria and theirapplication
Atsushi Kurata

Kindai University

Introduction:
The gastrointestinal tract is inhabited by a complex community of bacteria, the gut microbiota. The gut
microbiota and its host are exchanging various molecules, resulting in a complex interrelationship. The gut bacteriaproduced modulator toward host cells are not fully understood. Most bacteria release extracellular vesicles (EVs)with the size ranging from 50 to 400 nm. The EVs released by intestinal bacteria may play critical roles in the hostbacteria interactions. Against this background, the first objective of this study is to analyze functional characteristics
of EVs from intestinal bacteria and fermented food-derived bacteria. The second objective is to develop novel
expression systems for heterologous proteins using EVs-producing bacteria.

Results:
1. Functional characterization of EVs produced by intestinal bacteria
Lactobacillus plantarum isolated from human intestines produces EVs with the size of 50-100 nm. Proteinsof EVs were analyzed by LC-MS/MS. As the results, five kinds of lipoproteins were detected in the EVs. EVsfrom L. plantarum stimulated toward Raw264 cells to produce IL-1, IL-6, and IL-10, and toward Peyer's patch
cells to produce IgA. The EVs and one of the purified lipoproteins from L. plantarum were recognized by human
Toll-like receptor 2 of HEK293 cells. These findings elucidated the relationship of Toll-like receptor 2 and thelipoprotein of EVs as a novel modulator in the gut immune responses toward L. plantarum.

2. Analysis of regulatory mechanism for production of EVs
Shewanella vesiculosa HM13 isolated from intestinal contents of horse mackerel (Trachurus japonicus)
abundantly produces EVs and is considered useful as a host for production of heterologous proteins as cargoesof EVs. It was revealed that production of EVs by this bacterium is enhanced by increasing the concentration oflysine in the culture medium. A putative sensor protein with typical sensing and signaling domains was found toplay a major role in lysine-inducible EV production. This protein was also shown to be involved in lysineresponsive suppression of biofilm formation. These results suggest that regulations of EV production and biofilm
formation of this bacterium share a common mechanism to sense nutrients in the environment.

−93−

2020-94
合性分

による心

の

化
大学

日本における心
ることが
に有

者

実である。

であるが、

に

する

から心

者

の内科的、外科的

ク

によって

一

本的な

は心

を

する

ニ

れた心

ニ

報告され、

した。本化合しないことに
は深
的

の進行

成する心

が分 ・増
している。 症心である。 年、多能性に大は上分化能力をもつ。

と共に、心

グルー

、心

の心

を

用を

イミングで KY02111 を

加し、その

を

に入れ続けると、心一方、新学術する「先端モ

ウンでも、Z

合して Y との相互

見された化

分化から

した。

用を

と

することが
に

してい

々のグルー

は、心

分化の

した。KY02111 を心
分化

的 ン

用の心

分化

行した。このル動

支援ット

による A のによる A のをがーム」で KY02111 のロトコール

果は Y のされた。これにし、心せ果より、KY02111 は X と Y の合をすることで、Z シグナルを、Z シグナルにも

された。
グルー

と

文にまとめ、−94−

活性を評価してすることが見出された。また、X や Y の合を上の成果は上によって整に利用されている。しかし、は、X と Y の

することが

導する化合

する。

頂いたところ、KY02111 が Z

い KY02111 のと中辻グルーに見られるため、X と Y の相互は主に心は X との相互

と一

分化を

分化の大

い。実際、Y の

による

の

グルー

X を同定した。さらに KY02111 が X に

期から

ック

を

和と、

されていなかった。これまでの共同研究研究により、KY02111 の

ムは

として

能性が

の

が

であるが、ドナー

ロトコールがムをであり、強力な心

様々な

者の症状の

、

た

認された。Y のる法は心能となってきている。

KY02111 のその人と推定され、今後もさらに増加すさせることは出来ない。これは、心本研究では、京都大学化学研究所の上合120よりも多く、を能をほとんど

ことが

は

中である。

を

分化促進活性を有さなさなかった。
し、心

上

分化を促進

2020-95
Observation of spin wave propagation in polycrystalline
YIG thin films prepared by co-precipitation method
Keisuke Yamada

Gifu University

Introduction Recently, Y3Fe5O12 (YIG) is one of the most prominent materials for spintronic device applications
that utilize the spin pumping and spin Seebeck effects with its low Gilbert damping constant DThis paper reports
our latest experimental findings on the variation of longitudinal spin Seebeck (LSSE) voltage with microstructuralchange in YIG films chemically synthesized onto a Si substrate as a function of annealing temperature.
Experimental Method

YIG-film samples were synthesized by co-precipitation and spin-coated onto Si

substrates. The samples were subsequently annealed at temperatures ranging from 1073 K to 1273 K for 0.5 hourin an ambient atmosphere. Their structure and magnetic properties were characterized by X-ray diffractometry(XRD), scanning electron microscopy (SEM), ferromagnetic resonance (FMR) measurements and LSSE
measurements. FMR measurements were performed at ICR of Kyoto Univ.
Results and Discussion

The diffraction peaks associated with the garnet phase are observed in all the YIG

samples measured by XRD. When the annealing temperature Ta increases from 1073 K to 1273 K, the average
particle size <D> of the YIG crystals estimated by SEM increases from 50 nm to 68 nm which increases by 36%,
as shown in the left axis of Fig. 1. The areal fraction of voids v obtained from the SEM surface images is represented
in the right axis of Fig. 1. The values of v are in the range of 36v

42%, it indicates that the v is slightly

dependence on the annealing temperature. The value of thermoelectric performance (TP) estimated by LSSE
measurements decreases monotonically with increasing Ta from 1073 K to 1273 K, and it decreases by up to 24%(64%) in the YIG films with Pt = 5 nm (10 nm) (see Fig. 2). These results indicate the microstructural changes in
the YIG films by annealing temperature cause the decreased TP, which are corresponded with a reduced coherenceof the magnons in the YIG films. This result indicates that the coherence of the spin waves propagated in the YIG
films confirmed nanocrystal is affected on the magnitude of TP.

Fig. 1 <D> and v of the samples plotted asa function of Ta.
Achievement report

Fig. 2 Variation of TP with Ta
for each Pt thickness.

This research has been submitted to a journal as a manuscript which title isChange oflongitudinal spin Seebeck voltage with annealing in Y3Fe5O12 films formed by densely packed nanocrystals−95−.

2020-96
性

ドによるがん進展
大

目的

組

は

を

組

する能力や様々な種をんに見られるような組

しがんの

や

のがん

の存

であることからこれらの題である. がん

の

成の

の

存

の

組

の

な

が
法

を

が

能となれば, 深部がん

し, この

存

の

はがんの

するだけで
をが
は

後を

に向けての

は

期の

がん

期にあることや,

要な課

に
組

する

深部は

しない, 等があげられている.

として三次元

ドに

にも存

成と

ががん

ロー

大学

えられている. このようなしさの一つとしてがん分に化学本課題では, がんなの組出す能力を有し,のとしてはがん

しさなどからをとこれによる化させる要性がある. この要がの進行につながると

. がん

と

様の

若

（ス

し深部がん

ィ

）に

導に向けてのの的法の開果的な導入が能を行った. 深部がんとつながることが期

される.
実験方法 スロイド

種し三次元（CPP）をス
教

成

（ス
ィ

に

ート(EZSPHERE, IWAKI)に

ト大

）を

を

ィ

し,

た.

導

導

の評価を行なった.

がん

HT29

来

を

加した種々のドての CPP は共同研究者の二（京都大学化学研究所）より提供を頂いた.
実験
ィ

果と
に

シリン-

後,

ル

ジン染

は

なく

が分かる.
は内部に

ト

の存

存

を有意に

を連

定ス

ィ

リン

す（図）. ス

を

に

同

導

連

シリン強

ス様

導

が

CPP を

下させ, またス

ィ

法は
が期
組

の

化

び

される. ス

ィ

内部

能とする

内部においても

行型
法の

び内

点を有する

ィ

ィ

はス

ィ

に

導 CPP に

HT29

3
HE

CPP

(

)

,

ィ

の

された.
選択性を

を

導し,この

深部組
める

能な
入により有

した内部環境を有するとされ, 本的化を行うことにより, 組とつながることが期

−96−

.

.

導 CPP はスと.

な要で有り, ここに
組

で

ポトーシ

こっていることが
に

は

層

したス

ブリスが増加した. これらのことから,
導はスト成されているの

導 CPP

を認めた.

の
ィ

して

性の

した CPP をス

される.

内部の

の

にて
成

した
を

2020-97
Giant exchange reaction from H to D terminating on
nanocrystalline silicon surface and their use
Takahiro Matsumoto

Nagoya City University

The deuterium is attracting special interest for the manufacturing of silicon (Si) semiconductors, Simicrochips and optical fibers as well as the synthesis of isotopically-labeled compounds. However, the facile
production of deuterium in a controlled manner is a challenging task.
In this collaborative research program (grant # 2020-97), we determined the surface-localized vibrationalmodes for hydrogen- and deuterium-terminated n-Si using inelastic neutron scattering (INS) spectroscopy.
Because the determination of surface vibrational energies in the lower wavenumber region below 600 cm-1 isdifficult using FTIR spectroscopy as the localized modes completely overlap the bulk Si phonon bands.
Figure 1 shows the contour plot for n-Si:H0.15D0.85. In addition to the spectrum originating from the H
vibration (H2B), spectra are clearly observed at energy levels of ¾Z 67 meV (D2B), 60 meV (D1S), and 51
meV (D1B). These spectra and the energies are well described byharmonic oscillators with the same force constant as H. Thus, theሺ஽ሻenergy levels of Si-D vibrations can be expressed as ‫ܧ‬௜
ሺ஽ሻ

ሺ݊௜

ሺ஽ሻ

൅ 1Τ2ሻ԰߱௜

ൌ. Here, we note that the scattering crosssection of the H atoms in the INS measurements is more than 10times larger than that of the D atoms Vscatt(D)/Vscatt(H)7.64/82.03); therefore, despite the lower concentration of H
atoms (<10%), the Si-H mode results in an intense S(Q,¾Z)
spectrum, as shown by the H2B mode.
By determining the energy of surface vibrational modes forboth Si-H and Si-D as shown in TABLE I, we found that thephysical mechanism responsible for this enrichment originates

Figure 1. Localized vibrational modes for n-Si:D

from the quantum resonance between the bending modes of Si-

obtained by INS spectroscopy. B and S denote

deuteride and n-Si phonons.

bending and stretching modes, respectively.

TABLE I. Surface vibrational energies for Si-D and SiH. The values are given in meV.

Bend1

Bend2

Stretch1

Stretch2

SiD

51

67

60

190

SiH

59

79

61

261

−97−

2020-98
界

活性

を用いた

含

による

イ

ンの

大

大学

元 である Eu は
供 の

等

学

材 としてその 要の まる一方、主な 出国が 外であり、その

定さから、

である

からのリ イクルが注目されている。主要な

出法は、 価かつ境に有 な有機含なでル分 法の一つ的 い選択性が られる利点があるが、人 や環を大 に用いる 題がある。そこで、人 や環境に有 な有機ない分 法として、多 性のに 出 を含 させた

含

の

が

に 目した。先行研究では、を行う際に、 出 とともに界 活性 を含 させると、出 によるに含 させた の出 を向上させるだけではなく、 イ ン性界 活性 を含 させた 合は、の 出 を含 させなくてもは 価で多様な種 のな 出 の 用を
性

の

２

実験方法

が

元 を

相

出 能であることを見出した。界 活性されており、界 活性

でを 出できれば、 価

し、分 コストを大きく下げることができる。そこで本年度は、この界 活を用いた Eu の 出について、界 活性 の 性の含材とする多 性

として ル

を行った。

の Amberlite XAD-7HP を用いた。含 する界会

基が イ ン性である Sodium Dodecylsulfate (SDS)と Sodium Tetradecylsulfate (STS)を

活性 は
用した。

ールで

後、

1.0 g に して 0.01 M 界 活性 を含む

した

10 mL を加え、1 日含 させた。ロー リー バポ ー ーでさせ、目的の含た後、 相を分取し、pH を 定した。分取した 相は Ni を内(ICP-OES)を用いて Eu

分 分

ール

し、50 で 1 日をした。Eu を 0.2 mM 含むをで 意の pH に 整した。この 相に SIR を 0.1 g 加え、22.5 mL を HCl と NaOH

とうした。 とう後、 心分 しとして、 導 合度を 定した。

果と
基が共通で

ル

ル

長の

が

なる界

ある SDS および STS を含 させた果を図 1 に

す。多

性

に界

活性

による Eu
活性 のた 合、界 活性 の ル ル 長は Eu

を含 させ

出 にほとんどがに含ンである Na イ ン

された イ ン性界 活性 のと 相中の Eu イ ン 1

で出のを えないことが かった。これは、多 性

3

出

目的

１

３

相

されることで、Eu

出

図 1

ル

ル

させた

含

が こるためと えられる。
成果報告
1)

ら 第 80

分 化学

2)

ら 第 23

化学 学会学

会

教育大学
会
−98−

2020.5.

ン イン開催 2021.3.

の

なる界

活性

による Euを含出2020-99
Anomalous Hall effect of ultrathin Pt films grown on magnetic oxide
Taro Nagahama

Hokkaido University

Introduction: Recently, Spin Hall effect has been utilized to generate pure spin current, in particular, Pt is themost important element due to large spin-orbit interaction which is the source of the spin Hall effect.
Additionally, Pt is well known as the material which exhibits a large magnetic proximity effect. It is purely aninterface effect based on exchange interaction between magnetic and non-magnetic material, which could
cause novel spintronic phenomena at the interface.
In this study, we investigated the magnetic proximity effect and anomalous Hall effect in Pt/CoFe2O4. As aresult, the anomalous Hall effect was observed, which was sensitive to the interface states significantly.
Experiment: The films were grown on MgO(001) substrates by the molecular beam epitaxy (MBE) methodwith the base pressure of 8 10-8 Pa. The film structures were Al2O3(0001)/Pt(111)/ CoFe2O4 (111). The
epitaxial growth and the surface morphology were confirmed by reflection high energy electron diffraction(RHEED) and the crystal structures were investigated by X-ray diffraction (XRD). The anomalous Hallmeasurements were carried out in the cryostat.
Results and discussions: Results and discussions: By the Hall measurement of Pt(2nm)/ CoFe2O4 (50nm),
anomalous Hall effect that followed the magnetic hysteresis of CoFe2O4 was observed. Since CoFe2O4 is an
insulator, the AHE is considered to be originated from the electric current in Pt layer in which small magnetic
moments were induced by the magnetic proximity effect. To see the interface importance, we prepared thesamples with and without CoFe of 0.5nm (1~2ML) and post oxidation. The AHE of the samples is shown in
Fig.1. For the sample with CoFe and post oxidation, clear AHE was observed, on the contrary, no AHE wasobserved for the sample without interface treatment. In
the CoFe2O4 deposition process, the Co and Fe were
deposited in an oxygen radical atmosphere, therefore, theoxygen layer could exist at the interface between Pt and
CoFe2O4. The interface oxygen layer is considered to
disturb the proximity effect, meaning that the direct
exchange between Pt and the Fe and Co ions is important.
Publication and Conference: 1. S. Nodo et al., "Voltage
Control of Magnetic Proximity Effect and Anomalous
Hall Effect in CoFe2O4/Pt Bilayer by Ionic Liquid
Gating" APEX, 13, 063004 (2020). 2. S. Nodo et al.,Fig.1 Anomalous Hall effect measurement"Voltage Control of Magnetic Proximity Effect andof Pt(111)/ CoFe2O4 (111) films with orAnomalous Hall Effect in CoFe2O4/Pt Bilayer by Ionic

without CoFe deposition and post oxidation

Liquid Gating" 65 th MMM, online.

at the interface.

−99−

2020-100
価インを含む機能性

化

合成とその

性研究

ネル

状

や

は

化

は

状

が

状

を

型

LaCu3Cr4O12 が

イト

強

を

合成

おける

に

を

い

らかにすることが

報が

めることは

を

性

状

的

となる[1]。

すことを見出した。

した PbCu3Cr4O12 のの果の BVSられることから、これらは
を

状

を

行った。
研究

ンの価

を見

れ 3.2、2.3、3.4 であった。Cu、Cr の BVS

がそ

から

によって出

イ

えられる。また Pb の BVSしている

した。PbCu3Cr4O12 では

な

が出

や

を

について 300 K、100 K、50 K、4 K にでは見られない 001

にも新たな

の

中性

価 Cu3+/Cr4+を一部含むと

下において

状

SPICA を用い、化学研究所・

中性の BVS はそれ

深く、そのPb を含むため、

元しい。そこで PbCu3Cr4O12 の

いて d = 4.86と強される。PbCu3Cr4O12 の価要であるが、実験を行った。

また図 1 に す通り、100K

る。今後、

性的な

いということは、A’ イトにおいて Pb2+/Pb4 が

化の増加が

い

が強く 成した特要である。La3+Cu3Cr4O12 と同様、

状

れ 2、3 より大きいことから、
が 3 に

に

イト LaCu3Cr4O12

やもったところ、Pb、Cu、Crれロブス

した PbCu3Cr4O12 を合成し、これが A

で強価 Cu3+/Cr4+を含むと期
度の

型

ンの価

であることは

を利用して
中性

動

ち、また

J-PARC/MLF の BL09 に設 された
の

イト

イ

である一方で PbCu3Cr4O12 が強性

Pb2+Cu3Cr4O12 も

から

イト

器研究機

において

であり、Cu-3d、Cr-3d、O-2p

で Cu-Cr

する上でそのをXを果たしている。A

LaCu3Cr4O12 における La3+を Pb2+でロブスするためにはであるが、その機能

要な

つために

一方、申請者はイトにす

ン Cu3+/Cr4+を含む

価イ

な

広い機能を

ー加

が

能性を

している。

された

、 K にお150 K、20 K において強
した

であると

らかにする。

[1] T Saito, Y. Shimakawa, et al., Phys. Rev. B, 95, 041109 (2017).

図 1. 300 K、100 K、50 K、4 K における PbCu3Cr4O12 の

−100−

中性

ー

。

性的

えられ

2020-101
ウストポロジーを有する環状

ニ

ンの

性の
大 大学

シクロ

ニ

ン(CPP)は

れ れは、化学研究所のを 用することで、CPP

S

の

から

の

一

リ

ーである

に 来する

ンが環状に

合した分

深い 性により関心を めている。
に

分 分 等

状 および ジ ルイ ン状 などに関する新たな 見を報告し状

ニル基を導入することに成 している。本化合 は

において

性を

すが、

される。本研究ではス ン多 度の 化に うを目的とし、

ニ教らが合成した種々の CPP

教 ならびにグルー は CPP 内に

年、

すことが

ン環

と環状に整 した pであり、 いてきた。1)

ン

三

状

において

性を

性の 化を らかにすること定等を行うことで新たな 見を たので報告する。

本研究で用いた CPP

を Fig. 1 に す。これらの分 に し、の分

ルス ー ーをすることで 視外

ムト または コ定を行った。

ス クトルを として Fig. 2 に す。

本研究で 定した[6]CPP-DPA-1 の後において 600 および 1360 nm に 大を有するが じ、これらのに い新が 530 nm に 成することが

たな

認された。

化の

ns でありは 1.3と一 したことから、

定された
よる

定

化は

三

成

に

であることがされた。同様に の Fig. 1 の CPP

に

ついても

にともなう

化を

することに成 した。本 定

等より

に

う

Fig. 1. 本研究で用いた CPPの分

Fig. 2. 355 nm

ーのの 化を めたところ、トポロジーを有する CPP

ウス

は、同様のSを有する[6]-および[7]CPP よりも
三

における

が大きい

ことが された。本 果は、ス ン多
度の

化により

有する CPPがウストポロジーを性の化をす

ことを実 するものである。
文 : 1) Fujitsuka, M.; Cho, D. W.; Iwamoto,T.; Yamago, S.; Majima, T. Phys. Chem.
Chem. Phys. 2012, 14, 14585-14588.

[6]CPP-DPA-1 の

−101−

コ

ー

ス クトル

により

られた

2020-102
Study on electronic and magnetic behavior of perpendicularly magnetizedcobalt ferrite films
Masaaki Tanaka

Nagoya Institute of Technology

The spin-filtering effect where the spin current is generated using the electron tunneling through aferromagnetic insulator is one of the candidates for the spin injection method. It has been reported thatmagnetic insulator CoxFe3-xO4+ (CFO, 0<x<1) films grown epitaxially on MgO (001) substrates withnonmagnetic metal TiN buffer layers have large perpendicular magnetic anisotropy (PMA)[1], which meansthat they can be applied for PMA spintronics devices. In this study, the spin-filtering effect of CFO films with
PMA was investigated.
TiN (20 nm)/CFO (x=0.53, 3.5 nm)/MgO (1.0 nm)/CoFe (1.5 nm)/{Tb/Co}n (13 nm)/Pt (5 nm) films
were prepared on MgO (001) substrates using the pulsed laser deposition and electron beam deposition
technique. CFO films were grown at the substrate temperature of 300oC in background oxygen pressure of 6.0
Pa. The magnetic tunnel junctions (MTJs) with a junction diameter of 6

m were fabricated using

photolithography and dry etching by an ion-milling method. This microfabrication was carried out at ICR,
Kyoto University. The current-voltage and magnetoresistance measurements of the MTJs were performed
using a four-probe method at various temperatures.
The current-voltage measurements indicated that the CFO/MgO layer shows good tunnelingproperties. The resistance increased dramatically with decreasing temperature, which indicates that the
conductivity of the junction is governed by the tunneling current. Figure 1 shows the magnetoresistance of the
MTJs at 100 K at the bias voltage of 70 mV. The tunnel magnetoresistance (TMR) effect caused by themagnetization switching of CFO and CoFe layers was observed. The TMR ratio was about

10 %, and theratio of the spin-polarization caused by the spin-filtering effect of the CFO layers was about 18%.

Reference[1] K. Naruse, M. A. Tanaka, K.
Nomura, T. Taniguchi, S. Honda, T.
Ono, and K. Mibu, J. Magn. Magn.
Mater., 475, 721 (2019).

Fig. 1 Magnetoresistance of the MTJ at 100 K at the bias
voltage of 70 mV.

−102−

2020-103
ル

ス

ールシミュ

ーシ

ンによる
動度

型有機

導

材

の

二

大学

ーなどの有機

導

目的
有機

導

材

動度は、有機 EL や有機のバイスの性能を定する

Model (GDM) が一

的に

動特性と分

を

要な

の１つである。

れているが、このモ相関

題をする手法として、本手法では、有機

導

の化学

なく

終的な

動度を

を有する新規化を実ールにすることができる。

材

を開

の

上の

ル

実験方法・

材

ミ

応によって合成し、各種ス

ス

動度の大きな

クトル

び元

性を、UV-vis、PL ス

法 (PYS) により分

学特性を評価した。ついで、ンを用い、Time-of-Flight (TOF) 法で動度とシミュ

ーシ

ンの

果・

・今後の展

評価した

果、新たな材ーを用いること
ニル

活性化

ン

ン
の長

、外部

特性の向上のためには、

ールシミュ

ーシ

ンを行うことにいを分と関連づけてする。

ル、–2.4 eV の
めて

い

により同

ル

ス

られた

を行った。

T4DBFHPB は –5.7 eV のイ
和力、2.8 eV のス

TADF 型有機 EL で、

い三

ン化ポテ

ネル

ー、

点を有していた。このことから、三・長が期される。TOF 法によるを活用するリンと動度評価では、 界強度 5.6 x 105の 動度は、T4DBFHPB が 6.0 x 10–4 cm2 V–1 s–1、4DBFHPB が 1.5 x 10–4 cm2 V–1 s–1 であっ

た。

ル

ス

られた
参

ンがある 1。

クトル、ーシ

V cm–1ーシ、

している 2。さらなるールシミュ

171 C の能といった4DBFHPB は Buchwald-Hartwig

材

定した。TGA、DSC により

ンシ

が

果

T4DBFHPB と分しないため、

において 1000 cd/m2

TADF 有機 EL

の

新規材
化

ールシミュ

し、第三世代の有機 EL であるを実でなかった上ス

らは、動度化が次の課題である。本研究では、 ルより、これまでルでのにし、 意性のあるにした。その特性としては、

20%、1
材

を

では、Gaussian Disorder

をあら

、分

らの

ンジス

動度

ルでは、分

けることはでき

題点がある。この

分

、有機ト

ールシミュ

見に基づき、材

の

ーシ

ンとの

果を

動度化を図る。

文

1. H. Kaji et al., Sci. Rep. 2018, 8, 13462.
2. J. Kido et al., J. Mater. Chem. C 2020, 8, 7200.

−103−したところ、めていをえた。今後、

2020-104
DArP 法を用いた新規
有機

共ポリ ーの開
の応用

と

広 大学
研究
導 ポリ ーは有機

クトロニクスにおいて 要な材である。 々はール（NTz）を有する 導 ポリ ー（PNTz4T）（Figure 1）が、有機

ジにて 10%を える いを すことを報告した。本研究では、NTz に

環した新規

ナ ト ス

であるジ

（PTNT2T）を Stilleジ

相互 用を ち、 い

（OPV）
ン環が二つ

ール（TNT）を合成し、これを有するポリ ー

ッ リング 合（SP）法およびした（Figure 1）。TNT は拡 された 共、ナ ト ス

リール化 合（DArP）法により合成を有するため、これを基 とするポリ ーは強い分性を有することが期 できる。

果
SP 法にて合成した PTNT2T の 平 分

は40 50 kDa であったのに し、DArP 法にて合成した PTNT2T は 15 kDa
ン環のなどが度であった。これは、

での

応が

こったこと

と えられる。 イクリック ル

トリーから見 もった PTNT2T の HOMO
5.32 eV と、PNTz4T と べて 0.18 eV

は
い を

の X

定を行った

ところ、PNTz4T が Edge-on

向を すのに しした。ポリ ーて、PTNT2T は Face-on

Figure 1. Chemical structure of NTz and TNT (upper), andPNTz4T and PTNT2T (lower).

向を すことが分かった。PTNT2T を p 型 導 、PC61BM を n 型 導として用いた OPVをしたところ、

DArP 法で合成したポリ ーでは6%は5度であったが SP 法で合成したポリ
11%

上と、PNTz4T のーは9%に べてFigure 2. Current-voltage curves (left) and external
quantum efficiency spectra (right) of the OPV cells basedon PNTz4T and PTNT2T.

に い を した（Figure 2）。DArP 法にて合成したポリ ーの特性が い要 は、分 が いことにあると えられる。 上の 果から、PTNT2T は めて有 な 導 ポリ ーであることがされた。今後、さらに DArP 法による合成を行い、 分 化と化を目指す。

成果報告
論文(1) M. Wakioka, N. Torii, M. Saito, I. Osaka, F. Ozawa, ACS Appl. Polym. Mater., 2021, 3, 830.
(1)

学会発表
第 69

分

「分 内

合性相互 用を会（ ン イン）−104−

した 導 ポリ ーの分 設 」

2020-105
ス

ン・価

存強

性

ト

ンジス
京

本研究では、強 性スをする

Au25 強 性
の

ロ

ナ
スを

８

の

ッ

ンに

存する

長を有する強性材によるナの Au25 強 性

し、１

が つ

ト ンジス を果を利用するする

ィを用いて、ロ

スを組 化 ロ スによりナ
Au25 ク ス ー 強 性ド イン

したス ン・価存とス ンの 方を利用した次世代ナ

トンネ
バイスとしてすることを目指した。

けて、Si 基 上に 成した Pt/Co 二層
X

リ グ
を

ィにより イド ート き L10CoPt 強 性ナ

ームリ グ

すれすれ入

ッ

することにより、強 性 ースからなる 化の向き（平行・ 平行）の組 合 せに
果を

した バイ

することを目的とした。本研究では、研究代 者のこれまで

教 が合成する Au25 ク ス ーを、

に１つ化学

ル

トンネル

ロ スに関する ウハウ 見を かし、し、共同研究者のッし、ス

ト ンジス をト ンジスに１つの Au25 ク ス ーを化学

ッ

大学

ッ

の

に向

を ニールにより L10CoPt 規 相を ることをた。

法(Grazing Incidence X-ray Diffraction: GI-XRD@KEK 8B)により、GI-XRD

ーンを 定したところ、 ニール 度 800 において、CoPt 001 あるいは 100 にを 認した。001 あるいは 100
CoPt3、L10-CoPt、L12-Co3Pt に分能であり、それ れのするークは、L12することがは、41、36、23%であることを見出した。このことより、Pt/Co 二層を ニールすることにより Si 基 上で L10CoPt
強 性 を 成できることを 認した。このの 化特性を 定したところ、図１に すように
保 力 2.1kOe、 和 化 600 emu/cm3 であった。
L10CoPt 強 性 が 成される本 件を用いて、L10CoPt 強 性ナ
ト ンジス のッ

図１ CoPtと、Au25ニールの 化特性にそれ れ取り組んでいる。

成果報告（ 文、学会

等）

1. R. Toyama, S Kawachi, S. Iimura, J. Yamaura, Y. Murakami, H.Hosono and Y. Majima, Mater. Res.
Express 7, 066101 (2020).
2. R. Toyama, S Kawachi, J. Yamaura, Y. Murakami, H.Hosono and Y. Majima, Jpn. J. Appl. Phys. 59, 075504(2020).

−105−

2020-106−106−

2020-107
の外的スト

ス

性における

の機能
大学

目的 「

」は

(ADH) と
して

ル

が

度の
と
の分

める主要分

ロ

スである。内
リ

ム

中にほ

的に

され、

めて強い

育を

定

能とする
な関

の

があると

機能が注目されてきた。

がリンである。中でも

スト

ス

の関

を相同組

えによって

の目的の一つとした。一方、

の

で特に

そこで、

リン

を

の

で

動する

ールを基
活性を

と

すが、

ムを有している。

えられることから、その１つとして成する

分のうち、50% 上を

ジルコリン (PC) がス

されている。

来 PC

で

ニ

を

が

そこで

ルコール

し、

には

性

合型の

(ALDH) が関
は

共存下でも

の
の

する

ド

される。

は

の

を代

し、その
要な

い

で

型を
リン

らかにし、そのされ、することを本研究は同定されていない。

的意をすることも目指した。
方法・ 果 研究の一種である Acetobacter pasteurianus SKU1108には、Acetobacterを用いた。Phathanathavorn らの方法 [J. Biosci. Bioeng. (2019) 127, 690-7] に従って、 ス
ール
PC

ミン-N-

(PmtA) をコードする

ル基( pmtA) をした。実際に PC がを TLC 展開することで
を含む
下で

しい

特性も
ける

し、その

育

を

とあまり
に

に

で

する応

SKU1108
を

機

に関

には関

しており、本

に
の

で

含有

で

が

合にお
する

から
分を分取し

の

組成を

する

機

に関

件下) では、も加しなかった

加しなかったし、合としていることが合とと同様に相同組

リン

して PC の−107−が増加した。この

して

ール

ス

上の

ジル

果、

果からも、

ール存

えによって

された。

出した。そのされた。一方、4%のしても PE の増加が認められなかった。
は PE であることが存し、 られた法により定が増加した。しかし、上

は

された

リン定

に

リン

に

させたリン

分

出した

能であり、 育

リムリン

PC が

要な

も

を TLC 展開し、下では、 も

で

pmtA

出した

存

ル含有

して

が
能や

から

ール、または 0.4%のと下では pmtA

の

pmtA

した

来

された。

0.4%の

の

果、

果から、PC はールもしくは 0.4%の出した。続いて、は上のしないことが

を 4%の

た。各リン

ール存

させ、SKU1108

を 4%の

した。その

した。一方、がなかった。

する

しているかは、認した。続いて、PC
型を

を

ジル

下 (

ミン (PE)した ADH

では、

果から、

の

ー
で特に

2020-108
ルロースのが 点下で長期を成にげるため、様々な

た

、

ポリ

いった報告

における

・

動

ジ

ル

の

核

CNF）を

の

ークを

成

のグ

ト

果・

トされ

強度が保たれると

特性の

を

図して、

性 CPB を合成し、ブ
果、ブ

シ内部の

による

核

の融

シ内部

ークに

性 CPB 層内部における成果が年報告される。
性 CPBした CNF（CPBにロック）を N-methylpyrrolidone（NMP）
した。（2）

基導入 CNF（Br-CNF）を

た。
（3）グ

合開

加し、Ar
ト化

2-

基の導入
下、

開

一
動

ジ

ー（poly(ethylene glycol)methyl ether methacrylate (PEGMA)）

性モ合に供した。

中での CPBした CNF を

した後に、

件下で

に

合開

基である

2-bromoisobutyryl 基を導入する

応から

るが、

心分

を

する

度にグ

い

の

/ OH）と pyridine（2 等 / OH）を

従来、CNFは、 めKCールミルに供することで CNF を合（SI-ATRP）法により

が

を目指す。

ルロース（日本

応させることで、開が深い。本研究では、CPB をはの

bromoisobutyryl bromide（1.5 等

ル

材

など

合研究所

イバー（CNF）が注目されており、その

機能の

し、

型

ー

認した。これは、

ンなどのナ

ルロースナ

実験 （1）CNF の
させ、

、

術

がもたれる。 者は、京都大学化学

合（HP-SI-ATRP）により

30

として

による

に分

の応用に期

定（DSC）を遂行した。その

材

、

上にポリ

性 CPB 内部におけると見なされた。一方、グ

のナ

があれば、

コーティングらとともに、すると推定される、
の

らない

による

シ（concentrated polymer brush; CPB）は、

があり、

開

たり

と

分野に応用できる。

ーブ

研究所の辻井敬亘教

動の

に大

の

と

め

要とするため、大きな課題であった。本である NMP 中での

研究では、
を
1）の

20nm

たところ、
分 性 CNFを次のがられた。このFigure 1. FE-SEM image of CNF prepared in NMP.

応 に 供 し た と こ ろ 、 2-

bromoisobutyryl 基を

度かつ

の開

分

で導入

能であることが、FT-IR

な PolyPEGMA ブ

また、SI-ATRP 法により
は

度（図

に

するものと期

シを

される。
−108−

定等により

認された。

に導入できた。本研究でられた材2020-109
イ

モンドの

ナ

ルにおける

の

中心
規

イ
と

モンド中の
べ特

一ス

年、 れた実てに存していることがが 1 価に

状

化により

ン

の

めて

実験と

ットな

度の

の

えられる

状

、 度

ン

や

の存

ルでの

に関して、

が

化合成

ナ

では、 ン

定になることや、ス ンコ

性

を

つ

ー

とし

ンス

すべき課題がある。このの有力なえられる。本提案では、課題術を用いることによる、件出しを、共件を成することができる。成点

ーした。ここでスポットのルス

定、PL スをしていないが、その実

に向け議

なる

定化を行い、それらの定を目指している。

また、共同研究成果として、 々はドし、それを用いて
度分

の

感度

度

成したド

スト状

一性や
ン

のため

から

ナ

で

度

の

度

う

スト状

スの提案や合成

イ

で

れる

は

が

してし

定など NV であることを

クトル

成によるス

ンコ

ー

研究を行った[1]。 イ

できる

き

こされる

ンス

定

等を施して

の

いの長

モンド中の NV 中心は、の機能の研究におけされている。また、Aulter-Towns Splitting（ATS）法により

による共

の

ンシングにおける

化の

を

感度化が期

ンブル

の

存性を

定した。ド

スト状

の共

の

ン

としての有用性をけにくくなり、コ

される。今

の

度

ー

、 々は

で ATS 法によりドン

度となっていると一 NV 中心と

かった。

ル

件における

ル平

状から

ほど

化によって

の NV 中心からなる成し、その共
られ、ド

所的な

られ、 度

した、多

果が

スト状

としての応用が期が長くなることがにおいて、続している。課題として、新たな度感度向上の実

では方のによって行った。 々は

が実

化を実

ロ

強度もバルク中の NV 中心よりも 1状では ODMR や

Pm

たすと、

を

において、 ー

まうため、

ルー

が

の

平

できる点である。その応用において、NV 中心は感度向上のため下するなど、 要なルでの学特性を有する。 材を目指した。

されたが、

る

ン

、

び

果

で

内部の

ン

しく

モンドにおいて、ある CVD 合成

イ

出・

ましい。しかし、ナ

した NV のないい NV 中心

ン

ン特性

において

感度が

の一つとしてルのンを研究がなされてきた。NV 中心の

える

性

一ス

れたス

ローブとし、 一 NV 中心を用いたいの合 （NV）中心は

すべき点は、NV 中心では

ンを

ルの

一

大学

化が

スト状
とほ

ンス
大グ
を
合

した。

成果報告
1

Ernst David Herbschleb,

、
68

、2021

3

18

−109−

、

2020-110
イ

モンド中の

中心ス

ンの

的

と

的

野

イ
研究が

モンド中の

力的に行

れ、

合

である

れた特性が
ー

ンス

（T2）を

力、pH などの

感度

ン

として

広い分野での応用が期

感度なンいるが、従来の

ン

ルス

の

定による

なる
ル

度を

しつつ、

度の

イナミック

ムにより

中のス

い感度が実

し、

ンとしては

、

、

度、

される。

た研究では、

定

ンにより
ン

い感

合

せ

での

界

についてもシミュン

案した手法は
の

ー
の

を、感度を

に大きく

研グルー

の応用環境を広げる成果として期存するため、今が合成した n 型の成果はされる。また、 定定の

モンド中の NV 中心を用いて、

イ

を広げるこ

一 NV

イ

していたが、今

、リンドー

n型

イ

した NV 中心の T2 が、ドー していない

中に同じ

件で

した NV 中心の T2に術であり、 来ので世界べ長くなることも実
化にとって

存性が

用の大きさは

また、これまで注入を行って

推

も広い

を組

ン

される。

ン

ルス

を行った。今とにもつながると期

モンド

より、２

の成果は、

の相互

イ

果も報告され、学術的に関心が用でき、しつつ広げた今
との

なる

々はこの

の

にも

報告

する感度の

えるようにも見られる
たれていたが、今せ、それをした（図１, [1]）。これは 一

の
に

合

、

一 NV 中心において 7

ンジを実

ルス

イナミック

化することにより、におけるである。また、に術分野においてされて点があった。今を組(8 K)における

中心の

感度化と

することに
ルス

リ

としての応用が期

では、ンジを広げることをシ

つことにより合研究所

果NV 中心はを科学らかにされてきた。特に、NV 中心は

ンコ

実験と

術

合 （NV）中心は、

く長いス

を

出

感度を実

した[2]。イ要である。また、

ン注入法は状所的な NV 中心

要な

モンドにイ

などの成果もまとめることができた。[3]成果報告[1] E. D. Herbschleb, H. Kato, T. Makino, S. Yamasaki, N. Mizuochi, Nature Communications, 12, 306 (2021).
[2] A. Watanabe, T. Nishikawa, H. Kato, M. Fujie, M. Fujiwara, T. Makino, S. Yamasaki, E. D. Herbschleb, N.
Mizuochi, Carbon, 178, 294-300 (2021).
[3] T. Makino, H. Kato, M. Shimizu, M. Hatano, N. Mizuochi, Semiconductors and Semimetals, 103, part 1,
Chapter 5, Pages 137-159 (2020). Edited by C. Nebel, I. Aharonovich, N. Mizuochi, M. Hatano, Elsevier.
−110−

ン

2020-111
ロリジン
化学選択的

リジン型分
シル化 応の

による
的
中

教大学

目的
々は本申請課題を通して、 端らによって開機能について分

ルで

ル

シル化、
（２）1,5-ンジ

択的

シル化、（３）4-

シル

ミ

シル化について度は 4-PPY のリジン（4-PPY）のールのールの化学選ンジ

的機能についてンジ-1,7-

シル化、（ ） -L-グルコース
選択的モ

ロリジ

することを目的として研究を進めてきた。これまでに、（１）
性選択的

された

導

に

ールの
する 4

を行っており、本年

した。

果・
（１） （
いた

モ

果を

た。主

）について、4-PPY のルによって
成

基や OH 基）との状 （TS）の

える TS

を

ステル部

合が

の

での

と認識点までの
が

は

HO

NHX
Me

4PPY

HO

Ac2O

AcO

1 (X = SO2Ph)

HO

OH
3

4PPY
Ac2O

合ネットワークを的な分来しており、TSすることが見出されている。これは、認識に基づくことを認識による特定の TS のしており、一連の研究を通して、定化が有であることが分かった。

NHX
Me
( )-2

AcO

OH
4

4PPY
Ac2O
5

6
4PPY

(4)

Me
7

Ac2O

/

応点ま

い選択性が

を

することに

認識能は、この基

TS-1
(3)

向基（NH

5 であることが分かった。実験的にも、 向基から

ではなく分

(1)

の

シル化

能が

に

ミド基と基

した

認すると、

において、 も導の戦略として、分

(2)

果的な

5 となる基4-PPY の

HO

に

実に合

向基を認識点として、 ステル基や定化していることが分かった。4-PPY が有する特合ネットワークの

する O

合も実験

として、4-PPY の基とのに Ac2O を用ステルとし、れの成している。さらに選択性インドリル基などの 4-PPY 上のよって、TS をルを行い、いの共通した特

に強い

を

Ac

OMe
8
TS-3

−111−

TS-4

2020-112−112−

2020-113
Studies on the enantioselective total synthesis ofmarine natural product bohemamines and their derivatives
Tomoyuki Yoshimura

Kanazawa University

Bohemamines A (1) and C (2), which contain tetrasubstituted carbon in the pyrrolizidine framework, wereisolated from marine Streptomyces spinoverrucosus strain SNB-048 (figure).1) Compound 1 is thought to be abiosynthetic intermediate of spithioneines A (3) and B (4),which possess an amino acid, L-ergothioneine. Althoughsignificant biological activities of 1–4 have yet to bereported due to limited research, L-ergothioneine has attracted attention due to its relationship with chronic
inflammatory diseases such as rheumatism and Crohn disease. Compounds 1-4 have potential for discovering
new biological activities against inflammatory diseases. To synthesize bohemamines and their derivatives, we
initially planned the synthesis of bohemamine A (1).
The synthetic studies on 1 began fromchiral lactone 52) (Scheme). Amidation of 5with benzylamine and subsequent mesylation
afforded sec-alcohol. Then intramolecularcyclization with inversion at C (4) gave lactam
6. The lactam was converted into nitroolefin 7
by thiolactamization, formation of sulfonium
salt with iodomethane, and condensation with nitromethane. Stereoselective construction of tetrasubstitutedcarbon was achieved by convex-face selective 1,4-addition reaction of MeLi to nitroolefin 7. Treatment of
nitroolefin 7 with MeLi in THF at 78 °C followed by the addition of acetic acid gave pyrrolidine 8 in 81%
yield as the sole product. Reduction of nitro compound 8 into oxime followed by O-acetylation of the resultant
oxime and hydrolysis of O-acetyl imine provided aldehyde 9. Aldehyde 9 was converted into pyrrolizidine 10
in four steps: 1) change of the N-protective group from benzyl to Boc, 2) addition of the propiolate ester at thealdehyde , 3) oxidation of the resultant sec-alcohol, and 4) cyclization under high temperature. Deacetalizationof 10 with protic acids such as HCl and TFA was problematic due to stereoisomerization of 11. By contrast,
deacetalization with BiCl3 gave diol 11 in 63% yield. Regioselective tosylation of diol 11 gave tosylate 12 in
84% yield. The conversion from 12 to 1 is currently being investigated.
References
1) Fu, P.; MacMillan, J. B. Org. Lett. 2015, 17, 3046-3049.
2) Suh, H.; Wilcox, C. S. J. Am. Chem. Soc. 1988, 110, 470-481.

−113−

2020-114
能・

バイスの先端化学材の、）ICR MS

に

、

100

、

、

。
、

SEM

の

。

Lignin, Cellulose
に

、

の FT-

の

の

、

、

の

に

、

、

FT-IR

に
）の

。

の

Cellulose, Hemicellulose の

、

の

、

Lignin,

の

に

の

15 m

の

）

IRT-7200
400

1 m）
m x 1200 m

、

。 、

FT-IR

、50 m

(50 m

FT-IR

。

、FT-IR の ATR

Lignin, Cellulose, Hemicellulose の

の

の

の

FT-IR

に
、

) の

、
、

の

、

、

の

法の開

）

/

、

）

の

的

、

の FT-IR）

8 X 241265.1cm-1, 1511.9cm-1）、、Lignin

Cellulose(+Hemicellulose) (1029.8 cm-1, 1160.9cm-1, 1103.1 cm-1, 1153.2 cm-1）、Hemicellulose(810.0cm-1, 1731.8 cm-1) の、Lignin,

Cellulose, Hemicellulose の
。 、

に
。

の

、

ATR

の

に、

に

の

、Lignin

Cellulose にに、Hemicellulose にに、の、Lignin, Cellulose, Hemicellulose
に、

の

、
の

の

の
に、

の

、
の

、
FT-IR

MS Imaging, SEM,

に、 の
、

、

）

。

成
Osamu Hatano, Masumi Hayazaki, Akie Hamamoto, Hiroshi Takemori, Hikaru Takaya,
Takafumi Shanoh, Ken Ohnishi, Masaharu Nakamura. CLEM imaging of rhododendrol-induced
leukoderma in zebrafish and catalytic oxidation of Japanese cedar wood. ABiS Symposium:
Forefront and Future of Electron Microscopic Imaging. Feb.14-15, 2020 Okazaki, Japan
Armouti M, Winston N, Hatano O, Hobeika E, Hirshfeld-Cytron J, Liebermann J, Takemori H,
Stocco C.

Salt-inducible Kinases Are Critical Determinants of Female Fertility.

Endocrinology. 2020 Jul 1;161(7):bqaa069.

doi: 10.1210/endocr/bqaa069.

−114−

2020-115（国際）Determine the three-dimensional structure of 13C labeled -synuclein(61-95)
in the Langmuir-Blodgett film and supported phospholipids bilayers by
pMAIRS FT-IR
Chengshan Wang

Middle Tennessee State University

A. Objectives:
1.

13

C labeled -syn(61-95) containing residues 61-95 of -synuclein will be synthesized andpurified.
2. Screen the conformation and orientation of specific amino acid residue of -syn(61-95) in
Langmuir-Blodgett film.
3. Screen the conformation and orientation of specific amino acid residue of -syn(61-95) insupported phospholipids bilayers.
B. Experimental methods:
Peptide of 13C labeled -syn(6195) at position 93G was synthesized via solid phase(Fmoc) chemistry and purified by semipreparative reversed-phase high-performance liquid
chromatography (RP-HPLC) on Waters Breeze 2 separation system equipped with 1525 EF
binary pump. The success of the synthesis and the purity of the peptide were confirmed by a
Waters SYNAPT q-TOF tandem mass spectrometer. The surface pressure-area (A) isothermof -syn(61 95) were conducted in a A Kibron µtrough. The Langmuir-Blodgett (LB) filmsof-syn(6195) were made by transferring the-syn(6195) Langmuir monolayers toquartz slides and silicon (Si) slides under the surface pressure 10 mN/m. The circulardichroism (CD) spectra of the LB films of the 13C labeled -syn(6195) were measured by a

JASCO

Incidence

J-810

spectropolarimeter.

p-Polarized

Multiple-Angle

Resolution

Spectroscopy (pMAIRS) measurements were performed on the Nicolet IS50 FT-IR
spectrometer (Thermo Scientific, Waltham, MA) equipped with a pMAIRS accessory. The LB
film monolayer of the 13C labeled -syn(6195) at position 93G on Si substrate was put in thepMAIRS accessory and the IR beam transmitted trough the sample.
C. Experimental results:
The 13C labeled -syn(61 95) was synthesized and purified. Figure 1A shows theof the 13C labeled -syn(61-syn(61

A isotherm95) and the isotherm is very similar to that of the unlabeled95). This is not a surprise because replacement of a 12C by 13C in the backbone

carbonyl (i.e., C=O) should not change the overall biophysical behavior of the peptide, whichcontains hundreds of carbon atoms in it. Thus, the CD spectrum of the 13C labeled -syn(6195)

is also similar to that of unlabeled peptide as shown in Figure 1B. For the LB films of the 13Clabeled -syn(6195), two negative peaks at 222 and 208 nm in addition to one positive peak at

192 nm are detected. Therefore, the 13C labeled -syn(61−115−95) also transforms to -helix at theinterface. On the other hand, pMAIRS was used to determine the tilted angle of the axis of-syn(6195) at 93G and is very different to that of the unlabeled peptide. As shown in

Figure 1C, The In-plane Spectrum (SIP) result of the 13C labeled -syn(61-95) was
shown as the top curve in Figure 1C. Both regular amide I and II bands weredetected at 1655 and 1535 cm-1, respectively. A very strong 13C amide I band was also
detected at 1625 cm-1 in the SIP. The position at 1625 cm-1 shows that the 93G is in-helical conformation in the LB film. In addition, the 13C amide I band in the SIP
result is even more intensive than the regular amide I band which is the absorption
sum of all the other thirty-four residues in the sequence of -syn(61-95). Such an
intensive 13C amide I band suggests a very small tilt angle (i.e., parallel orientation)of the 13C amide I transition moment. The out-of-plan Spectrum (SOP) shown in thebottom curve of Figure 1C also detects the amide I band at 1659 and 1645 cm-1. More
importantly, the 13C amide I band at 1625 cm-1 was not detected in the SOP result,even though the 13C label does exist at position 93G. According to the selection ruleof pMAIRS, the tilt angle of the 13C amide I transition moment at 93G is ~0º.
Because the tilt angle of the axis of-helix is equal to that of the 13C amide I

0.0009

30

(A)

10

1625

4

1655

Absorbance20

CD signal, mdeg

Surface pressure, mN/mtransition moment, the tilt angle of the axis of -helix at 93G is also ~0º.

0.0006(B)

00.0003-40.0000

1535

(C)
SIP
SOP

1659

0
100

200

300

400

Area, Å2/molecule

500

200

220

240

Wavelength, nm

260

1800

1700

1600

1500

Wavenumber, cm-1

Figure 1. (A) Surface pressure-area isotherm of the 13C labeled -syn(61water, (B) CD spectra of the LB films of the 13C labeled -syn(6195) on pure95) on quartz

slides. (C) p-MAIRS results of the LB monolayer of the 13C labeled -syn(6195)

transferred under 10 mN/m.
D. Discussion
X-ray crystallography and NMR are two major methods to determine protein’s structure. However,neither of them can elucidate the high resolution structure of membrane proteins, which weighs ~30-35% of the total proteins, in monolayer structure. Dr. Wang and Dr. Hasegawa are developing amethod for membrane proteins in monolayer structure with residue resolution by pMAIRS, which
will be a supplement to X-ray crystallography and NMR.
E. Publication.
One paper about Figure 1 was submitted to Colloids & Surfaces B: Biointerfaces. Positive
comments was received and the revision has been submitted for the final decision.
−116−2020-116（国際）Hydrophilic dendrimers as additive for polyvinylidenedifluoride
based membranes
Mona Semsarilar

University of Montpellier

This project is a collaboration between Dr. Mona Semsarilar from University of Montpellier(France), Prof. Shigeru Yamago and A/Prof. Yangtian Lu from University of Kyoto (Japan).
Objectives:
The aim of this project is to prepare porous polyvinylidene difluoride (PVDF) membranes withhydrophilic character for water filtration. PVDF is hydrophobic and incompatible (immiscible)
with all other polymers apart from polymethyl methacrylate (PMMA). PVDF is normallyblended with hydrophilic polymers in order to confer hydrophilicity to the prepared membranes.
However, due to the immiscibility of PVDF with other polymers this method would result inmembranes with inhomogeneous and short-lived hydrophilic character. To solve this major
problem in preparation of hydrophilic PVDF membranes, the idea here is to synthesize an
amphiphilic block copolymer where one block is a linear hydrophobic PMMA or PVDF
(miscible with the membrane forming high molecular weight PVDF) and the other block is adendritic hydrophilic polymer. The linear PMMA or PVDF block will fully blend with the highmolecular weight PVDF and allow the homogeneous dispersion of the hydrophilic polymer
segments within the PVDF matrix.
Experimental methods and results:
As per the original design of the project, Prof. Yamago’s team was in charge of synthesis of theamphiphilic

dendritic

block

copolymers.

These

block

copolymers are prepared using
TERP controlled polymerization(Figure 1). Up to now, a library of
six polymers (fully characterized)
have been prepared (Table 1). Now
a second library containing threeother block copolymers are in thecourse of being prepared.

−117−Meanwhile the French team has been studying the blending properties of the synthesized block
copolymers with the high molecular weight PVDF used for membrane fabrication using
thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The block
copolymer samples that gave better blends (samples D7, 15 and 31) with PVDF were used toprepare the porous membranes using solvent/ non-solvent phase inversion method (SNIPS). The

performance of the resulting membranes were verified via a dead-end filtration set-up. Currently,
aging tests are being performed to evaluate how long the added copolymers would stay in themembrane matrix. In the next step, the same sequence of experiments will be carried out on blend
samples that would be prepared using the polymers currently being synthesized in the team ofProf. Yamago (the second sample library).
Publications:
The start of this collaborative project was March 2020, which was coincided with COVID19
pandemic. As in both countries (France and Japan), travelling were banned and in France
universities were closed for long period between March-June and October-December, 2020, theproposed tasks in the project could not be carried as planned. Despite these restrictions, we
decided to start the collaboration and do as much as we could in each team (with some imposed
modifications) and exchange samples via post. This has affected the progress of the projectvastly. Up to date we have managed less than 50% of the work initially planned. Regardless of
the unfortunate circumstances, both partners are enthusiastic about the project and are committed
to carry on with the collaboration and take the project to completion. We are positive that during
the course of 2021 we will be able to complete the study and prepare an article based on the work
performed. We hope that we would be able to present this joint work to the scientific community
in the next coming year.

−118−

2020-117（国際）−119−−120−

2020-118（国際）Rheology Symposium in IUMRS-ICA 2020 - MRS THAILAND 2021
Instead of the 16th International Workshop for East Asian Young Rheologists
Tadashi Inoue

Osaka University

Purpose of project The i-JURC/ICR budget was initially proposed for organization of the 16
International Workshop on Young Rheologist in East Asia (IWEAYR-16, Thailand). This workshop has
a mission to promote international exchange among young faculties and graduate students in cooperation
with researchers from various countries in East Asia, in several research fields such as polymer scienceand materials science. The workshop is anticipated to deepen our research activities and form the basis
for future cooperation. Unfortunately, COVID-19 prevented to have the workshop on site. Considering
the importance of the workshop, we had decided to have an alternative meeting. Fortunately, Prof. Visit
Vao-soongern, one of the core members of our society, was planning to have a rheology symposium in
IUMRS-ICA 2020 - MRS THAILAND 2021 on line. Therefore, we joined his rheology symposium tosupport his task and also to complete our mission. The participation of many undergraduate and graduate
students fulfilled our original mission to enhance shearing new research results. The budget was
effectively utilized to support the participation of as many Japanese researchers as possible.
Place and schedule of workshop Instead of IWEAYR-16, we had a special international rheology
symposium in IU-MRS, which was held on Feb 24 and 25, 2021 on the web, chaired by Prof. Visit Vaosoongern of Suranaree University of Technology, Thailand.
Purpose of the symposium From the beginning, the purpose of this workshop is to promoteinternational exchange and collaboration among young faculties and graduate students who will be themain researchers in the field of rheology and material science in the near future, and therefore, to provide
a place for research presentation and discussion, and to revitalize related fields. The symposium provides
an opportunity for participants to present their research results, discuss and exchange research ideas ina very friendly atmosphere. At the same time, in order to further develop joint research activities among
several research groups, it is to provide a place for people exchange.
Background of workshop This workshop has been held annually since the first IWEAYR in Seoul(February 2006). After that, it has been organized in Kyoto (January 2007), Shanghai (January 2008),
Nakhon Ratchasima (January 2009), Busan (January 2010), Yamagata (January 2011), Beijing(February 2012), Phuket (January-February 2013), Seoul (February 2014), Fukuoka (February 2015),
Shenzhen (January 2016), Pattaya (February 2017), Jeju Island (January 2018), Nagoya (January 2019),
and Changchun (January 2020), in a circulating order of Korea, Japan, China, and Thailand.
Participants The number of participants in this rheology symposium was over 40, which was about
one-third of the average in recent years, from seven countries, USA, Japan, Korea, China (Tunisia),
Thailand, and Colombia. The main participants were:
Jaewook Nam, Professor,
Seoul National University,
Korea
Youngdon Kwon, Professor,
Sungkyunkwan University,
Korea
Wei Yu, Professor,
Shanghai Jiaotong University,
China
Kang Sun, Professor
Shanghai Jiaotong University,
China
Quan Chen, Professor,
Changchun Institute of Applied Chemistry China−121−

Exkarach Deenang, Assoc. Professor,
Hiroshi Watanabe, Professor,
Yuichi Masubuchi, Professor,
Takashi Taniguchi, Assoc. Professor,
Hiroshi Suzuki, Professor,

Udon Thani Rajabhat University
Kyoto University
Nagoya University
Kyoto University
Kobe University

Thailand
Japan
Japan
Japan
Japan

A snapshot of the meeting on screen. Left side: participants. Right side: PowerPoint by the presenter(by the invited speaker, Prof. Hidema, Kobe University).

Overview of the symposium Total number of submitted papers was 30, including one keynote andtwo invited talks. On the first day, Prof. Ronald Larson, University of Michigan, provided a plenary
lecture on “Progress in Modeling Polymer Melt Rheology and Crystallization”. After this plenary lecture,a Keynote lecture was presented by Professor Ruri Hidema (Kobe University), long invited
presentations by Professor Jaewook Nam (Seoul National University) and Professor Quan Chen
(Changchun Institute of Applied Chemistry), and 27 short presentations by mostly doctoral students. 5
poster presentations were also given on web throughout the symposium. The best presentation award
was celebrated by participant's vote.
In the symposium, there were many rheological studies on new polymer materials such as
nanocomposite and associating polymers. In addition, there were many kinds of basic research on theanalysis of various physical and rheological properties and hierarchical structure of reinforcing materials
such as particle dispersion systems. Some issues such as theory, simulation, and flow control of soft
matter were presented.
Summary

In spite of the web style, the discussion was very active. It was an excellent opportunity

for students to learn new ideas and deepen their research. Last year, we heard the first report ofcoronavirus, COVID-19, when leaving from Japan for the IWEAYR-15 venue, Changchun, China.
Since then, COVID-19 has been significantly affecting our life and research. However, I strongly felt
the high activity of the field during the rheology symposium. Success of this symposium was very
helpful to keep our community. We appreciate the financial support from i-JURC/ICR. I would like tofinish this report hoping to have IWEAYR-16 on-site, in Udon Thani, Thailand, in the next year.

−122−

2020-119（国際）Study on the mechanism of the crystal structural evolution ofpolydimethylsiloxane
Liangbin Li

University of Science and Technology of China

Objective: Crystallization of polydimethylsiloxane (PDMS) is mysterious. Professor Tosaka,
Institute for Chemical Research (ICR), Kyoto Univ., found unusual transformation of the 2D
WAXS patterns of PDMS crystal, and subsequently, four crystal forms based on the electron
diffraction of the single crystals. The transformation of the 2D WAXS patterns was tentatively
explained considering coexistence of the four crystal forms. More detailed studies by Professor
Liangbin Li gave the structural evolution diagrams in strain-temperature space and clarified
pathways of transformation between the different structures (forms) during the stretchingprocess through in-situ synchrotron radiation experiments. However, the crystallization of
PDMS is still difficult to understand by the existing concept of structure formation. Therefore,
Prof. Tosaka and Li planned to collaborate on researching the evolution of crystal structureduring the crystallization process of PDMS.
Experimental method: The nano-scale dynamic structural analysis X-ray system in ICR wasplanned to be used for the research. The SAXS experiments about the crystallization of PDMS
in the wide range of temperature were expected to reveal the mechanism of the dynamic
structure evolution. The cryo TEM in ICR (JEM-2100Plus equipped with a cryo sample
holder) was also planned to be used for more detailed observation of single crystals. Based on
the obtained data, the structural analysis of the PDMS crystal was expected. In order to build
the molecular model to explain the mechanism of the structural transitions, the software ofMaterials Studio was planned to be used. A post-doctor Jingyun Zhao was scheduled to visit
ICR and perform these studies with the help of Professor Tosaka.
Results: Because of the worldwide pandemic of COVID-19 diseases, the international travel toperform the experiments in ICR was not possible during the period of the Joint/Usage Research2020. Therefore, some other experiments related to this theme were performed in individual
countries. For example, cooling experiment of PDMS sample under constant strain byProfessor Tosaka revealed increase of tensile stress after the onset of crystallization, which
seems to be inconsistent with the proposed crystal structures. The influence of filler contents
has been found to significantly influence the crystallization of PDMS at low temperature
region, while the detailed formation mechanism requires further investigation.
Discussion: Some of experimental results related to crystallization of PDMS were very
difficult to explain according to the currently-proposed crystal structure models. Further
refinement of the models is quired for consistent understanding of all the experimental results.

−123−2020-120（国際）High-pressure synthesis of potential multiferroic oxides
Kunlang Ji & J. Paul Attfield University of Edinburgh
Objectives: High pressure-high temperature (HPHT) synthesis is used to stabilize unusual
oxidation states and coordination environments in transition metal oxides, resulting in interesting
physical properties. In collaboration with Professor Shimakawa in ICR at Kyoto University, aunique high-pressure multianvil apparatus which reaches up to 20 GPa and 2273 K is available touse. This equipment provides a good opportunity for synthesize the double corundum/perovskite
with small tolerance factor and develop their potential multiferroics.
Experimental methods: Due to the Covid-19 special circumstance, we developed ourcollaboration by communicating e-mails. We focus on writing paper of the new double corundum
Co2InSbO6 synthesized at Kyoto University during early 2020, while Professor Shimakawa
providing very useful scientific guidance for the paper through emails.
Experimental results: A new double corundum Co2InSbO6 has been successfully synthesized withpolar NTO-type R3 symmetry and lattice parameters a = 5.28813(3) Å and c = 14.0294(1) Å.
Magnetic susceptibility and hysteresis loops indicated ferrimagnetic like behavior with TC = 40 K.
Temperature dependent synchrotron x-ray diffraction show adynamic cation site exchange at all temperatures and particular aphase transition to ordered ilmenite type structure above 850 K,
inducing the unit cell shrink along the a and b directions, show
in Fig.1. The compound was turned back to NTO-type above 950
K with normal thermoal expansion.
Discussion: The selective site exchange only between Co2+ andIn3+ at different temperatures results from the small size andcharge mismatch between Co2+ (rVI = 0.745 Å) and In3+ (rVI =0.8 Å), compare to that between Co2+ and Sb5+ (rVI = 0.6 Å).
Publication: K. Ji, M. Amano Patino, E. Solana-Madruga, Y.
Shimakawa and J. Paul Attfield, Pressure and temperatureinduced order-disorder double corundum Co2InSbO6, in preparation

Fig. 1 Temperature dependentlattice parameters and cellvolume from SXRD data
show phase transition from
NTO-OIL-NTO
temperatures.

−124−

at

higher

2020-121（国際）Micro- and nano-structural characterization by advanced transmission electron
microscopy of novel functional materials for battery development
Torranin Chairuangsri Chiang Mai University
Our research group in Thailand has been collaborating with researchers at the ICR including Hiroki KURATA, Mitsutaka
HARUTA and Tsutomu KIYOMURA in micro- and nano-structural characterization by advanced transmission electron
microscopy of novel functional materials for battery development. Two publications have been completed as summarized
below;
I. Novel TiO2(B)/Nitrogen-doped Graphene Hybrid-composites (TNG) as Anode in Advanced Power Batteries(Ultrafast -charging and long cycle-life anode materials of TiO2-bronze/nitrogen-doped graphene nanocomposites for high-performance lithium-ion batteries, T. Autthawong, Y. Chimupala, M. Haruta, H. Kurata,
T. Kiyomura, A. Yu, T. Chairuangsri and T. Sarakonsri, RSC Adv., 2020, 10, 43811-43824)

Novel TiO2(B)/Nitrogen-doped graphene hybrid-composites (TNG) were prepared by hydrothermal method and investigatedby TEM at the ICR. Different morphologies of TiO2 dispersed on nitrogen-doped graphene sheet were confirmed as anatasenanoparticles, TiO2 nanotubes and TiO2 depending on the reaction time. The best battery performance was obtained from thenanorods TiO2(B)/nitrogen-doped graphene (TNG-24h) electrode with high specific capacity of 500 mAh g-1 at 1C (539.5 mA
g-1).
II. Novel Sn(SnO2)-SiO2/Graphene-based nanocomposites as Anode in Lithium-ion batteries(Improved electrochemical performance of anode materials for high energy density lithium-ion batteries through Sn(SnO2)-SiO2/graphene-based nanocomposites prepared by a facile and low-cost approach, O.
Namsar, T. Autthawong, V. Laokawee, R. Boonprachai, M. Haruta, H. Kurata, A. Yu, T. Chairuangsri and T. Sarakonsri, Sustainable Energy Fuels, 2020, 4, 4625-4636)

Novel Sn(SnO2)-SiO2/Graphene-based nanocomposites wereprepared by facile and low-cost technique. The materials werestudied by TEM at the ICR. The successfully synthesizedmaterials can be confirmed by distribution of Sn, Si, C and O
elements (Fig 1). The highest capacity was achieved in theSn(SnO2)–SiO2/rGO composite. The enhancement ofelectrochemical characteristics of the nanocomposites wasdue to the combined advantages of graphene and thenanoparticles with high theoretical capacity (Sn, SnO2, SiO2).
Moreover, the flexible graphene matrix was capable ofbuffering the volume change of the nanoparticles during thedischarge–charge process, resulting in the enhanced
electrochemical properties.

Fig. 1 elemental maps of Sn, Si, C and O for the Sn(SnO2)–SiO2/NrGO
nanocomposite and the corresponding high-angle annular dark-field(HAADF) STEM image

Two manuscripts are being prepared for publication inrefereed journals. The results can be summarized as follows:
I. Novel Zn-Mg Alloys as Anode in Metal-Air BatteriesZn-(0-5wt.%)Mg and Zn-3Mg-(0-3wt.%)Bi alloys were investigated. ZnO, ZnO2 and amorphous ZnO were found as surface
oxides on the pure zinc, whereas MgO4 has been found in addition as a surface oxide on Mg-rich phases (Mg2Zn11 and MgZn2)
on the Zn-Mg alloys. The corrosion current density of the ternary alloys significantly increased with increasing Bi content.
The highest corrosion current density was from Zn-3wt.%Mg-0.5wt.%Bi alloy, which is about 15.8 A/m2. For self-corrosion
test, the alloys were immersed in 6 M KOH solution. It was found that self-corrosion rate of the alloys significantly increased
with increasing Bi content as compared with the cases of pure zinc and Zn-3wt.%Mg alloy. The findings are useful forenhanced understanding on passivation behavior of these novel Zn-Mg-Bi alloys as compared to that of the pure zinc andbinary system Zn-Mg alloys.
II. Novel Nano Crystalline/Amorphous Vanadium Lithium Borate Glasses as Cathode in LIBs
Structural and local chemical analyses of vanadium-lithium-borate glasses containing V2O5 35-60 mol.% and prepared by amelt-quenched method were studied. Nanocrystalline phase of LiV3O8 was found by HRTEM. The size of the crystalline
phase depends on the vanadium content. It seems likely that the larger amount of vanadium, the larger the crystalline size is
as can be compared. The oxidation state of vanadium was confirmed by XANES showing the majority of V5+. These evident
can support the presence of vanadium in two environments as in amorphous matrix and nano-crystalline LiV3O8.

−125−

2020-122（国際）Electron energy loss spectroscopy analysis of hexagonal multilayer graphene
Cheng-Yen Wen
Ob e ti e: M ltila er graphene sheets prepared b
as the ernal t pe o
the Ahemi al apor deposition (D) is generall regarded

hi h the sta ing order o graphene sheets ollo s that in nat ral graphite so alledt pe sta ing. It is re entl

primiti e he agonal

National Taiwan Universityo nd that the m ltila er graphene prepared b

D e hibits thenit ell (AA sta ed). The opti al and ele tri al properties o s

h AA sta ed

m ltila er graphene sho ld be di erent rom those theoreti all predi ted based on the ernal sta ing.
e there ore initiate ollaborati e resear hsta edD graphene andith Pro .

rata and Pro .

rther e plore its phonon dispersion properties.

E perimental Methods: The graphene samples
and h drogen and methane as the gas prerea tor prior to graphene gro th (Oere prepared b

rsors. O gen

D singse tional spe imens ere prepared b a otheontrastross

sed ion beam s stem.

D graphene an be

i l

(a)

(b)

and

and on enientl determined baman spe tros op based on an empiri al r le.

o e er the

20 vm

la er n mber o graphene is nderestimated. Fig re 1 ill strates
the in onsisten : the area in Fig re 1(a) is regarded asmonola er graphene in agreement ith aman anal sis b t theross se tional TEM anal sis in Fig re 1(b) sho s that the area
is a t all m lti la er graphene. S

h in onsisten

20 nm

Fig re 1. (a) SEM image oDm ltila er graphene. (b)ross
se tional TEM image o graphene in
the region labeled in (a)also appears in the graphene prepared b O

m ltila er regions in Fig re 1(a) e hibits e en larger n mbers o graphene sheets. The
prepared in this st dDgrids and o idi ed Si s bstrates

aman spe tros op anal sis respe ti el .

hange in opti al mi ros op

s anning ele tron mi ros op

lo ed into theD) or in estigating the a tors leading to the n s al AA sta ed

or transmission ele tron mi ros op anal sis andO t omes: The la er n mber oas the gro th s bstrate

as also intentionall

gro th. The graphene la ers ere et trans er method to s pportingo nted b

ar ta to hara teri e the AAo ld ha e a di erent sta ing order so that the

D grapheneaman empiri al r le is notappli able. The sta ing order is hara teri ed b di ra tion anal sis. The res lts sho
di ra tion intensit bet een ሼ101ത 0ሽ and ሼ112ത 0ሽ no matter

D. Thethat the relati e

hat the la er n mber is is lose to 1.1

hi h is the ratio or monola er graphene. The intensit ratio sho ld

i l drop do n

ith thein reasing la er n mber or the sta ing orders other than the AA sta ing.
Anal sis: AA sta ed graphene in o nd in both reg lar

D and O

D. S

h gro th is s ggested to be

attrib ted to in orporation o o gen in the gro th s bstrate. The he agonal (AA sta ing) m ltila ergraphene has been o erloo ed or a long time. Theoreti al al
better arrier transport propert . Prodtion o s

lation sho s that he agonal graphene has

h he agonal m ltila er graphene an be generali ed

or appli ation.
−126−

2020-123（国際）Electronic excitations in charge-density-wave systems
Ming-Wen Chu

National Taiwan University

This proposed research aims at tackling the electronic excitations in charge-density wave (CDW)systems. CDW instabilities have been a well-accepted notion in electronic phase transitions ofsolids and are generally considered to be entangled with the characteristic Fermi surface nesting(FSN). In recent years, systematic examinations of the established CDW phases such as NbSe2,
however, revealed that FSN is not a robust ingredient to the electronic transition, but possibly
the concomitant electron-phonon coupling. The establishment of a firm methodology in sortingout a relevant electron-phonon coupling, therefore, becomes growingly important and electronenergy-loss spectroscopy (EELS) that can capture excited phonon and electronic characteristics
in matters turns out to be a plausible solution in addressing the correlated physics.
The realization of such EELS experiments calls for the simultaneous achievement of two
essential aspects, (i) a high energy resolution of better than 50 meV in order to picture the spectralfeatures of phonon excitations and (ii) a cryogenic specimen environment considering the typical
CDW onset at low temperatures. The two tasks are no routine and expected to be tested together
with Profs. Kurata and Haruta in ICR in 2020. Nevertheless, the COVID-19 pandemic prevents
this current PI from travelling to ICR for the experiments. It is hoped that the upcoming
availability of safe vaccines can twist the situation and international travels to ICR will become
possible again in late 2021 for the proposed research. If not, this PI will try to conduct somepreliminary remote experiments under the assistances of Profs. Kurata and Haruta. Indeed, thisPI deeply appreciates the support of this joint initiative and does look forward to fruitfulcollaboration results in the near future.

−127−

2020-124（国際）Synthesis and characterization ofnovel organoselenium and -tellurium compounds
Mao Minoura Rikkyo University
In recent years, organoselenium and -tellurium compounds have attracted an explosive
increase in research interest regarding their synthesis, structural characterization, reactivity not
only in chemistry but also in biological application.1) It is generally known that
germanium-selenium and -tellurium double bond compounds are highly reactive species andsuch double bond compounds can easily dimerize. By utilizing the bulky protecting group, it ispossible to synthesize and isolate the germanium-chalcogen double bond compounds. Tokitoh
et al. reported the synthesis of the germanium-chalgogen double bond compounds bearing
large aromatic Tbt group. However, in the case of alkyl substituted species, the stable
germanium-chalcogens double bond compound has never been reported due to the difficulty of
the ligand design. Recently, our group has designed and synthesized Trp*, i.e., a novel
triptycene (Trp)-based aliphatic bulky group that bears bulky fused ring-type substituents at the
periphery of the Trp framework. In the present study, we took advantage of the stericprotection of the Trp* group to synthesize the thermally stable germylene Trp*2Ge: and thecorresponding germanium-tellurium double bond compounds.
The treatment of the Trp*2Ge:, which was synthesized by the reaction of Trp*Li andGeCl2,

with elemental tellurium afforded the germanetellone (Trp*2Ge=Te). The isolated

Trp*2Ge=Te is thermally very stable and moisture sensitive, the molecular structure wasdetermined by X-ray crystallographic analysis.
We thank Professors Norihiro Tokitoh, Yoshiyuki Mizuhata, Mariko Yukimoto (ICR,
Kyoto University) and Professor David G. Churchill (KAIST, Korea) for their kind discussions.

1) David G. Churchill et al. Molecules, 2021, 26, 692. doi:10.3390/molecules26030692−128−

2020-125を用いた、含 ッ 共 分
ル
ス相互 用の

の

における

大学

ッ

基は化合 の能を向上させるの なら 、

中での分

にも

するため、n 型有機 導 材 の開 において含 ッ 共 化合 が注目されている。しかし、含ッ 共 分 の
グに ルと分

相互 用の関 には未ス相互 用を的に活用するまでに っていない。特に、ロシ ニンといった平共 分 は有機 導 の 要なXを 成しやすいため基を導入した含ッは共分

ス相互 用に基づいた 共

ル

用X

研究代 者が合成した含 ッモ ー であるが、

ス相互

用の実験的

X

ロシ ニンのに 要な ッス相互 用を活用した含 ッ

基のことを けて、長
を

ッ

しつつ環境

基の

・

性、

と 性

基の開 を

ン ニットが ニ ン ニットで

された長

ル

ル ロ

は じない一方で、長を実するために本

PFOA

ッ

となる長

なり、

ッ

基に期 される特性は

ル

ロ

ル

性を つことが らかとなり、本 ッことがされた。今後は、本 ッ
による ル

基が「

性有

に 加された

ル

ル

ル基を

ロ

）
つ

基が ル

した。
された

ル基と

基を導入したポリ（
ル

ッ

を目指す。

性、クリス ル ンジニ リング特性

基は ル ル ロ ル
ル

し、 ル

国会議（COP9）」でが 能な新規 ッい。

化する。この 見に

共 分 の

第9

に関するストック ルム

見はほとんどをを

本年度の研究では、 ル ル ロ ク ル基に代 される 存の長機 染

共 分 に ッである VariMax を用いて、ン、ポル ィリンやのン やポル ィリン、であることが多く、これらの平における本研究では、化学研究所の基づいて、 ルの点が多く、クリス ル ンジニ リン

ク ンであり、COP9 で指定（PFOA）等の

ート

ッ

ス相互 用

を合成したところ、
と同等の

成果報告

−129−

・

性、

のために有 である

基を導入した含 ッ 共 分 を合成し、ス相互 用評価を実施する。

性されると えられる。このクリ存のした新規 ッX2020-126
Synthesis and structural characterization of low-valent species ofheavier group 14 elements
Tsukasa Matsuo

Kindai University

In this collaborative research, we have planned to investigate the synthesis andstructures of low-valent species of the heavier group 14 elements by taking
advantage of the steric protection using the fused-ring bulky Rind group (Rind =1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl).
The bulky Eind-based bromostannylene, (Eind)BrSn: (1), has been synthesized
by the reaction of SnBr2 dioxane with 1 equiv. of (Eind)Li in THF (Scheme 1). In
contrast, the less bulky EMind-based bromostannylene, (EMind)BrSn: (2), has beenobtained by the ligand redistribution between the diarylstannylene, (EMind)2Sn: (3),and SnBr2 dioxane in toluene. The arylbromostannylenes 1 and 2 can be isolated as
room-temperature-stable orange crystals, and their structures have been clearly
determined by X-ray diffraction methods. While the dimer
formation is found for the bulky Eind-based 1 in which two
Sn atoms are asymmetrically bridged by two Br atoms, theless bulky EMind-based 2 shows a unique one-dimensional
polymeric structure with alternating Sn and Br atoms,
supported by the perpendicularly-oriented EMind groups.

Scheme 1. Synthesis of 1 and 2.

−130−

2020-127
DNP-NMR を利用した

材

能基

法の開
後

ー

ン材

の一つとしてグンやくの研究が行れている。化学的にグ

ン

て

層を

することで

ポリ

ー等との

応用が期

合

化グ

されている。また

いても、

用

ィ

ーなど

があり、そこには
めこの

基や

能基の状

応

化グ

ル

れらの方法では
に

して

を

た。

能基の
的な

を

シ基などの

することが材ない rGO

を Hummers 法により

元した「

開

ン

-7-

ス(3,11-ジ

ジス

べて、S/N

トルとロ[5.1.5.3]

が 1.5 2

度のを有しているため分

動に

な外部

の大きさを

化させながら DNP-NMR

大で 2 3度の感度上本年度は、2020 年
感染拡大による度
い期

が

年

なる出

た。これらについて外部

9.4 T 下に

端の

定を行った

トリ

シ)]

の 13C NMR

ジイル(AMUPol)定で られたスク

認できたが、Hyd-rGO ではほとんど

ングリング

ンドに

化したことが果、S/Nする

えられるため、外部

し、13C NMR にが(2 月 )のしてなど、新型コロナウィルスのがあったため実験を進展できなられたものの、定における S/N
ながら

な

能基

続できるなら

元手法により rGO にどのような

存するかを

ー

ン-1-イル)ウ

成することができた(図 1)。

上に亘った。そのため、rGO

らかにし、様々なナ

能基

ジンを用いてを京都大学化学研究所との共同研究としてば、各種要となっている。従来、ドまで研究を進めることができなかった。2021 年度も本研究テーしている。そのた

ールまたは

果、通

の大きさが

や 2021 年という成果までは
分

を

多くの(NMR)が用いられてきたが、こ共されることが層

や、ン(rGO)」につン-15,7-ジイル

認できなかった。rGO は強度の増強が

担

化グ

能基が存

には[1-(3,6,9,12-テト

定を行った

化し

ルなど多種多様な(DNP)法を用いて、rGO のられる動的核を用いた。MeOH-rGO の 13C DNP-NMRを能であった。本研究では、従来の NMR

は元することで 2 種 の rGO (MeOH-rGO、Hyd-rGO)を定を行った。分

多

テリ

には

において

(XPS)や核の端化して合成した GO を、て 13C DNP-NMR

元

ナ

されている。GO や rGO の分

出感度向上が能な手法として、、バイ

シル基、 ポし、が合成る方法がある。GO はンの能基については X

の

を大

、

の利用が

を

材

ン(GO)をとして化学大学が注目されており、その応用に関して

ンの

能基が

能基

することを目指してさらに研究を進めたいと

手法として
えている。

−131−

Intensity (Arb. Units)

ナ

和

13

C DNP-NMR

13

400
図1

300

C NMR

200 100
0-100
Chemical Shift / ppm

MeOH-rGO の 13C DNP- NMR
および 13C NMR ス クトル

2020-128
平

シリ

ンナ

リ

ンの

設

と新しい動

の

究

まさえ

目的

本研究は研究代

者が設

した平

の

イ

Takahashi Sci. Rep. 2017, 7, 10855.]を ースに二次元に拡
状

シリ

ンナ

す。
「

イ

グ

ある

イ

を

リ

ンを

し、 存の動ン」ともばれる新材 「シリったシートです。グ
めなく、シリンの実

ンとはなり、一部のがのグめて定です。多くの研究者の
ンは

リ

方法

京都大学化学研究所スー

い、

られた

が

は

ンナ

動

ン」は、
に

リ

ン分

をもとに平

平

シリ

ン分

イ

を

定

しました。しかし、新しい拡でがないため、ンは、平、これまで、平のシリ

中できンおよびシリシステムの Materials Studio を用いて第一には、定であることを2 次元シートの設に二次元ッをとるため、ら

つりに同じ 14

した

、

ともに

化を行

認しました。

2018 年度より本共同利用に採択していただき、研究代

果と

ー

を

究を目的としていま

の代

ネル

ール

されています。しかし、シリ

ュー

ンの設

により

の

ス

[M.

ン分

られていません。

ーコン

リ

のナ

なる動

き上がって

的にも実験的にもを行いました。シリ

とは

力にもかか

ンナ

し、平

ンは

の応用が

員環からなるシリ大学者が見出した平を進めてまいりました。研究代しただけでは目的とする平によりようやく平のナリ者が見出した二次元シートは

ンの設

のシ

られ

にたどりつきました。

2020 年度はコロナ感染症拡大のため、 うように共同研究を進めることができませんでしたが、をすすめる中で、この平

シリ

バンド

から、 られた平シリることがかりました。 平

ンナ

設

した平

シリ

*

による

よび
ィ

ク点の存

ンナ
な

リ

リ

深い

性を有することが
バンド

リ

ンは

の

のジグ

グシリ

ンナ

リ

ンは

性を

しました。

的分

ンナ

ンが

特性がバンドにンがイッ

かってきました。

を有する性を有するのとは
の 3p

に 来する

され、

ルミ

の

が見出されました。

成果報告
文
・M. Takahashi, M. Kowada, H. Matsui, E. Kwon, Y. Ikemoto, J. Phys. Chem. A 2021, in press.

−132−

であ
なり、今
外の

お

か上に

2020-129−133−

2020-130
Synthesis and structures of cationic aromatics
bearing thiopyrylium units
Noriyoshi Nagahora

Fukuoka University

Introduction
A variety of organoelectronic devices are based on thiophene derivatives and therefore thiophene
derivatives/analogues with improved properties are highly sought after. In this regard, thiophene-fused
thiopyrylium salts can be expected to exhibit promising potential. However, examples on the synthesis ofthiophene-fused thiopyrylium compounds have so far remained scarce. In this work, we present the synthesisof a new family of thiophene-fused thiopyrylium salts 1 and 2 together with the experimental and theoreticalexamination of their electronic structures.

Results and Discussion
The reaction of bromothiophene 3 with 4-tert-butylbenzenethiol provided thioether 4 in moderate yield.
We attempted the synthesis of thiopyrylium salt 1 via a Rieche formylation followed by a Friedel Crafts
cyclization. Thioether 4 was treated with Cl2CHOCH3 in the presence of the Lewis acid SnCl4, which afforded
thiopyrylium salt 1. Subsequently, we performed the Lewis-acid-promoted intramolecular reaction of 7. In asealed vessel, we carried out a literature method for the In(OTf)3-induced cyclization on 7 in Cl2CHCHCl2.
Cold hexane was added dropwise to the resulting solution and the thus obtained reddish brown powder ofstable bisthiopyrylium salt 2 were isolated in 66% yield by centrifugation.
Crystallization from a saturated solution of 1 in CH3CN afforded single crystals. The molecular structureof 1 was determined by X-ray diffraction analysis using a high-flux diffractometer for single crystals in
Institute for Chemical Research, Kyoto University. The sum of the internal bond angles of all the 5- and 6membered rings in 1 are close to 540° and 720°, respectively, which indicates that the ring framework of 1
exhibits a highly planar structure in the solid state.

Publications
1. Nagahora, N.; Kitahara, K.; Mizuhata, Y.; Tokitoh, N.; Shioji, K.; Okuma, K. J. Org. Chem. 2020, 85,
7748–7756.
2. Nagahora, N.; Tanaka, R.; Tada, T.; Yasuda, A.; Yamada, Y.; Shioji, K.; Okuma, K. Org. Lett. 2020, 22,6192–6196.

−134−

2020-131−135−

2020-132

−136−

2．

研究

報告

．成果

（別刷りは印刷体のみに掲載する）

．

京都大学化学研究所
化学関連分野の深化・連携を基軸とする先端・学際グローバル研究拠点
令和 年度国際共同利用・共同研究公募要領
京都大学化学研究所は、「化学に関する特殊事項の学理及び応用の研究を掌る」ために、化学を中心とする分野で基礎研究に重点を置いた先端研究に邁進してまいりました。平成２２〜３０年度の期間には、文部科学大臣から国立大学共同利用・共同研究拠点としての認定を受け、化学研究所の活性を基盤とする「化学関連分野の深化・連携を基軸とする先端・学際研究拠点」として国内外の化学関連分野の研究者との共同利用・共同研究を推し進めてまいりました。この拠点活動におけるグローバル共同利用・共同研究が評価され、平成３０年化学研究所は文部科学省から国際共同利用・共同研究拠点に認定されました。これを受けて、平成
３１年度からの国際共同利用・共同研究拠点活動においては、多様でグローバルな化学分野の共同研究を一層強力に推進すべく、さらなる事業展開を図っております。
つきましては、化学が関わる分野でご活躍の皆様のご意見・ご要望を尊重しつつ、世界の化学の基礎・応用研究を皆様とともに一層推進することを念頭に置き、下記の要領で令和 2 年度の拠点共同利用・共同研究の課題公募をさせて頂きたく存じます。
この公募に当たりましては、分野選択型（計画研究型）、課題提案型、連携・融合促進型および施設・機器利用型の四つに分けて研究課題を募集いたします。これらの課題の実施に際しては当研究所の専任教員または客員教員との共同研究を基調といたしますが、いずれの課題でも後述の共通設備・機器・資料等のご利用が可能です。なお、各課題とも、海外研究者を研究代表者あるいは研究協力者とする国際共同研究（この場合、英語フォームで申請下さい）と、国内研究者を研究代表者とする国内共同研究を実施致します。これらの点も勘案いただき、本公募要領の詳細について十分ご確認の上、期日までにご申請下さいますようお願いいたします。
京都大学化学研究所長
辻井敬亘
共同研究ステーション長 寺西利治

1．研究期間１年間（令和２年４月１日から令和３年３月３１日まで）。
2．研究課題分類
下記のような分類（型）ごとに研究課題を募集いたします。いずれの課題についても、分類ないし分野の担当者もしくは当研究所で対応する共同研究者にご一報の上、ご申請下さい。また、研究経費に関しては、. の表をご覧下さい。
2-1．分野選択型（計画研究型）研究課題
分野選択型（計画研究型）研究課題は、あらかじめ設定された分野に関して化学研究所内の研究者と共同で遂行する課題です。令和２年度は下記の５分野について課題を公募いたします。５分野を合わせて、萌芽的な課題と発展的な課題をそれぞれ２０件程度、採択の予定です。
ビーム科学分野（担当者：若杉 昌徳； a asu i.masan ri.
ut u.a . ）基本テーマ：先進量子ビームの開発と新奇診断分析手法の創出
趣旨：レーザー、 線、電子線、イオンビームなどの量子ビームの高度化とその先端的診断分析法への応用を進めます。また、これらの量子ビームを複合的に用いて、極微細領域での超高速化学・物理現象の解明を目指します。
元素科学分野（担当者：中村 正治 masa aru s l.
t u.a . ）基本テーマ：元素科学に基づく物質創製・機能創出
趣旨：元素の新たな特性を引き出し、この特性をもとに優れた機能を有する新物質を創製します。元素と社会との関わりを俯瞰した元素戦略研究も推進します。物質の機能は、構成元素の特性を相乗的に反映して発現します。この発現機構を明らかとし、望みの機能を意のままに創出することを目指します。

−159−

バイオ 報学分野（担当者：
ata
ui r.
t u.a . ）基本テーマ：バイオ 報を
複合 報の融合解析
趣旨：
ム
ムに代表される 新バイオ 報に立 して、バイオ 報がいかに
内における化学現象と関わっているかを明らかにし、システムについての化学的理解の深化を図ります。さらに、その成 を応用して、
ム創ーイなどへの展開も目指します。
物質合成分野（担当者：村asu irs l.
t u.a . ）基本テーマ：複合機能 料の戦略的創製
趣旨：
料の イ
化・複合化ならびに
イ 化に重点を置き、新料の創製を目指すとともに、の認 、応 、反応などの 機能を担う料と、機能物質と現象の化学的相関の解明も目指します。

な機能をもつ新世代
等も複合機能現象解析分野（担当者：寺西 利治 teranisi s l.
t u.a . ）基本テーマ：複合 定に基づく物質解析
趣旨：化学を基盤とする多 の分 学的手法・解析的手法を複合的にして、および物質の構 ・
性質を分子レ ルから的レ ルまで 層的に理解・記述することを目指し、一 、そのを元することによって新たな物質科学のみを構 する
みも目指します。
2-2．課題提案型研究課題（担当者：
a i s l.
t u.a . ）課題提案型研究課題は、 項１で設定した一つの分野に まらない分野、あるいはそれ 外の分野について、化学関連分野の研究者からにご提案いただく課題です。萌芽的な課題と発展的な課題を、それぞれ２０件程度、採択の予定です。新分野の開 につながるような課題を特にいたします。なお、性・重要性が極めて高いと 断した課題については、 記の応募期日にかかわらず、に採択することもあります。
2- ．連携・融合促進型研究課題（担当者：
ir s i s l.
t u.a . ）連携・融合促進型研究課題は、化学関連分野における国内外の研究連携の強化を 目的とする共同研究課
題です。国外も念頭に置く場合は、化学研究所の部 間国際学
先 ( tt ://. ui r.
t u.a . /sites/internati nal e
an e/a reement/)との共同研究を開 する場を めていただくことも可能です。また、この目的に った研究集会の開 も本課題として応募いただけます。５件程度を採択する予定です。
2- ．施設・機器利用型研究課題（担当者：
基 urata eels. ui r.
t u.a . ）施 設 ・ 機 器 利 用 型 研 究 課 題 は 、 tt ://. ui r.
t u.a . /sites/researa tivities/ int resear /a eninstr/(拠点 ーム ー )に記 の共通設備・機器・資料等の利用を とする共同研究課題です。
１５件程度を採択する予定です。

−160−

令和２年度国際共同利用・共同研究経費
経費上国際共同研究分野選択型萌芽的研究）
国内共同研究1
1

分野選択型発展的研究
課題提案型萌芽的研究

件（

1
1

課題提案型発展的研究
連携・融合促進型研究1

施設・機器利用型研究1

表中のは目 です。予 のに応じたもあり ますことをご 解下さい。
経費内での備 費、費、 費の 分は、申請者と化学研究所の共同研究者が協 して 定下さい。特に、 費については、 域性を勘案してご 定下さい。

．共同研究応募 法-1．申請資国公 立大学、国公 立研究機関、 立行

法 等の専任研究者、または、これにずる者。

-2．申請 記 要領
申請に当たっては、 当する募集分類・分野の担当者もしくは当研究所で対応する共同研究者と、事 に研究課題、研究内 、研究経費に関して、 ずご協 下さい。対応する共同研究者は、当研究所の専任教員
または令和２年度客員教員からお選び下さい。なお、教員の ス は下記の化学研究所 ーム ー をご
下さい。
教員 ス
tt ://. ui r.
t u.a . /sites/researa tivities/ emist/
また、対応する共同研究者をお めになれない場合は、各分類・分野の担当者に、まず、ご相 ください。
上記の表の経費上 は目 です。特に、経費内での備 費、費、 費の 分については、当研究所で対応する共同研究者と十分にご協 の上で申請下さい。特に、 費については、 域性を勘案してご申請下さい。
課題申請は、本要領にの分野選択型共同利用・共同研究申請 （様 １）、課題提案型共同利用・共同
研究申請 （様 ２）、連携・融合促進型共同利用・共同研究申請 （様 ３）、施設・機器利用型共同利用・共同研究申請 （様 ４）に 要事項を記 し、下記の要領で、化学研究所共同研究推進 にご提出下さい。
なお、各課題とも、海外研究者を研究代表者あるいは研究協力者とする国際共同研究も実施可能です。この場合、英語フォーム（F rms 1 ）のの にを れて、ご申請下さい。
記 上の 意事項
1. を した事項は当研究所で記 します。
. 当研究所で対応する共同研究者は ずご記 下さい。
. 申請者（研究代表者）と共同研究者の分担を明記して下さい。事 に共同研究者のを てい
ただくことが 要です。
. 申請 は内にまとめて下さい。
- ．提出期 および提出先応募に当たっては、 記の申請 にご記の上、令和２年１月２０（月）までに、

い合わせ先
京都大学化学研究所共同研究推進
国際共同利用・共同研究
mail: i r ub s l.
t u.a .
電 : ( 77 )
1 1

−161−

申請して下さい。

．課題選 と採択通
応募課題の採 は、当研究所の共同研究 員会でし、評 会の 認を経て 定されます。
に際しては、共同研究の申請内 だけでなく、予、共通設備・機器・資料の 用 間等も
いたしま
す。採 の
（内定）については、令和２年３月に当研究所の所長から研究代表者に通 いたします。
．研究の実施および研究成報-1．研究経費等
研究代表者と当研究所で対応する共同研究者には、予 の内で、研究経費（備 費および費）と 費がされます。また、研究協力者（学 も めることが可能です ）にも予 の内で 費がされます。共同研究の実施に当たっては、まず対応する共同研究者にご連 下さい。なお、当研究所には、共同研究者のための施設はありませ 。
研究協力者について、学 の場合はとして大学といたします。なお、等にしていることが 要です。
-2．研究成 報採択された研究課題については、研究成 報を に記す 成要領に って記 ・提出していただきます。その報は、まとめて当研究所の国際共同利用・共同研究報集として公開させていただく予定です。また、その内 を研究成 報 会でご報 いただくことがあります。なお、報 会についての詳細は、採択課題の研究代表者に後日お らせいたします。
- ．研究成 報の 成要領
分野選択型研究、課題提案型研究、施設・機器利用型研究については１ 、連携・融合促進型研究については２ の報を（様 ５）を用いて 成下さい。 ４ の用 には１ あたり１ ２００ 程度が記できます。図表など
ーを用いても構いませ が、報集 行の際はロになることもありますので、その点をお み置き下さい。
１ の１行目の中 に研究課題 、３行目にめで研究代表者のと所 、５行目から本文を記 して下さい。なお、当研究所で対応した共同研究者は報の共 者とはせず、 要に応じて本文中に明記して下さい。また、国際共同研究の場合、報は英文でご 成ください。
- ．報
の内
は
ですが、
、実 的研究では、目的、実法、実、、成 報 （ 文、学会
発表等）をお き下さい。なお、連携・融合促進型研究で研究集会を開 した場合には、研究集会の ログ
ム、者（所 機関・部 ・を明記）、および、 成された場合は要旨集または ロシー
ン
グスをして下さい。
- ．報の提出
提出
日は、令和３年２月 日とします。電子フ イル（ r フ イルとF フ イル）を、から提出してください。なお、フ イル は「課題代表者 （ ）」として下さい（ ：1 中.
1 中. ）。
い合わせ先
京都大学化学研究所共同研究推進
国際共同利用・共同研究
mail: i r ub s l.
t u.a .
電 : ( 77 )1 1、

- ．研究成 の公開
学
文などによる研究成 の公開に際しては、京都大学化学研究所の国際共同利用・共同研究として行われたことを明記して下さい。英文でのを に します。
:
is
r
as su
rte b t e nternati nal C llab rative esear
r ram
nstitute r
C emi al eseartniversit ( rant).
日本語でのは、この英文表記に ずるものとして下さい。

−162−

−163−

2

研究

研究

2
研
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2

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2 2

2

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−164−

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−165−

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−166−

2 2

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−167−

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−169−

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サイズ：A4（210×297mm） 背幅：6.5mm

京
都
大
学
化
学
研
究
所
国
際
共
同
利
用
・
共
同
研
究
拠
点

令
和
2
年
度
成
果
報
告
書

京都大学化学研究所 令和 2 年度

国際共同利用・共同研究拠点 成果報告書
化学関連分野の深化・連携を基軸とする
先端・学際グローバル研究拠点