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 年度 成果報告書

4

京都大学化学研究所 令和 4 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 4 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。国際共
同利用・共同研究拠点活動第二期初年度にあたる令和４年度には、化学研究所教員が一丸となって、１９５件の応募の中から採択された１３６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、国際共同研究枠を採択数の４６％に当たる６３件（若手国際枠７件を含む）を遂行しました。しかし、令和２年度から続く世界的な新型コロナウイルス感染症拡大のため、国際・国内共同研究の実施にあたり対面交流が制限される状況が未だ続いております。これを補完する拠点活動支援として、本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・
教育環境整備に引き続き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４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 青山 卓史令和4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
分岐構造を有するらせん状金ナノワイヤーの合成および光学特性評価
2022-1
大阪産業技術研究所
中川 充
2022-2Crystal Structure Analysis of GraE from Root-Nodule-Forming Bacterium
Kansai University Tadao Oikawa
ナノ構造を持つ ISOL 用標的の開発
2022-3
理化学研究所 大西 哲哉
プリパルス付与による高変換TNSA イオン加速機構実証2022-4
光産業創成大学院大学 花山 良平
2022-5
Verification of radiochemical reactions with ultra-high dose rate electrons
National Institutes for Quantum Science and Technology Satoshi Kodaira
元素科学分野2022-6※
Design and Tailoring Advanced Functional Materials: Symmetry Operation andHigh Pressure Synthesis
National Taiwan University Wei-Tin Chen
2022-7※
Carboboration and Carbosilylation by Merging Iron and Visible-Light
Photocatalysis
Visva-Bharati University Alakananda Hajra
2022-8※Computational mechanistic study on the Co-catalyzed nitrogenase model reactions
University of Colombo W. M. C. Sameera
2022-9※Development and device evaluation of new D-π-A emitters based on rigidified
triarylborone acceptors
Julius-Maximilians-Universität Würzburg Todd B. Marder2022-10※ High pressure synthesis of novel hexagonal perovskite oxides containing unusually
high-valence Fe ions and investigation of their magnetic properties
Chinese Academy of Sciences Zhenhong Tan
2022-11※ Preparation and Characterization of Novel Magnetic Quadruple Perovskites byHigh Pressure
CNRS Midori Estefani Amano Patino
2022-12※ High-pressure synthesis and ionic conducting study of novel Na-antiperovskites
containing hydride and cluster anions as solid electrolytes in batteries
Chinese Academy of Science Koedtruad Anucha
2022-13※ Small molecule activation using anionic crypto-FLPs
University of Bonn Rainer Streubel
2022-14※ Development of Unsymmetrical π-Electron Systems of Heavier Main Group
Elements and Elucidation of Their Property
Tohoku University Takeaki Iwamoto
2022-15※ Development of 1,4-Addition Reactions via Iron Catalysis
Indian Institute of Engineering Science and Technology, Shibpur Laksmikanta Adak
2022-16※ Peptide Bolaamphiphile Anchored Nickel-based Metallohydrogel as
Electrocatalyst for Hydrogen Production
Indian Institute of Technology Indore Apurba K. Das※ 国際共同利用・共同研究

－i－

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2022-17Synthesis of Fe-containing Phosphorus Ligands and Their Application in the
Preparation of Metal-Cluster Molecules
Tokushima University Masamichi Ogasawara
自己集合性含ホウ素化合物の合成、集合過程解明ならびに機能開拓
2022-18
鈴鹿医療科学大学 若林 成知
MR-TADF 発光材料を用いた高効率塗布型有機EL 素子の開発
2022-19
関西学院大学小田 晋
2022-20
Synthesis and its catalysis of dinuclear complexes utilizing a pincer-type
N,N,P ligand
Yokohama National University Yoshitaka Yamaguchi
2022-21
Synthesis of Alkyl Ethers Using Two Different Alcohols Catalyzed by
Organosilane Compound
Sanyo-Onoda City University Toru Hashimoto
2022-22Development of heteroacenes with excellent photophysical and electrochemical
properties
Okayama University Koichi Mitsudo
2022-23
Creation of Effective Oxidation Scavenger for Efficient Perovskite-based Solar
Cells
University of Tsukuba Takahiro Sasamori
バイオ情報学分野
2022-24※ Developing machine learning approaches for prediction of protein stabilitychanges upon missense mutations
Monash University Jiangning Song2022-25※ Integrating omics data and module-based network with deep learning to develop
cancer type predictive models
National Yang Ming Chiao Tung University Jinn-Moon Yang
2022-26※ Evolution of giant viruses and relationships with the origin of Life
CEA/Genoscope Morgan Gaïa2022-27※ Revealing marine microbial-viral interactions through community interactome
analyses
CNRS Samuel Chaffron
2022-28※ A Study on Statistical Machine Learning for Efficient Graph Structured Data
Analysis
Nagoya Institute of Technology Masayuki Karasuyama
オミクスデータと流束均衡解析に基づく高温適応進化の機序解明
2022-29
東邦大学 岸本 利彦
2022-30
Control and Analysis of Complex Networks via Probabilistic Minimum
Dominating Sets
Toho University Jose Nacher
2022-31Development of a comprehensive detection method for coronaviruses originatedin wildlife
Osaka University Tokiko Watanabe
2022-32
Microbial ecology in the dark sea
Kyoto University Takashi Yoshida
効果的な分子ネットワーク解析方法の発展と医学・農学への応用
2022-33
帯広畜産大学 茅野 光範※ 国際共同利用・共同研究

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物質合成分野
2022-34※ Investigations into Catalytic and Biochemical Behaviors of Nitrogenase Fe
protein using 57Fe labeling
University of California, Irvine Markus W. Ribbe2022-35※ Precise synthesis and controlling higher order structure of tadpole-like Janus
cellulose nanocrystal
Nanyang Technological University Atsushi Goto
2022-36※ Exploration of perovskite solar cell composition: correlating device performanceand fundamental property
Osaka University Akinori Saeki
2022-37※ Precise synthesis and viscoelastic properties of ring polymers with high purity
and high molecular weight
Nagoya University Atsushi Takano
2022-38※ Exploration of Cycloaddition Properties of Guanidine Functionalized Isatins
Rudjer Boskovic Institute Davor Margetic
2022-39※ Synthesis of Novel Nanotube Molecules with Different Hole Directions by
Introducing a Double Heptalene Structure
Inner Mongolia University Chaolumen
金属酵素化学モデルの創製と材料・医化学への応用
2022-40
山口東京理科大学 太田 雄大
2022-41
Dinitrogen Fixation based on nickel→Z-type (σ-Electron Acceptor) Ligand
Interaction
Osaka Metropolitan University Hajime Kameo
キラルシリカの構造と分子認識との相関解明
2022-42
大阪工業大学 平井 智康
フロー合成法を用いた官能性ビニルテルリド合成法
2022-43
北海道大学 永木 愛一郎
環状ヘキサ-2,7-アントリレンエチニレン誘導体と環状パラフェニレンとのホス
2022-44
ト-ゲスト化学に基づく複合化

2022-462022-472022-482022-49

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小林 健二

44

東北大学
髙橋 裕
Synthesis of Highly Strained Macrocyclic π-Conjugated Molecules via aMultinuclear Au(I)-Pt(II) complex
Tokyo University of Science Yoshitaka Tsuchido
有機電子材料を指向したアザアズレン３量体の合成と応用
久留米工業高等専門学校
黒飛 敬
Development of Organometallic n-Type Materials with High Electrical
Conductivity
Osaka Institute of Technology Michihisa Murata
未踏超不安定構造の単離および物性解明による新概念材料設計指針の創出
東北大学
上野 裕

45

静岡大学
2022-4534

超分岐構造高分子の滑剤作用の解明と最適化

現象解析分野2022-50※ Non-linear viscoelasticity of unentangled polymers
Università degli Studi di Napoli “Federico II” Giovanni Ianniruberto
2022-51※ Nonlinear Extensional Rheology of Entangled Poly(n-alkyl methacrylate)
Melts with Fixed Number of Entanglements and Kuhn Segments per Chain
Chinese Academy of Sciences Shilong Wu※ 国際共同利用・共同研究

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2022-52※

Trace metal elemental and isotopic composition in the North Pacific Ocean:sources and internal cycling (3)Academia Sinica Tung-Yuan Ho
2022-53※ Resolving the structure-dynamics-property relationship in polymer
nanocomposites under uniaxial stretching-II
Stony Brook University Tadanori Koga
2022-54※ High Frequency Response of Polymeric Liquids: Rheology and Dielectric
Relaxation
Yamagata University Sathish K. Sukumaran
2022-55※ Control of Mechanical Properties in Polymer Blend Materials by Hydrogen
Bonding Interaction
Osaka University Osamu Urakawa
2022-56
Analyzing Structural Fluctuation in Thermally Activated Delayed Fluorescence
Materials with Ultralow-Frequency Raman Spectroscopy
Osaka University Hikaru Sotome
2022-57
Effect of microplastics on distribution of trace heavy metals in sea water
Kindai University Yuzuru Nakaguchi
2022-58
Exploration of liquid membrane transportation of metal ions with a polymer
membrane containing ionic liquid by use of electric field response of ions
Kyoto University of Education Hiroshi Mukai
硫黄ポリマー材料におけるナノ構造不均一評価
2022-59
関西学院大学 藤原 明比古
2022-60
Conformation analysis on polymer in food-grade oil
Okayama University of Science Noboru Osaka
プラズモニック合金ナノ粒子を設計するための理論的指針の構築
2022-61
北海道大学 飯田 健二
新規ハイブリッド型部分フッ素化リン脂質二分子膜の構造・物性の解析
2022-62
群馬大学 園山 正史
2022-63
Identification of active gibberellins in the basal land plant Marchantia polymorpha
Kyoto University Takayuki Kohchi
量子情報・スピントロニクス分野
2022-64※ Characteristics of quantum magnon in magnetic insulators
Korea Advanced Institute of Science and Technology Kab-Jin Kim
2022-65※ Observation of orbital Hall effect in transition metal dichalcogenides
University of Ulsan Sanghoon Kim
2022-66※ Investigation on high efficient spin-orbit torque effect in multilayers withcombine anisotropy and DMI
Far Eastern Federal University Alexey Ognev
2022-67※ Research on the efficiency enhancement of the NV centers creation in
nanodiamond
ETH Zürich Takuya F. Segawa
2022-68※ Research toward stable NV centers at shallow region and spin dynamics in diamondHelmholtz-Zentrum Dresden-Rossendorf Gopalakrishnan Balasubramanian2022-69
Demonstration of topological phase control in chalcogenide superlattices
AIST Misako Morota
人工反強磁性体のマグノンを用いた量子情報演算素子の基盤技術開発
2022-70
東京大学 石橋 未央※ 国際共同利用・共同研究

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2022-71

ダイヤモンド量子情報素子のための表面状態研究

金沢大学 徳田 規夫
量子センサの高感度化に向けたリンドープダイヤモンド合成と量子科学技術研究
産業技術総合研究所 牧野 俊晴
課題提案型共同研究
2022-73※ Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune Therapy
Tsinghua University Yan-Mei Li
2022-74※ Evaluation of CaCO3 dissolution rates in deep-sea sediments by a novel tracer
methodXiamen University Pinghe Cai
2022-75※ Advanced Oxygen – mediated Flow Chemistry
Cardiff University Thomas Wirth2022-76※ Novel strategy for intracellular delivery of nanomedicines
Institute for Advanced Chemistry of Catalonia Sílvia PUJALS
2022-77※ Structural and functional analysis of curvature-inducing peptides and application
Karlsruhe Institute of Technology Anne S. Ulrich
2022-78※ In-depth analysis of efficiency roll-off in highly efficient TADF-based organic
electroluminescence devices
The University of Queensland Ebinazar B. Namdas
2022-79※ Intracellular delivery of biofunctional proteins using artificial protein nanocages
Jagiellonian University Yusuke Azuma
2022-80
Real-Time Visualization of Cellular Phase-Separating Proteins
Osaka University Kazuya Kikuchi
合成小分子化合物による細胞の遠隔操作
2022-81
東京理科大学 西川 元也
有機合成・単分子測定・計算化学の協同による2 次元ドナー・アクセプター
2022-82
分子系の構築71

2022-72

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大阪公立大学

三枝 栄子

83

公立小松大学粕谷 素洋

84

大阪公立大学

中瀨 生彦

85

三重大学

江口 暁子

86

Peking University QU, Li-Jia
Construction of heterologous protein secretion system at low temperatures byusing cold-adapted microorganisms
Southwest University Xianzhu Dai
Structural and functional analysis of the surface polysaccharides of outermembrane vesicles released by bacteria
University of Naples Federico II Maria Michela Corsaro
Molecular mechanisms for the inactivation of a growth hormone in rice
Chinese Academy of Sciences Zuhua He

87

2022-842022-85

エクソソームの細胞内への送達設計

2022-86

細胞外小胞の標的細胞への移行メカニズムの解明

2022-90※7582

フッ素系樹脂の摩擦界面における分子挙動の解明

2022-89※

74

木村 謙介

両親媒性希土類錯体を利用した薄膜発光体の作製

2022-88※73

理化学研究所
2022-832022-87※

72

Role of PIP5K Genes in Pollen Tube Development※ 国際共同利用・共同研究

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Analysis of novel transporters for strigolactones or their biosynthetic
intermediates
University of California San Diego Yunde Zhao 91
2022-92※ Phase separation in mixture of nematic liquid crystal and solvent
Japan Women’s University Ryoko Shimada 92
2022-93※ Chromatin, epigenetic and proteolytic regulation of RNA processing in plantmorphogenesis
National Center of Biotechnology RUBIO, Vicente 932022-94※ Site-Selective Protein Acetylation and Phosphorylation by Small Molecules
Fudan University
Lu Zhou 94
2022-95※ Developments of highly efficient and high color purity organic
electroluminescent devices based on thermally activated delayed fluorescentmaterials exhibiting ultrafast reverse intersystem crossing process
Tsinghua University Lian Duan 95
2022-96※ Fabrication of nanotopographical polymer surfaces for bactericidal properties-IV
Stony Brook University Maya Endoh 96
2022-97※ Verification and Development of Dynamic Stiction Theory
Yokohama National University Ken Nakano 97
2022-98※ Synthesis of Polyether Nanocomposite Solid Polymer Electrolytes for Lithium
Ion BatteriesMichigan State University Robert C. Ferrier, Jr. 98
2022-99※ Development and characterization of metal oxide nanocrystalline films for solar
water splitting
RMIT University Yasuhiro Tachibana 99
2022-100※ Interdisciplinary Approach to Nanostructured Materials for Applications
Université de Strasbourg Jean-Pierre Bucher 100
2022-101※ Search for four-wave-mixing in the vacuum - Unveiling dark components in the
Universe Hiroshima University Kensuke Homma 101
2022-102※ Tin-perovskite thin film crystallization on new hole-transporting materials
Helmholtz-Zentrum Berlin Antonio Abate 102
2022-103
Biochemical characterization of aldehyde dehydrogenases involved in thebiosynthesis of plant volatile benzenoids
Yamaguchi University Takao Koeduka 103
2022-104
Regulatory Role of Phytohormone Cytokinin on Leaf Epidermal Cell
Differentiation
Nara Institute of Science and Technology Shiori Aki 104
2022-105Electronic and spintronic properties of multilayer system including NiCo2O4 andFe3O4Hokkaido University Taro Nagahama 105
アルツハイマー病治療に向けたアミロイド光酸素化触媒の構造最適化
2022-106東京大学
金井 求 106
動的効果を考慮した熱活性化型遅延蛍光速度論の確立
2022-107
早稲田大学 浦谷 浩輝 107
2022-108
Analysis of the physiological functions of extracellular vesicles produced byintestinal bacteria and their application
Kindai University Atsushi Kurata 108※ 国際共同利用・共同研究－vi－

2022-1092022-1102022-1112022-1122022-1132022-1142022-1152022-1162022-1172022-118

2022-1192022-1202022-1212022-122

2022-123

Analysis of membrane lipid-dependent fermentation stress response in acetic
acid bacteria
Ritsumeikan Universiy Yosuke Toyotake 109
擬秩序ガラスの熱伝導弘前大学 増野 敦信 110
電気化学的プロトン脱挿入を利用した金属酸化物の新奇物性探索
物質・材料研究機構 土屋 敬志 111
高圧合成による新規フッ化物イオン伝導体の探索
高エネルギー加速器研究機構 齊藤 高志 112
界面活性剤を利用した溶媒含浸樹脂による金属分離
大阪公立大学工業高等専門学校 倉橋 健介 113
全反射近赤外分光法による高分子ブラシ層内の水の構造解析
富山大学
源明 誠 114
3D プリンタを用いたモノリスの3 次元構造制御
共立女子大学 村瀬 浩貴 115
単電子トランジスタにおける巨大磁気抵抗効果の検討
東京工業大学
真島 豊 116
担持金属表面に金属酸化物クラスターを修飾した二元機能触媒の創製
東京都立大学 山添 誠司 117
電子顕微鏡内での単一三次元量子ドット超格子の電子輸送特性と構造相転移挙動の同時観測名古屋工業大学
浅香 透 118
再生可能資源・木質バイオマスの先端化学材料への効率的変換法の開発
奈良県立医科大学
秦野 修 119
Functional analysis of non-canonical strigolactones as plant hormones androot-derived signals
Meiji University Yoshiya Seto 120
Preparation of multi-stimuli-responsive polymer via controlled radical
polymerization
University of Hyogo Shinichi Yusa 121
積層CNT ターゲットへの高強度レーザー照射による高圧ガス生成に関する実験研究
京都大学 松井 隆太郎 122
高強度レーザーと構造性媒質の相互作用による高エネルギー密度プラズマの生成・保持に関する実験研究京都大学 岸本 泰明 123
連携・融合促進型共同研究
2022-124※ Determine the three-dimensional structure of 13C labeled α-synuclein(61-95)
in the Langmuir-Blodgett film and supported phospholipid bilayer by MAIRS2
Middle Tennessee State University Chengshan Wang 124
2022-125※ The 16th International Workshop for East Asian Young Rheologists
Osaka University Tadashi Inoue 126
施設・機器利用型共同研究
2022-126※ Tackling the Electronic Instability of Charge-Density Waves by Electron
Energy-Loss Spectroscopy
National Taiwan University Ming-Wen Chu 128※ 国際共同利用・共同研究－vii－

2022-127※ Micro- and Nano-structural Characterization by Advanced Transmission
Electron Microscopy of Novel Functional Materials
Chiang Mai University Torranin CHAIRUANGSRI 129
2022-128※ High-pressure synthesis of transition metal oxides with novel physical properties
University of Edinburgh Kunlang Ji 130
2022-129※ Synthesis and Characterization of Novel Group 16 Element Compounds
Rikkyo University Mao Minoura 131
2022-130※ Analyzing chemical properties and origins of dissolved organic matter in lakes
and soils by FT-ICR-MS
Kobe University Morimaru Kida 132
2022-131
Preparation of high-efficiency spin-injection materials using optimization ofmagnetism and crystal structure
Nagoya Institute of Technology Masaaki Tanaka 133
2022-132
Development of a highly efficient CsPbBr3 scintillator
Kyushu University Hikaru Saito 134
核融合プラズマ対向材料中の水素・ヘリウム挙動の高精度測定
2022-133
島根大学 宮本 光貴 135
2022-134
Synthesis and Structural Characterization of Lewis Base Adducts of Tetrylenes
Kindai University Tsukasa Matsuo 136
2022-135
Synthesis and structures of cationic aromatics bearing chalconenopyrylium units
Fukuoka University Noriyoshi Nagahora 137
2022-136
Theoretical design of low-dimensional silicon material embedded in a flat
two-dimensional sheet and exploration for operating principles
Tohoku University Masae Takahashi 138※ 国際共同利用・共同研究－viii－

２．国際学会、シンポジウム・研究報告会
国際会議
・24th International Colloquium on Magnetic Films and Surfaces (ICMFS2022)

139

シンポジウム・研究会
・分子材料化学セミナー

141

・第 6 回 MAIRS ワークショップ

143

145

３．成果発表論文（令和 5 年 3 月までに刊行された論文で、平成 22－令和 3 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)* Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes, Nature, 607, 86–90 (2022).
2)* Field-free superconducting diode effect in noncentrosymmetric superconductor/ferromagnet
multilayers, Nat. Nanotechnol., 17, 823–828 (2022).
3) Synthesis of perfluoroalkylene-vinylene-arylene copolymers via the Mizoroki-Heck copolymerization of 1,4-divinylperfluorobutane and 1,6-divinylperfluorohexane with dihalogenatedarylene monomers, J. Fluor. Chem., 261–262, 110033 (2022).
4) Boron complexes of π-extended nitroxide ligands exhibiting three-state redox processes and nearinfrared-II (NIR-II) absorption properties, Dalton Trans., 51, 13675-13680 (2022).
5) Synthesis and characterization of a polystyrene-type polymer bearing a cyclic perfluoroalkylenegroup, Polymer, 265, 125588 (2023).
6) Utilization of sym-tetrazines as guanidine delivery cycloaddition reagents. An experimental andcomputational study, J. Mol. Struct., 1272, 134207 (2023).
7) Consecutive Utilization of Mechanochemical and Microwave Methods for the Synthesis of Boc2-amino-quinazolin-4(3H)-ones and DFT Study of Mechanism 6π-Diazaelectrocyclization
Process, ChemistrySelect, 7, e202200633 (2022).
8) Formation and Stability of Cs2SnBr6 Perovskite Nanocrystals from CsSn2Br5 Nanocubes, J.
Photopolym. Sci. Technol., 35, 199-204 (2022).
9) Hot hole transfer at the plasmonic semiconductor/semiconductor interface, Nanoscale, 15, 657666 (2023).
10) Determine both the conformation and orientation of a specific residue in α-synuclein(61–95) evenin monolayer by 13C isotopic label and p-polarized multiple-angle incidence resolution
spectrometry (pMAIRS), Anal. Sci., 935–940 (2022).
11) Optimized carrier extraction at interfaces for 23.6% efficient tin–lead perovskite solar cells,
Energy Environ. Sci., 15, 2096-2107 (2022).
12) Molecular Engineering of Enamine-Based Hole-Transporting Materials for High-Performing
Perovskite Solar Cells: Influence of the Central Heteroatom, Sol. RRL, 6, 2200590 (2022).
13) Synergistic Surface Modification of Tin–Lead Perovskite Solar Cells, Adv. Mater., 35, 2208320(2023).
14) A Universal Surface Treatment for p-i-n Perovskite Solar Cells, ACS Appl. Mater. Interfaces, 14,56290–56297 (2022).
－ix－15) Composition–Property Mapping in Bromide-Containing Tin Perovskite Using High-Purity
Starting Materials, ACS Appl. Energy Mater., 5, 14789–14798 (2022).
16) Topotactic Oxygen Release and Incorporation in AFeO3 with Fe4+, AFeO2.5 with Fe3+, andAFeO2 with Fe2+ (A = Ca and Sr): Dedicated to the Occasion of the 100th Birthday of Prof. John
B. Goodenough, ECS J. Solid State Sci. Technol., 11, 043004 (2022).
17) High-Pressure Synthesized Perovskite CdMnO3 with C-Type Antiferromagnetic Spin
Configuration, Inorg. Chem., 61, 21011–21015 (2022).
18) Orientation-dependent electrochemical reduction and proton evolution in the oxygen-deficientperovskite SrFeO2.5+y, Appl. Phys. Express, 16, 015506 (2023).
19) Film growth mechanism of mist-chemical-vapor-deposited magnetite, Jpn. J. Appl. Phys., 61,065505 (2022).
20) Charge Transfer between Fe and Ti Induced by Ln Substitution and Temperature in the B-SiteDisordered Perovskites Ln2(FeTi)O6 (Ln = La, Pr, and Nd), Bull. Chem. Soc. Jpn., 95, 1011-1015(2022).
21) LiNbO3-Type Polar Antiferromagnet InVO3 Synthesized under High-Pressure Conditions,Angew. Chem. Int. Ed., 61, e202203669 (2022).
22) Orthogonal antiferromagnetism to canted ferromagnetism in CaCo3Ti4O12 quadruple perovskite
driven by underlying kagome lattices, Communications Materials, 3, 51 (2022).
23) A New Cation-Ordered Structure Type with Multiple Thermal Redistributions in Co2InSbO6,
Angew. Chem. Int. Ed., 61, e202203062 (2022).
24) Incorporation of an Asymmetric Mo-Fe-S Cluster as an Artificial Cofactor into Nitrogenase,
Chembiochem, 23, e202200384 (2022).
25) Transition metal catalyzed cross-coupling and nitrogen reduction reactions: Lessons fromcomputational studies, Adv. Organomet. Chem., 78, 35–78 (2022).
26) Activation of unsaturated small molecules by bio-relevant multinuclear metal-sulfur clusters,
Coord Chem Rev, 475, 214838 (2023).
27) Diastereo- and Enantioselective Metathesis Dimerization/Kinetic Resolution of Racemic PlanarChiral Vinylferrocenes, Org. Lett., 24, 7355–7360 (2022).
28) n-type diamond synthesized with tert-butylphosphine for long spin coherence times of perfectlyaligned NV centers, J. Appl. Phys., 132, 174504 (2022).
29) Low-Frequency Quantum Sensing, Phys. Rev. Appl., 18, 034058 (2022).
30) Electroluminescence of negatively charged single NV centers in diamond, Appl. Phys. Lett., 122,
072101 (2023).
31) Magnetic-field-induced polarity oscillation of superconducting diode effect, Appl. Phys. Express,
15, 113001 (2022).
32) Temperature dependence of domain wall creep motion in ferrimagnetic Tb/CoFeB/MgO
microwires, J. Magn. Magn. Mater., 553, 169251 (2022).
33) Polarization-Selective Excitation of Antiferromagnetic Resonance inMagnetized Synthetic Antiferromagnets, Phys. Rev. Appl., 18, 014032 (2022).

Perpendicularly34) Bismuth composition, thickness, and annealing temperature dependence of the spin Seebeck
voltage in Bi-YIG films prepared using sol–gel solution and spin-coating method, J. Magn. Magn.
Mater., 556, 169416 (2022).

－x－35) Generation of spin-polarized electronic currents using perpendicularly magnetized cobalt ferrite
spin-filtering barriers grown on spinel-type-conductive layers, Appl. Phys. Lett., 122, 042401(2023).
36) Comprehensive understanding of multiple resonance thermally activated delayed fluorescencethrough quantum chemistry calculations, Commun. Chem., 5, 53 (2022).
37) Near-infrared-red-orange thermally activated delayed fluorescence emitters using a strong
tetracoordinated difluoroboronated acceptor, Jpn. J. Appl. Phys., 61, 081001 (2022).
38) Promoting Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence via the
Heavy-Atom Effect, J. Phys. Chem. A, 127, 439–449 (2023).
39) Thioxanthone-containing blue thermally activated delayed fluorescent emitter, Appl. Phys.
Express, 16, 011006 (2023).
40) Imidazole Acceptor for Both Vacuum-Processable and Solution-Processable Efficient Blue
Thermally Activated Delayed Fluorescence, ACS OMEGA, 7, 16740–16745 (2022).
41) A multifunctional hole-transporter for high-performance TADF OLEDs and clarification offactors governing the transport property by multiscale simulation, J. Mater. Chem. C, 10, 86948701 (2022).
42) Dynamic nuclear polarization - nuclear magnetic resonance for analyzing surface functionalgroups on carbonaceous materials, Carbon, 206, 84-93 (2023).
43) Search for sub-eV axion-like particles in a stimulated resonant photon-photon collider with twolaser beams based on a novel method to discriminate pressure-independent components, J. HighEnergy Phys., 176 (2022).
44) Rice husk-derived nano-SiO2 assembled on reduced graphene oxide distributed on conductive
flexible polyaniline frameworks towards high-performance lithium-ion batteries, RSC Adv., 12,14621-14630 (2022).
45) Low-Cost Production of Fe3O4/C Nanocomposite Anodes Derived from Banana Stem Waste
Recycling for Sustainable Lithium-Ion Batteries, Crystals, 13, 280 (2023).
46) Structure-Based Design of Dual Bactericidal and Bacteria-Releasing Nanosurfaces, ACS Appl.
Mater. Interfaces, 15, 3420–3432 (2023).
47) Rheo-Dielectric Behavior of Unentangled Poly(butylene oxide) under Steady Shear: Preliminary
Evaluation of Non-Equilibrium Parameters at the Onset of Nonlinearity, Nihon Reoroji Gakkaishi,
50, 371-385 (2022).
48) Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the Seas of Japanand Okhotsk, Mar Chem, 241, 104108 (2022).
49) A carlactonoic acid methyltransferase that contributes to the inhibition of shoot branching in
Arabidopsis, Proc. Natl. Acad. Sci. USA, 119, e2111565119 (2022).
50) Controlled lipid β-oxidation and carnitine biosynthesis by a vitamin D metabolite, Cell Chem.
Biol., 29, 660-669 (2022).
51) Self-assembling small-molecule adjuvants as antigen nano-carriers, J. Hazard. Mater., 58,
12228-12231 (2022).
52) Magnetic Control of Cells by Chemical Fabrication of Melanin, J. Am. Chem. Soc., 144, 16720–
16725 (2022).
53) Polysaccharide corona: The acetyl-rich envelope wraps the extracellular membrane vesicles andthe cells of Shewanella vesiculosa providing adhesiveness, Carbohydr. Polym., 297, 120036(2022).

－xi－54) Tight association between microbial eukaryote and giant virus communities in the Arctic Ocean,Limnol. Oceanogr.,67, 1343-1356 (2022).
55) "Mamonoviridae", a proposed new family of the phylum Nucleocytoviricota, Arch. Virol., 168,80 (2023).
56) MSNet-4mC: learning effective multi-scale representations for identifying DNA N4methylcytosine sites, Bioinformatics, 38, 5160-5167 (2022).
57) Densest subgraph-based methods for protein-protein interaction hot spot prediction, BMC
Bioinform., 23, 451 (2022).
58) iFeatureOmega: an integrative platform for engineering, visualization and analysis of featuresfrom molecular sequences, structural and ligand data sets, Nucleic Acids Res., 50, W434–W447(2022).
59) Demonstration of efficient relativistic electron acceleration by surface plasmonics with sequential
target processing using high repetition lasers, Phys. Rev. B, 5, 013062 (2023).
60) Stearylated Macropinocytosis-Inducing Peptides Facilitating the Cellular Uptake of Small
Extracellular Vesicles, Bioconjug. Chem., 33, 869–880 (2022).
61) Control over Ligand-Exchange Positions of Thiolate-Protected Gold Nanoclusters Using StericRepulsion of Protecting Ligands, J. Am. Chem. Soc., 144, 12310–12320 (2022).
62) One-Pot Preparation of (NH)-Phenanthridinones and Amide-Functionalized [7]Helicene-like
Molecules from Biaryl Dicarboxylic Acids, J. Org. Chem., 87, 5510–5521 (2022).
63) Small molecule-based detection of non-canonical RNA G-quadruplex structures that modulate
protein translation, Nucleic Acids Res., 50, 8143–8153 (2022).
64) Chiral Open-[60]Fullerene Ligands with Giant Dissymmetry Factors, J. Am. Chem. Soc., 144,
18829–18833 (2022).
65) Multivariate Analysis of Mixed Ternary and Quaternary A-Site Organic Cations in Tin Iodide
Perovskite Solar Cells, ACS Materials Lett., 4, 1124–1131 (2022).
66) Phosphorus ylides of cage-opened sulphide [60]fullerene derivatives, Dalton Trans., 51,
17804-17808 (2022).
67) Aniline-Mediated Imination and Reduction of a Cage-Opened C60 Derivative, Asian J. Org.
Chem., 11, e202200357 (2022).
68) Reaction of an Overcrowded 1,2-Diaryl-1,2-dibromodisilene with 1-Vinylcyclohepta-1,3,5triene: Isolation of a 2-Vinylsilacyclopropane Derivative and Its Thermal Conversion to a
Silacyclopent-3-ene Derivative, Heterocycles, 104, 389 - 396 (2022).
69) Selective Addition of Aniline to a Cage-opened Diketo Anhydride Derivative of C60, Chem. Lett.,
51, 949-952 (2022).
70) Discovery of a phase-separating small molecule that selectively sequesters tubulin in cells, Chem.
Sci., 13, 5760-5766 (2022).
71) A noncanonical endocytic pathway is involved in the internalization of 3 μm polystyrene beads
into HeLa cells, Biomater. Sci., 10, 7093-7102 (2022).
72) Synthesis and structure–activity relationship of 16,17-modified gibberellin derivatives,
Phytochem Lett, 49, 162-166 (2022).
73) Characterization of resonance structures in aromatic rings of benzene and its heavier-element
analogues, Phys. Chem. Chem. Phys., 24, 22557-22561 (2022).
74) C2-insertion into a fullerene orifice, Chem. Commun., 59, 1645-1648 (2023).

－xii－75) Electric field effect on spectroscopic g-factor and magnetic anisotropy in a Pt/Co/MgO ultrathin
film, Jpn. J. Appl. Phys., 61, 103001 (2022).
76) Near-Infrared-Absorbing Chiral Open [60]Fullerenes, Angew. Chem. Int. Ed., 62, e202215380(2023).
77) Perovskite/Perovskite Tandem Solar Cells in the Substrate Configuration with Potential for
Bifacial Operation, ACS Materials Lett., 4, 2638–2644 (2022).
78) Pulse-width dependence of spin–orbit torque switching in Mn3Sn/Pt thin films, Appl. Phys. Lett.,
122, 122405 (2023).

４．参考資料159
163

4-1.令和４年度公募要領
4-2.令和４年度採択課題一覧－xiii－

－xiv－

1．共同研究成果報告2022-1分岐構造を有するらせん状金ナノワイヤーの合成および光学特性評価
中川充 大阪産業技術研究所【目的】局在表面プラズモン共鳴に由来した特異な光学活性を示すナノ材料は、不斉合成やメタマ
テリアルなどへの応用が期待されることから、盛んに研究されている。しかし、キラルな貴金属ナノ構造の複雑な制御やそれらの光学特性を調節する技術については改良の余地が多く残されている。本研究では、これまでに合成法を確立したらせん状金ナノワイヤー（Au NWs）について、分岐構造を修飾することでその特異な光学特性を制御、増強させることを試みた。
【方法】先行研究で合成に成功している直径 3 nm で分岐のない右巻きらせん状 Au NWs に化学的処理を施すことで分岐構造を形成させた。修飾はシード粒子となる Au NWs の水分散液に、金前駆体として塩化金酸、保護剤として長鎖アミン誘導体、還元剤として L-アスコルビン酸を添加し、23 ℃で 7 日間撹拌することにより行った。
【結果と考察】得られた Au NWs のナノ構造を
透過型電子顕微鏡（TEM）により観察したところ、分岐構造の形成を確認した。シードとして用いた Au NWs は多結晶であり、「幹」となる部
分の表面には結晶粒界などの格子欠陥を多く有している。今回試みた分岐修飾処理では、これらの格子欠陥を起点とした分枝の生成および異方成長が起こっていると推測される。そこ

Fig. 1. TEM images of branched Au NWs. Yellow
area shows crystalline domain.

で、分枝状 Au NWs の枝および幹の部分について、高分解能 TEM 観察による結晶構造の評価を行った。幹の部分についてはシードとして用いた Au NWs と同様に多くの結晶粒界や Au の面心立方格子に由来する様々な周期の格子縞が観察された。一方、枝の部分は幹の部分と比べて非常に大きな結晶ドメインにより形成されていることが分かった（Fig. 1）。また、これFig. 2. Dis-symmetry factor (g-factor) of Au NWs.

らの結晶ドメインの多くから Au(111)に由来する格子縞が観察されたことから、枝の部分は主にAu(111)方向への異方成長によって形成されたと考えられる。
続いて、得られた分枝状 Au NWs について光学特性の評価を行った。分枝状 Au NWs はシードとして用いたらせん状 Au NWs と同様、近赤外領域に強い吸収帯を有し、円二色性を示すことが分かった。興味深いことに、吸光度に対する円二色性（g-factor, Fig. 2）が、分岐構造の形成後大幅に増大した。円二色性の増強が Au NWs のどのような構造変化に起因するか現在調査中である。

－1－

2022-2
Crystal Structure Analysis of GraE from Root-Nodule-Forming Bacterium
Tadao Oikawa

Kansai University

Rhizobium is a genus of tubercle-forming bacteria. It grows in symbiosis with the root of aplant to fix nitrogen from the air. During a screening experiment, Rhizobium sp. strain MTP10005 was isolated from natural river water. Enzymological and genetic studies showed that thetranslational products of the gene cluster graRDAFCBEK in the bacterium (GraR, GraD, GraA,
GraF, GraC, GraB, GraE, and GraK, respectively) were probably involved in the degradation
pathway of γ-resorcylate. To reveal the structure and function of all these proteins, I havecollaborated with Dr. Tomomi Fujii and Prof. Emeritus Dr. Yasuo Hata, Institute for Chemical
Research, Kyoto University, and have performed already X-ray structural studies of GraA, GraC,
and GraD. In this study, we focused on GraE, whose function and role in the degradation pathwayof γ-resorcylate are currently unknown. The protein consists of 112 amino acid residues. The Xray crystal structure of GraE is expected to reveal its function and role in vivo.
N-terminal His-tagged GraE was overexpressed in Escherichia coli BL21 (DE3), purified, andused for crystallization. Thin plate-shaped crystals were obtained using a crystallization solution
consisting of 1.17 M NaH2PO4・K2HPO4, pH 8.4. Diffraction experiments were performed on
beamline BL-17A, Photon Factory, KEK, Japan. The crystal was mounted with a cryoloop andcooled with a cold stream of nitrogen. Diffraction data were collected up to 2.2 Å resolution. The
crystal belonged to space group P21212, with unit-cell parameters of a = 89.84 Å, b = 165.31 Å,and c = 45.20 Å. The structure was determined using the molecular replacement method withthe structural model determined in the P21 crystal. The solution model was subjected to iterativemodel-building and refinement. The structure was refined to an R-factor and Rfree of 20.5 and27.6%, respectively.
In the present crystal, three homodimer GraE molecules exist in an asymmetric unit. The
subunit structure consists of three α-helices and five β-strands, and it roughly resembles abacterial-type ferredoxin fold. The dimer interface is formed by packing the four-stranded βsheets from the two subunits against each other. The putative active site is located in a cleft madeof an α-helix α1 and two β-strands β2 and β3 from one subunit and C-terminal loop from theother subunit. In a dimer molecule, the phosphate ion in the putative active site binds to the side
chains of arginine, histidine, and tyrosine residues. The arginine and histidine residues areconserved among related proteins and may be involved in substrate binding or catalysis.
Additionally, the side chains of glutamic acid and aspartic acid residues presented on themolecular surface of an adjacent molecule, form hydrophilic interactions with the entrance of
the active site of another dimer molecule.

－2－2022-3－3－

2022-4
プリパルス付与による高変換 TNSA イオン加速機構実証
花山良平

光産業創成大学院大学

我々は Target Sheath Normal Acceleration(TNSA)イオン加速機構で得られる MeV 以上の高エネル
ギーイオンを利用し、高輝度（点光源）、短パルス（数 10 ナノ秒以下）で比較的コンパクト（規模に比較して高フラックス）なレーザー駆動中性子源の実現を目指している。これを高時間分解中性子検出器と組み合わせることにより、共鳴散乱イメージングなど、レーザー加速中性子源の特徴を生かした研究展開が期待できる。
これまでの研究で、高強度フェムト秒レーザーパルスに先行して、適切なタイミングでプリパル
スをターゲットに照射することにより、加速イオンのエネルギと粒子数を増大させる手法の実証を京都大学化学研究所のレーザー施設を用いて行ない、加速プロトン数と最大エネルギの増大を確認した。本課
題では、プリパルスが初期ターゲット条件及び TNSA 機構に及ぼす影
響を物理的に解明し、これを制御する手法の構築を目指した。
まず、昨年度の実験でプロトンエネルギー解析に用いたプラスチッ

図 1 プロトンエネルギ
ー解析用 CR39

ク飛跡検出器 CR39 のエッチピットの顕微鏡観察を行った。図 1 の 5
本のトレースの内、4 本目の 1MeV 付近では中央部が暗くなっている部分が存在した（図 2）。これを拡大して観察したところ（図 3）、無数のピットで埋め尽くされ、全体的にエッチングが進んだために暗くなったと考えられることが分かった。
次に、昨年度見出したレーザーシャインスルーがターゲットの初期状態に及ぼす影響について検討を行った。TNSA レーザーイオン加速

図 2, 顕微拡大 300 倍の計算と実験結果の乖離を説明するためにレーザーシャインスルー数(4 本目, 1MeV 付近)

値モデルを構築して解析を行った。その結果，プリパルス照射によりプラスチックターゲットのレーザー照射側（前面）がブレークダウン
する際、ターゲットの反対側（裏面）の自由電子密度もほぼ臨界密度に到達することがわかった。このことはプリパルスのシャインスルー
によりターゲット裏面の状態が変化し、TNSA によるイオン加速が阻
害される可能性を示唆している[1]。
この結果を元に、レーザー照射点近傍のターゲットやプラズマの挙

図 3, 顕微拡大 4000 倍動を実験により詳細に観測することとした。ターゲット形状の計測や(4 本目、1MeV 付近)

プラズマ観察用の干渉計などの準備を進めている。
1) 砂原淳, “高強度レーザーシース加速における“シャインスルー”,” フォトニクスニュース,

8, 2, 72-77 (2022).

－4－2022-5
Verification of radiochemical reactions with ultra-high dose rate electrons
Satoshi Kodaira

National Institutes for Quantum Science and Technology

The radiotherapy for cancer that is performed at an ultra-high dose rate (>40 Gy/s) has attracted great interest
because the tumor cell-killing effect is maintained while the damage to surrounding normal tissues isminimized. This sparing effect is related to the yields of water radiolysis products, which contributes to theindirect action toward DNA strand breaks. In this study, we verify the radiation chemical yields of products inwater by irradiation of ultra-high dose rate electrons.
20 MeV electron beam irradiation was performed in ambient air condition at electron linac, KEL of ICR. The
mean dose rates were 0.08 and 0.3 Gy/s, which correspond to the pulsed dose rates of 2.7 and 10 kGy/s,
respectively. Aqueous solutions containing 2.5 mM sodium nitrate (NaNO3) were prepared to measure yieldsof hydrogen peroxide. Ultra-pure water was also irradiated to compare yields with/without sodium nitrate.
After the irradiation, we analyzed the yields of hydrogen peroxide produced using an electro-chemical detector(ED743) connected to HPLC system (Shimadzu, Japan).
Figure shows yields of hydrogen peroxide produced in a 2.5 mM sodium nitrate solution (solid symbols) andultra-pure water (open symbols) at low and high dose rates as a function of the absorbed dose. In NaOH3
solution, the slope at high dose rate is steeper than that at low dose rate. This result implies that reactions
between OH radicals more efficiently occur in high dose rate region, resulting in high yields of hydrogen
peroxide. The G values of hydrogen peroxide in NaOH3 solution were 0.99 sp/100 eV and 0.78 sp/100 eV athigh and low dose rates, respectively. The value at low dose rate was in agreement with the previous study of
gamma rays (0.7 sp/100 eV) at similar low dose rate of 5.6 Gy/min (~0.09 Gy/s). A similar trend that the slopeof hydrogen peroxide generated becomes steep with increase of the dose rate was observed in ultra-pure water.
The G values of hydrogen peroxide in ultra-pure water were 0.63 sp/100 eV and 0.36 sp/100 eV at high andlow dose rates, respectively, which were much lower than that in NaOH3 solutions at the same dose rate ineach. The sodium nitrate works as a scavenger of hydrated electrons, which disassemble hydrogen peroxide,
thereby the hydrogen peroxide produced was maintained by suppressing roles of hydrated electrons. To explain
the roles played by hydrated electrons in a wide scavenging time scale, we will address the hydrogen peroxide
measurements by varying the concentration of sodium nitrate.

Figure. Dose dependencies of yields of hydrogen peroxide produced in a 2.5 mM sodium nitrate solution (opensymbols) and ultra-pure water (closed symbols) at two dose rates of 0.08 Gy/s (low) and 0.3 Gy/s (high).

－5－

2022-6（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. With various advanced sample
preparation approaches, high pressure synthesis techniques are one of most important
methods in preparation of such novel functional materials. It is aimed to design andrealize metastable oxide materials with exotic phase transitions contributed from thelattice/charge/orbital/spin degree of freedom. The joint collaborative research has been
carried out with Advanced Solid State Chemistry Laboratory (Prof. Shimakawa) utilizing
extreme pressure and temperature synthesis conditions, and high resolution synchrotron
x-ray diffraction (SXRD) at Taiwan Photon Source (TPS) for structure analysis.
[Results and discussion] The joint research remains difficult with the situation ofpandemic in year 2022. Nevertheless, the idea exchange and online discussion werecarried out, and high pressure experiment and diffraction data collection were conducted
at ICR and TPS, respectively. For instance, an unreported A2+Mn4+O3 perovskite member
CdMnO3 were realized with high pressure synthesis condition. The SXRD experiment
reveals that the compound crystallized in distorted perovskite structure, and magnetic
susceptibility shows an antiferromagnetic behavior, in which First-principles calculation
indicates a C-type magnetic structure. [1] The followed up investigation of previously
reported on PrFe0.5Cr0.5O3 system [2] are continued. A series of praseodymium-containing
perovskites were synthesized, and the evolution of crystal and magnetic structures were
carefully examined. From neutron diffraction results, it is shown that with increasing Mn
doping into PrCrO3 parent compound, themagnetic structure changes drastically fromG-type dominant to A-type dominant. The
further detailed analysis is ongoing and themanuscript is in preparation. [3][Results and discussion]
1. Y. Xu et. al., Inorg. Chem., 61, 21011 (2022)
2. C.-W. Wang et. al., JMMM, 538, 168273 (2021)
3. Y.-H. Tung et. al., manuscript in preparation－6－

Fig. 1 Compositional magnetic phase diagram of
PrMnxCr1-xO3 perovskite series.

2022-7（国際）Carboboration and Carbosilylation by Merging Iron and
Visible-Light Photocatalysis
Alakananda Hajra

Visva-Bharati University

ICR partner researcher’s name: Prof. Masaharu NAKAMURA
Objective: Development of carboboration and carbosilylation reactions using earth-abundant
non-toxic Fe-catalysis under visible light photo-catalysis at room temperature

Visible-light photocatalysis has become an impressive tool in organic synthesis. In thisrealm, the merger of transition metal catalysis and visible light photoredox catalysis offers an
exciting opportunity to perform the organic transformations in mild conditions. Organosiliconcompounds are one of the vital synthetic building blocks in the field of organic chemistry and they
have widespread applications in material science, polymer science and agrochemistry. Notably, thesilicon analogues of biologically active molecules and organosilicon compounds exhibit exceptional
physicochemical properties, allowing them to be extensively used in medicinal chemistry. Presently
we are studying a three-component carbosilylation of alkenes with imidazoheterocycles and silanes
by merging visible light photocatalysis and iron(II) catalysis .

Presently we are focusing on the precise role of FeCl3 and visible light, and late stage modificationof the compound.
A review has been published. This work was also supported by the International Collaborative
Research Program of Institute for Chemical Research, Kyoto University (grant # 2022-7).
Title: Recent Advances in Carbosilylation of Alkenes and Alkynes
Authors: Prajna Paramita Pal, Sumit Ghosh, and Dr. Alakananda Hajra*
Org. Biomol. Chem., 2023, Accepted Manuscript
https://doi.org/10.1039/D3OB00230F－7－

2022-8（国際）Computational mechanistic study on the Co-catalyzed nitrogenase
model reactions
W. M. C. Sameera

University of Colombo

Transition metal clusters can be used as catalysts to perform chemically or
biologically relevant reactions.1,2 Relationships between the electronic structure andreactivity can be established by employing density functional theory (DFT). We havedeveloped [Mo3S4M]-type clusters (M = Fe, Co, Ni), consisting of bulky
cyclopentadienyl ligands (CpXL, C5Me4SiEt3). CO can be coordinated to [Mo3S4M]
cubes. According to experimental data, [CpXL3Mo3S4M(CO)]+ (M = Co, Ni) is stable,
while [CpXL3Mo3S4Fe(CO)]+ complex revealed unexpected instability. DFT
calculations analyzed their M-CO interactions.
An energy decomposition analysis (EDA), together with the natural orbitals forchemical valence (NOCV), was performed to rationalize the M-CO interactions. Theinteraction energy between M and CO follows the order of Fe-CO (-101.1 kcal/mol)> Co-CO (-81.5 kcal/mol) > Ni-CO (-77.3 kcal/mol). In all three cases, orbital
interactions
dominant
electrostatic,

becomecomparedtodispersion,and solvent interactions.
According to EDA-NOCV,
π back-donation from Co to π*(CO) is stronger than 𝜎𝜎 CO to M(d) 𝜎𝜎 donation for all
three systems. These findings give quantitative insights to develop bio-mimetic
catalysts for the direct conversion of CO into hydrocarbons.
Joint Publications of this fiscal year
(1) Y. Ohki, K. Munakata, R. Hara, M. Kachi, K. Uchida, M. Tada, R. E. Cramer, W.
M. C. Sameera, T. Takayama, Y. Sakai, S. Kuriyama, Y. Nishibayashi, K. Tanifuji,
Nature, 607, 86-90 (2022).
(2) W. M. C. Sameera, Y. Takeda, Y. Ohki, Adv. Organomet. Chem., 78, 35-78 (2022).
(3) K. Tanifuji, Y. Sakai, Y. Matsuoka, M. Tada, W. M. C. Sameera, Y. Ohki, Bull.
Chem. Soc. Jpn., 95, 1190-1195 (2022).

－8－

2022-9（国際）Development and device evaluation of new D-π-A emitters based on
rigidified triarylborone acceptors
T. B. Marder

Julius-Maximilians-Universität Würzburg

Thermally activated delayed fluorescence (TADF) emitters are a promising avenue for thedevelopment of organic light-emitting diodes (OLEDs) for flat displays and solid-state lighting
applications, as they show improved efficiency. Planar 3-coordinate boron can be used as an
acceptor moiety due to the vacant pz orbital. Triarylboranes have been employed for a number ofapplications such as linear and nonlinear optics, sensors, and OLEDs. One of the most successful
examples of the use of triarylboron acceptors is their application to TADF emitters. We haverecently reported methodologies to enhance the accepting properties as well as the stability ofboron by the introduction of ortho-trifluoromethylaryl moieties. We computationally designed aseries of D-π-A TADF emitters with fluorinated triarylboron acceptors. We synthesized sufficientquantities of 3 blue to red emitters with relatively short delayed fluorescence lifetimes, implying
efficient reverse intersystem crossing (RISC) from the triplet to singlet excited states (A. K.
Narsaria et al., Adv. Funct. Mater. 2020, 30, 2002064). These studies demonstrate the effectivenessof our design strategy for triarylboron-based TADF emitters based on accurate theoreticaldescriptions of the local and charge-transfer states. The Kaji group has been constructing OLED
devices by both wet and vacuum processes from these compounds and examining their properties.
A PLQY of 70% and an EQE of 10% have already been achieved for one of the compounds. They
are continuing to attempt to improve device performance for the other compounds. In addition, theKaji group has carried out computational work to design a new family of boron-based TADF
chromophores employing a rigidified triarylboron core. Based on those calculations, my group has
begun to synthesize a series of these new chromophores. We have already been successful in
preparing the desired rigidified diboron-containing core and, using Ir-catalyzed borylation, haveborylated it selectively at the 2 sites required for subsequent cross-coupling with a specific seriesof donor moieties. As the chromophore synthesis and purification is completed, we will send eachcompound to the Kaji group for incorporation into OLED devices.
This past year, due to COVID-19 relateddifficulties, and the inability to travel to
Kyoto, our group and the Kaji group have
independently advanced the project: ourgroup carrying out the chemical synthesis of
the chromophores and the Kaji group
Figure 1. Fabricated OLEDs by the Kaji groupcarryingout
thephotophysicalusing our designed materials.
measurements, device fabrication andtesting (Figure 1). Very promising results have been obtained from new OLED devices preparedfrom our original compounds. We will continue to prepare the new series of chromophores and theKaji group will evaluate their device performance in the coming year. We anticipate that abreakthrough in OLED performance can be achieved by continuing our collaborative work, andthis is highly desired in both the academic and industrial communities.

－9－2022-10（国際）－10－2022-11（国際）Preparation and Characterization of Novel Magnetic Quadruple
Perovskites by High Pressure
Midori E. AMANO PATIÑO CNRS
Objectives. We set out to investigate the formationof A-site ordered quadruple perovskite materials withformula CaA’3Ti4O12 (A’ = Mn2+, Fe2+, Co2+, Ni2+, Cu2+)
and to characterize and compare the physical properties
throughout the series. The transition metal cations in thesematerials take square-planar coordination geometry at theA’ sites (Fig. 1). In addition to this coordination being rare,
when only the A’ sites are magnetic, their orthogonalarrangement in the quadruple perovskite structure leads to Fig. 1 The quadruple perovskite
complex magnetic interactions and exotic magnetic orders structure adopted by CaA’3Ti4O12
materials.
that are not yet well understood.
Methods. Stabilizing quadruple perovskite structures is often challenging, and their
preparation requires high pressure and temperature. In this collaboration, the high-pressure
apparatuses at the Advanced Solid State Chemistry Laboratory led by Prof. Yuichi Shimakawa
made it possible to investigate the preparation of the target CaA’3Ti4O12 series. Following our
success in stabilizing the member with A’ = Fe2+,[1] we focused on preparing A’ = Mn2+, Co2+
and Ni2+. Initial exploration of the phases was carried out using laboratory X-ray diffraction(D8 Advance, Bruker) and SQUID magnetometry (MPMS-XL and 3, Quantum Design). For
the Mn2+ and Ni2+ compositions, further detailed exploration of formation was required (highpressure synchrotron X-ray diffraction, BL04B1, SPring-8). Meanwhile, neutron powder
diffraction (NPD) measurements were performed for our product A’ = Co2+ (ECHIDNA, OPAL
reactor, Sydney, Australia).
Results and Discussion. Data collected in situ during the formation of the A’ = Mn2+, Ni2+
materials (from CaTiO3 and A’TiO3) at BL04B1, using several pressure and temperature
combinations, revealed that the stabilization of the target materials is challenged by competing
phases which are thermodynamically favored (e.g., CaMnTi2O6 and NiO, respectively).
Therefore, isolation can only be achieved within a very narrow window of P, T conditions. The
discussion of these results is being prepared for publication.
For the A’ = Co2+ material, NPD confirmed the successful stabilization of the target
structure. Additionally, unusual features detected by SQUID magnetometry led us to explore
NPD under applied magnetic fields. The results reveal that in the absence of an external
magnetic field, the Co2+ spins adopt antiferromagnetic ordering at 9.3 K. This magnetic
arrangement consists of three interpenetrating spin sublattices perpendicular to each other.
When a magnetic field is applied, the antiferromagnetic structure transforms into a canted
ferromagnetic arrangement. In comparing this magnetic behavior with the A’ = Fe2+ member
and other quadruple perovskite systems previously investigated at Prof. Shimakawa’sLaboratory, we discovered that underlying Kagome lattices (formed by 2nd A’ neighbours) inthese systems are crucial in determining the adopted spin structures.[2]Outcomes. This collaboration has been successful in yielding many important results.
Our investigations on this quadruple perovskite series provides a relevant contribution inunderstanding the composition-structure-property relationships in this class of materials. We
have gained valuable insights into the underlying factors that govern these relationships.
Acknowledgements. MAP thanks Prof. Shimakawa’s Laboratory members, and the beam scientists at BL04B1
and ECHIDNA, for their help and fruitful scientific discussion. References. [1] Amano Patino, M. et al. Phys.
Rev. Research, 3(4), 043208 (2021). [2] Amano Patino, M. et al. Commun Mater, 3(1), 51 (2022).

－11－

2022-12（国際）High-pressure synthesis and ionic conducting study of novel Na-antiperovskites
containing hydride and cluster anions as solid electrolytes in batteries
KOEDTRUAD Anucha CAS
Research background and objectives
All-solid-state Na-ion batteries are considered next-generation energy storage devices. As the key
component in the batteries, solid electrolytes with Na-ion conducting properties have been intensively
investigated. Recently, hydride-based Na-antiperovskites, Na3HCh (Ch = S, Se and Te), have been
revealed as potential electrolytes [Nat. Commun. 2021, 12, 201]. Therefore, herein, we aim to explore
new Na-antiperovskites containing hydride and cluster-anions (CA) with general formula (Na)n(H)(CA).
Initially, Na3(H)(SO4) is focused.
Materials Synthesis and Characterization
The materials were prepared via a high pressure high temperature technique using an ELEPHANT
high pressure apparatus in the Advanced Solid State Chemistry laboratory in ICR. Starting materials,
NaH and Na2SO4 were mixed and grinded in a glovebox. The mixture was then loaded into a Pt or Au
capsule (capsule size is about 10 mm diameter and 15 mm height). The capsule was then assembled
before transferring from the glovebox to the high pressure apparatus. The applied pressure was between
60 - 250 ton and the temperature was 350 oC. The obtained materials were then characterized by aconventional XRD. Its phase was analyzed with rietveld refinement method.
Results and discussion
Figure 1 shows XRD patterns of Na3(H)(SO4)prepared under different pressures. At high pressureof 250, 200 and 100 ton, the patterns indicate mixed
phases. With reducing pressure to 60 ton, the target
antiperovskite phase becomes dominant with theminor NaH and Na2SO4 phases remained.
Figure 1. XRD patterns of the Na3(H)(SO4)prepared at different pressures
With grinding the sample and repeating the synthesis at
60 ton and 350 oC for two times, yield of the
antiperovskite phase is enhanced, accompanying with
reduced impurity phases, as shown in Figure 2a. The
best sample is then chosen for the rietveld refinement foranalyzing structure (Figure 2b). The result indicatesnearly phase-pure antiperovskite structure with atetragonal unit cell, space group P4/nmm. The structure
comprises of HNa6 octahedral networks and SO4 groupin cavity of the network. However, the detailed structureneeds further characterization with high resolution
synchrotron XRD and/or neutron powder diffraction
techniques. Conductivity of the compound will be next
examined with AC impedance spectroscopy.
Figure 2. XRD patterns of the sample after grinding and repeating the synthesis
for two times (a) and refinement result and refined structure of the sample (b).

－12－2022-13（国際）Small molecule activation using anionic crypto-FLPs
Rainer Streubel

University of Bonn

This collaborative research project was carried out with Prof. N. Tokitoh and Prof. Y. Mizuhata(ICR, University of Kyoto), and 1 PhD student from Bonn was hosted in Japan.
Objectives: The project targeted the synthesis of anionic FLPs, featuring an anionic phosphorus
center as Lewis base and a tetravalent chloro(organo)silicon compounds as masked Lewis base.
Experimental methods: Inert-gas synthesis techniques, analytical methods (NMR, IR, UV/vis,
CV, X-ray).
Experimental results:
The project focused on a more reliable starting point using robust P-bound triphenylmethyl derivatives (Trityl, Trt).
Discussion: Firstly, we examined a route using HOAc to get 1, then by reaction with LDA thedesired precursor 2b, but the product quality varied in an unpredictable manner. We then developed a new route relying on the imidazole-to-phosphorus adduct complex 3 which react withwater to 4 and which was obtained in good yields, high purity and can be stored. Complex 4 waseasily deprotonated with several bases, e.g. NEt3, nBuLi or KOtBu; 2c was used to access 2d.
2a was treated with Me3SiCl, Me2SiCl2, iPr2SiCl2 and tBu2SiCl2, and the resulting siloxyphosphane complexes 5a-c were obtained in good yields, except for 5d as no reaction occurred.
(OC) 5W
H

Bisyl

P

(OC) 5W

O

P

LDA

Trt

H OAc
1

[Li(12-c-4)](OC)5W

I(OC) 5W

P
N

P
H O
M
2a-d

Trt

N

H2O

(OC) 5W

-MeIm

H

3

P

Trt

Trt

base

M = HNEt3 ( a)
Li
( b)
K
(c)
PPh4 (d)OH

4

SiRnCl3-n+1- MCl(OC)5WP

Trt

H O
RnCl3-nSi

5a-d
R = Me, n = 3 (a)n = 2 (b)i
R = Pr, n = 2 (c)R = tBu, n = 2 (d)Complexes 5b,c react with KHMDS via deprotonation to giveroom temperature stable K/OR phosphinidenoid complexes 6b,cbeing under current investigation.[1](OC) 5W

P

Trt

KHMDS

H O
Cl SiR2 - HMDS
5(OC) 5WP

Trt

O
Cl SiR2
6

K

Publications:[1]P. Brehm, D. Biskup, G. Schnakenburg, Y. Mizuhata, N. Tokitoh, R. Streubel, to be published.
－13－2022-14（国際）Development of Unsymmetrical π-Electron Systems of Heavier Main
Group Elements and Elucidation of Their Property
Takeaki Iwamoto

Tohoku University

Objectives: We aimed at developing unsymmetrical π-electron systems containing adouble bond between group-14 and group-13 elements, which remain scarce comparedto other heavier π-electron systems but expected as prospects for advanced materials andreagents for small molecule activation.
Experimental Methods: Reactions of B-(2,2,6,6-tetramethylpiperidyl)dialkylborasilene
1 (Chart 1) was various reagents were examined.
Outcomes: Borasilene 1 reacted with CO2 to provide 2 which is a product resulting fromthe activation of two CO2 molecules. The detailed analysis of this reaction revealed thatthe initial product of this reaction is a formal (2+2) adduct of 1 and CO2 (3). Then theelimination of CO from 3 provides borasilaepoxide 4, which converts to 2 in the presenceof CO2. Compound 4 was alternatively obtained by the reaction of 1 with N2O. To
synthesize an aluminum analog of 1, we examined the reaction of silylene 5 with AlI3 andobtained the corresponding 1:1 adduct.
Analysis: All new products were fully characterized by a combination of NMR
spectroscopy, elemental analysis, and MS spectrometry.

This project was done in collaboration with Professors Yoshiyuki Mizuhata (ICR Partner
Researcher) and Shigeyoshi Inoue (International Collaborating Researcher, Technical
University of München, Germany).
Publications: S. Abe, T. Iwamoto, “Synthesis, Structure, and Small Molecule Activationof Silicon-Boron Doubly-Bonded Compounds Having Alkyl Substituents on theUnsaturated Silicon Atom”, the 32nd Sympsium on Physical Organic Chemistry,
September 20-22, 2022.

－14－

2022-15（国際）Development of 1,4-Addition Reactions via Iron Catalysis
LAKSMIKANTA ADAK Indian Institute of Engineering Science and Technology, Shibpur
Objectives
Iron is the highest ample transition metal in the Earth’s crust, It is inexpensive,
environmental and toxicology benign in nature. My interest is to explore the catalytic
properties of ecologically and economically attractive iron catalysts. Institute for
Chemical Research (ICR), Kyoto University is a well-furnished research institute. It has
all the up-to-date research services to achieve each type of reactions. Our studies willcertainties help the entire scientific people to realize the basic properties of iron-catalysis.
Our goal is to acquire new reactions and new molecules to be helpful for expansion of
new science and technology.
Experimental Methods
The first goal of the present project is the development of iron-catalyzed 1,4-addition
reactions of aryl-, alkenyl- and alkynylboron reagents to α,β-unsaturated carbonylcompounds.Initially, we focused on the development of 1,4-addition reaction ofphenylborate (2) (J. Am. Chem. Soc. 2010, 132, 10674) to enone (1) catalyzed by iron salt
in combination of ligand to provide the product 3 (eq 1). The reaction may involve the BFe transmetalation as the key step.
O
Ph

Ph
1

+
Bu

B

2

O
O

Li

cat. FeX2
cat. Lcondition

O
Ph

Ph

1

3

To optimize and increase the yield of this reaction various reaction conditions including
iron precursors, ligands/additives, reaction temperature, solvents have been studied. After
optimization of reaction protocol (eq 1), we examined the scope of 1,4-addition reactionof various α,β-unsaturated acyclic and cyclic ketones with diverse aryl/heteroaryl-,
alkenyl- and alkynylboron reagents.
Outcomes and Perspective
The development of iron-catalyzed 1,4-addition reactions of aryl, alkenyl andalkynylboron reagents to α,β-unsaturated carbonyl and related compounds andmechanistic studies have been pursued. The most significant point is that the toxic andexpensive rhodium or palladium catalysts can be replaced by modest iron catalyst. The
iron catalyst will advance the known catalytic method as well as in innovation of novel
synthetic methodologies for the synthesis of fine chemicals and drug molecules. Not only
will the effect on the useful chemical synthesis, the new catalyst makes an academic
interest. Thus, we believe that these studies will have very broad impacts in both academic
and industrial standpoints of view.
Publications
The corresponding manuscript is in preparation.

－15－

2022-16（国際）Peptide Bolaamphiphile Anchored Nickel-based Metallohydrogel as
Electrocatalyst for Hydrogen Production
Apurba K. Das

Indian Institute of Technology Indore

Electrochemical water splitting is considered as a green method for the generation ofsustainable and environmentally friendly energy conversion. The hydrogen evolution
reaction is associated with two electrons transfer for the formation of the H-H bond andproduced hydrogen energy with zero CO2 emission. However, OER's intrinsicallysluggish kinetics hinders water splitting's efficiency, which required 1.23 V
thermodynamic overpotential due to the involvement of multiple proton-coupled electrontransfer processes.
Objectives: The main aims of this project proposal are:(a) Design and develop peptide bolaamphiphile-anchored Ni-based electrocatalyst,(b) Experimental validation of electrocatalysts for electrocatalytic hydrogen generation,(c) To study the mechanistic insights for electrocatalytic hydrogen production.
Experimental Methods: Here, we have prepared a sonication induced boladipeptide(HO-YF-AA-FY-OH (PBFY); AA = Adipic acid, F = L-phenylalanine and Y = L-tyrosine)anchored self-assembled nickel-based coordinated polymeric nanohybrid hydrogel (NiPBFY). The metallo-hydrogel (Ni-PBFY-3) prepared by mixing of 3 mg NiCl2.6H2O
metal salt along with 20 mM (15.33 mg) of boladipeptide (PBFY) in 1 mL final volume.
The xerogel of Ni-PBFY has been used to fabricate the electrodes and utilized in OER(oxygen evolution reaction).
Discussion: Ni-PBFY-3 displays an ultralow Tafel slope of 74 mV dec-1 and lower
overpotential of 164 mV at the current density of 10 mA cm-2 in 1M KOH electrolyte thanother electrocatalysts under the same experimental conditions. Furthermore, the NiPBFY-3 is witnessed as a highly stable electrocatalyst during chronopotentiometry
performance for 25 h. The biomolecule assisted electrocatalytic results open a new route
to design efficient electrocatalysts for the significant implications in green energy
conversion. The mechanism of OER shows that the easy availability of hydroxide ions in
KOH promotes the formation of Ni-OOH species which facilitated the kinetics of the
OER. However, the electrocatalyst does not show the HER in 1M KOH due to theadditional energy required to generate the proton by breaking the water molecule. In an
alkaline medium prior to adsorbed H*, extra energy is required to break the strong
covalent bond of H-O-H. Besides the water dissociation, the electrocatalyst has strong
interaction with hydronium ions than the water molecule, which is another challenge inan alkaline medium to produce M-H bond. On the other hand, the catalysts perform good
HER activity in an acidic medium due to the maximum number and large availability of
H+ facilitating the activity of electrocatalysts and making them more suitable for acidic
HER performance.

－16－

2022-17Synthesis of Fe-containing Phosphorus Ligands and Their Application in the
Preparation of Metal-Cluster Molecules
Masamichi Ogasawara Tokushima University
Olefin metathesis reaction has been proven to be a powerful tool in organic synthesis, and theenantioselective extension is a recent trend in the metathesis chemistry. The ring-closing metathesis reactions(RCM) were applied to the highly enantioselective synthesis of diverse planar-chiral transition metal
complexes using the Schrock-Hoveyda chiral molybdenum-alkylidene precatalysts.[1] Here, an additional
protocol for the asymmetric metathesis reaction is reported, which is asymmetric metathesis dimerization(AMD)/kinetic resolution (KR) of racemic planar-chiral vinylphosphaferrocenes.[2]The phosphaferrocene substrates for thisstudy
(rac-1a-e)
featurean5 -(2-vinylphospholyl) ligand, which is an
origin of the planar chirality in rac-1. Screeningof the chiral precatalysts was examined using
rac-1a as a prototypical substrate. A KR reaction
using the chiral Mo/(R)-L1 precatalyst at 60 °C,
which facilitates the metathesis dimerization of(S)-1a preferentially and leaves most (R)-1a
intact, attained 50% conversion in 24 h. The
dimerized product consisted of the twodiastereomers with a chiral-2a/meso-2a = 97/3
molar ratio. The enantiomeric purity ofremaining (R)-1a was 74% ee and that of(S,S)-2a was 90% ee (Table 1, entry 1). The krel
value for this reaction was estimated to be 130
based on a second-order equation. The catalytic
activity of Mo/(R)-L2 was much lower and only
13% conversion was attained under theotherwise identical conditions (entry 2). The
Mo/(R)-L3
precatalyst
showedgood
enantioselectivity with the krel value of over1000 but with poorer diastereoselectivity (entry
3). A reaction with Mo/(R)-L1 at 20 °C showed
the near-perfect diastereoselectivity withexcellent enantioselectivity of krel = 880 (entry 4). The Mo/(R)-L1 species was applied to the AMD/KR ofother substrates rac-1b-e. While 1b and 1d were resolved as above with excellent
diastereo-/enantioselectivities with krel = 950 and 870, respectively (entries 5 and 7), propenyl-substituted
rac-1c was lowly reactive and needed higher temperature (60 °C) to attain the reasonable conversion, andthe dimer was obtained in 98% ee (entry 6). The AMD/KR of diphosphaferrocene derivative rac-1e needed ahigher temperature (40 °C) due to its lower reactivity. The excellent diastereo-/enantioselectivities wereretained as above, and rac-1e was resolved with krel = 410 (entry 8). In the present AMD/KR, the dimerized
products were obtained in >98% ee due to the VERY high krel values even with near 50% conversions.
Publication from this joint project:[1] Ogasawara, M. Chem. Rec. 2021, 21, 3509–3519.
[2] Nishimoto, K.; Taue, H.; Ohji, T.; Funakoshi, S.; Ohki, Y.; Ogasawara, M. Org. Lett. 2022, 24, 7355-7360.

－17－2022-18
自己集合性含ホウ素化合物の合成、集合過程解明ならびに機能開拓若林成知

鈴鹿医療科学大学【緒言】 我々はボリルピリジンにおける分子間ホウ素－窒素配位結合に着目し、幾つかの自己集合を達成し、超分子構築におけるユニット分子としての有用性を明らかにしてきた。昨年度の当共同研究において、フロー合成により得られた化合物 1 は溶液中、室温で環状 3 量体と 4 量体の平衡混合物を形成し、その平衡は溶媒および濃度に依存して移動することを示した。本研究では化学研究所の大木靖弘教授と共同し、類似挙動を示す既報告の化合物 2 との相違点を DFT 計算により明らかにし、さらに 1 のつくる多量体間の平衡移動に要する時間をフローNMR を用い検討した。
【結果と考察】DFT 計算により得られた 1 の二面角 (25°)、および CH/N 結合距離 (2.51 Å)から、2 のフェニレン部水素とピリジン環水素との立体反発は緩和され、かつ分子内での CH/N 水素結合により、両芳香環間の平面性は高いことが確認された。重ベンゼン中、3 量体の比率は同程度濃度での比較で、例えば 56% (1, 5.0 mM) vs 78% (2, 3.7 mM)であり、1 のつくる 3 量体の比率は 2 のそれより低い。1 の多量体間の平衡の熱力学的パラメータは ΔHº = −4.5 kcal mol-1、ΔSº = −3.1 cal mol-1 K-1 であり、2 のそれら (ΔHº = −8.8 kcal mol−1, ΔSº = −23.7 cal mol−1 K−1) と比較し、小さなエントロピー変化が特徴的である。これらは、1 は平面性が高いので、両芳香環が捻じれざるを得ない 3 量体形成は不利で、結果として 4 量体が優勢に存在することを示唆する。DFT 計算においても、2 の二面角 (40°)
はその 3 量体 (39°)、4 量体 (38°) とほぼ同じであるが、1 の二面角 (25°)、および CH/N 結合距離(2.51 Å) は、その 3 量体 (30°, 2.55 Å) より 4 量体
(23°, 2.50 Å) において維持され、4 量体において平面性が保持されていることが再現された。二面角のわず
かな相違は結晶構造においても反映されていた。
次に、多量体間の異常に早いと想定される平衡過程
を Spinsolve 60 を用いフローNMR により追跡した（Figure 1）。1 の重アセトン溶液に重ベンゼンを種々の比率で混ぜたところ、平衡移動は 1 分以内に起こっていることを示すことができた。
【成果報告】Wakabayashi S, Takumi M, Kamio S, Wakioka M, Ohki Y, Nagaki A. Chem. Eur. J. 2023, 29,e202202882. [DOI: 10.1002/chem.202202882]－18－

2022-19
MR-TADF 発光材料を用いた高効率塗布型有機 EL 素子の開発
小田晋 関西学院大学

有機 EL 素子は，高いエネルギー効率や，高コントラスト比，薄型軽量などの優れた特性を有することから，液晶に代わるディスプレイ技術として社会実装が進んでいる。近年，貴金属を用いず，最大で 100%の内部量子効率を可能とする新たな発光材料として，熱活性化遅延蛍光（TADF）材料が注目されている。しかしながら，TADF 材料は既存の発光材料に比べ，幅広な発光スペクトルを示すため，色純度の向上が望まれている。これに対し応募者の所属する研究室では，ホウ素と窒素の多重共鳴（Multiple Resonance: MR）効果を利用することで，世界最高レベルの色純度を持つ青色
MR-TADF 材料（-DABNA）の開発に成功している。本研究では，MR-TADF 分子を発光材料として用いて高効率な塗布型有機 EL 素子を開発することを目的とする。
まず，塗布型有機 EL 素子に適した波長をもつ発光材料として，共役系を拡張した超高色純度

緑色 MR-TADF 材料（-DABNA）の開発を行った。その結果，one-pot ホウ素化反応と one-shot
ホウ素化反応を組み合わせることにより，高収率で-DABNA を得ることに成功した。合成した-DABNA の極大蛍光波長は 509 nm であり，有機 EL ディスプレイの緑色素子に要求される蛍光波長（520–530 nm）と比較して近い値を示した。さらに，発光スペクトルの半値幅は 22 nmと幅狭であり，蛍光量子収率は 87%と比較的高い値を示した。また，逆項間速度定数（kRISC）
は 1.2  105 s–1 と，従来の高色純度緑色 TADF 材料よりも高い値を示した。さらに，-DABNAの有機 EL 素子を作製し，特性を評価したところ，発光極大波長は 512 nm，半値幅は 25 nm と
有機 EL ディスプレイに適した狭帯域緑色発光を示した。また，最大外部量子収率は 31.1%，1000 cd m–2 における外部量子収率は 29.4%であり，そのロールオフは 1.7%と従来の緑色 MRTADF 材料と比較して小さい値となった。
今後，大きな kRISC を示す TADF 分子と組み合わせることによって，有機 EL 素子の高性能化を目指す。具体的には，大きな kRISC をもつ TADF 分子で生成したエネルギーを-DABNA に移動させる“Hyperfluorescence”機構を利用することで，高い色純度，発光効率および素子耐久性を併せ持
つ高性能緑色有機 EL 素子の開発を行う予定である。

－19－

2022-20
Synthesis and its catalysis of dinuclear complexes utilizing a pincer-type
N,N,P 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 aminoketonato or -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 witharylmagnesium reagents (Dalton Trans. 2018, 47, 8003.; Eur. J. Inorg. Chem. 2019, 126.). We intended todevelop a highly effective catalyst system for the activation of inert chemical bonds such as C-F and C-Obonds. The use of dinuclear complexes as catalysts has been considered as an efficient way to achieve this aim.
Dinuclear catalysts have attracted considerable attention in recent years since a dinuclear complex containing
two metals in close proximity would exhibit abimetallic cooperative effect. Therefore, thebimetallic cooperativity can achieve to activate
inert chemical bonds, which is difficult bymononuclear complexes. On the basis of theachievements of dinuclear catalysts reported soThis work

Previous work
O
N Ni

N
Cl

PPh2

N Ni

N
Cl

PPh2

Mononuclear complex

N Ni

spacer
Cl

PPh2

Cl

N
Ni N

Ph2P

Dinuclear complex

far and the studies of pincer nickel complexes by us, we designed dinuclear nickel complexes supported by a-diketiminato-based pincer ligand.
1,4-Phenylenediamine was selected as a spacer for the construction of an N,N,P-type ligand precursor for adinuclear complex. The condensation reaction of 1,4-phenylenediamine with 2 equivalents of acetylacetone in
the presence of catalytic amount of H2SO4 in toluene refluxing conditions afforded the phenylene-bridgedbis(-diketimine) 1a in 82% yield. Next, we examined the preparation of the ligand precursor 2a by thereaction of 1a with 2-(diphenylphosphino)ethylamine under various conditions, whereas the desired product2a was not obtained. In this reaction, amine exchange reaction occurred mainly to afford the O,N,P-type proligand 3. It was found that, for the preparation of an N,N,P-type pro-ligand, existence of the ortho substituentson the aromatic ring connected nitrogen atom is crucial preventing from the exchange reaction of amines. Thus,
2,3,5,6-tetramethyl-1,4-phenylenediamine was employed and the phenylene-bridged bis(-diketimine) 1b was
obtained. However, the reaction of 1b with 2-(diphenylphosphino)ethylamine afforded complicated results
and the desired ligand precursor 2b was not obtained. The tetramethylphenylene unit as a spacer might be toosterically congested to construct the desired product 2b. Finally, 4,4'-methylenebis(2,6-diethylaniline) wasused as a spacer, and thus the formation of the desired ligand precursor was confirmed by NMR spectroscopy.
The preparation of the dinuclear complex supported by this ligand is currently underway in our laboratory.

－20－

2022-21
Synthesis of Alkyl Ethers Using Two Different Alcohols
Catalyzed by Organosilane Compound
Toru Hashimoto

Sanyo-Onoda City University

Objective:
Alcohols and aryl alkenes derivatives are cheap and environmental benign substrates. Compared to fossil
resources, these compounds are sustainable source and their direct use to access bulk and fine chemicals is ofincreasing interest. As environmental issues are growing concern, finding efficient, atom-economical and step-

economical strategies for directly transformation using these compounds is a major challenge in organic
chemistry. In this research project, we are challenging the development of a highly efficient andenvironmentally friendly synthetic process for alcohols and aryl epoxides by utilizing main group catalysts.

The ring-opening reactions of epoxides with alcohols provide access to synthetically important alkoxy alcohols. However, these reactions require either strongly acidic or basic conditions due to the usuallypoor nucleophilicity of alcohols; these harsh reaction conditions have spurred a search for new and milder
methods. The use of Brønsted or Lewis acids is the most common method for the ring-opening of epoxides.
Lewis-acidic metal salts have also been successfully applied in ring-opening reactions of epoxides withalcohols. Although these catalytic reactions generally lead to high product yields with good regioselectivity,
the use of toxic and/or non-air-stable, expensive reagents restricts their widespread applicability.
In this study, we have developed an organosilicon–catalyzed ring opening reaction of epoxide. The
screening of reaction conditions for this ring opening reaction of epoxide were performed. Variousorganosilane catalysts were used for the optimization of reaction conditions. After screening of the reaction
parameters, we found that the commercially available hydrosilane showed the catalytic activity for the ring
opening reaction of epoxides with alcohols to afford the -alkoxy alcohols in good yields.

－21－

2022-22
Development of heteroacenes with excellent photophysical andelectrochemical properties
Koichi Mitsudo

Okayama University

Thienoacenes, acene molecules bearing thiophene rings, have received considerable
attention due to their excellent semiconductor properties and are used as active materials inorganic field-effect transistors (OFETs) and organic photovoltaic cells (OPVs). Therefore, avariety of thienoacenes have been synthesized and their physical properties were investigated. It
is well-known that the thiophene ring is an electron-rich donor aromatic ring. In contrast,
thiophene dioxide, which is obtained by oxidation of the thiophene ring, loses its aromaticity andworks as an electron-deficient acceptor molecule. In recent years, some π-extended molecules,
having a thiophene dioxide skeleton, have been reported for their unique luminescent properties
and have begun to attract attention. However, there have been few reports on the synthesis ofthienoacene derivatives containing multiple thiophene-dioxides, even though
they are expected to have interesting properties, and little is known about their
physical properties. In this study, we focused on synthesis of thienoacenes whichhave benzo[1,2-b:4,5-b′]dithiophene 1,1,5,5-tetraoxide (BDT-teraoxide, 1) as a
key skeleton.
Even though BDT is one of the most common skeletons inthienoacenes, few reports have been on synthesizing theiroxides. In the previous period, we developed synthetic methods
for the construction of BDT tetraoxide derivatives 2 and 3. In
this period, we carried out the reaction of BDT tetraoxide 3 with several phenol and thiophenol
derivatives to afford O- or S-linked BDT tetraoxides 4 via addition–elimination reaction. Thusobtained 4 exhibited good fluorescent properties, and they are under investigation. We next
examined Pd-catalyzed dehydrogenative double cyclization of 4 under several conditions, but
the scission of C–X bonds proceeded predominantly and the desired thienoacenes 5 were notobtained. We screened several conditions and found that a cyclization reaction proceeded fromthe substrates without oxygen on the thiophene ring while the yield was still unsatisfactory.
Further study revealed that the choice of oxidant was quite important for cyclization, and we
successfully developed an efficient condition to construct C–C bonds on BDT derivatives. Now,
we are applying this strategy to several BDT and BDT tetraoxide derivatives.

－22－2022-23
Creation of Effective Oxidation Scavenger for Efficient Perovskite-based
Solar 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 (R2Si:) are attractive intrinsically extremely reactive species, which would
exhibit possible ability of working as effecting oxidation scavengers. Isolable silylenes remain
scarce, and in most hitherto reported examples, the silylene center is stabilized byelectron-donating substituents (e.g., heteroatoms such as nitrogen), which results in electronic
perturbation. We have been interested in the chemistry of redox-active silylenes withcarbon-based substituents such as ferrocenyl groups. Furthermore, we have designed aferrocene-based phosphenium ion with “reversible” intramolecular donor coordination, FcP2Si:(FcP = 1’-dicyclohexylphosphino-1-ferrocenyl). The FcP group ascribes both stability andreactivity for the silylene center with its “switchable” donor coordination caused by therotation of the cyclopentadienyl moiety Accordingly, the possible precursor for the silylene
such as FcP2SiCl2 and FcP2Si(OCH3)2 were synthesized.1 The attempted synthesis of thecorresponding silylene is currently investigated. We are grateful to Prof. Wakamiya (ICR,
Kyoto Univ.), Prof. Yoshida (Nagoya Univ.) and Prof. Tsuchiya (Kitasato Univ.) for theirsupport on the research, and fruitful discussions.

1.

Sasamori, T.; Ueno, H.; Morisako, S. Inorganics 2022, 10, 22.

－23－

2022-24（国際）Developing machine learning approaches for prediction of protein
stability changes upon missense mutations
Jiangning SongMonash University

Objective. It is important to predict the stability of a protein against mutations
because even a single missense mutation of an amino acid can change a protein’s
structure and stability. Existing studies show that missense mutations can be harmful
to health and disease-related by causing changes in the stability of a protein.
Therefore, the accurate estimation of protein stability change (∆∆G) measured as
Gibb’s free energy change is crucial for studying and understanding the relationshipbetween protein missense mutation and function. Therefore, we will develop novel
machine learning methods for this problem, by combining state-of-the-art machinelearning techniques and various types of informative protein sequence and structuralfeatures. In this project, building upon these successful collaborative researches, wewill continue and extend our development of next-generation bioinformatics methods
for improved prediction of protein stability change. We may also study other related
bioinformatics problems in the areas of sequence analysis and structural informatics.
Results. As a result of this project, we have developed a novel sequence-based
method termed PROST for the protein stability change (Gibb's free energy change,
ΔΔG) upon a single-point missense mutation [1,2]. In addition, we have also
developed an open-source, Python-based software package iFeatureOmega [3],which is a powerful tool to generate, analyze and visualize 189 representations forbiological sequences, structures and ligands.
Publications[1] Iqbal, S., Ge, F., Li, F., Akutsu, T., ...., Song, J. PROST: AlphaFold2-aware
Sequence-Based Predictor to Estimate Protein Stability Changes upon Missense
Mutations, J Chem Inf Model. 2022 Sep 12;62(17):4270-4282 (2 citations).
[2] Iqbal, S., Li, F., Akutsu, T., …, Song, J. Assessing the performance ofcomputational predictors for estimating protein stability changes upon missense
mutations, Briefings in Bioinformatics, 202, 22(6):bbab184 (15 citations).
[3] Chen, Z., Liu, X., Zhao, P., Li, C., Wang, Y., Li, F., Akutsu, T.,…,

Gao, X.,

Kurgan, L., Song, J. iFeatureOmega: an integrative platform for engineering,visualization and analysis of features from molecular sequences, structural and ligand
data sets, Nucleic Acids Res. 2022 May 7;50(W1):W434-47. (7 citations).

－24－

2022-25（国際）Integrating Omics Data and Module-based Network with Deep
Learning to Develop Cancer Type Predictive Models
Jinn-Moon Yang

National Yang Ming Chiao Tung University

Objective. Classification and prediction of cancer subtypes have been a major topic
both in biomedicine and bioinformatics. To tackle this important issue, various
machine learning methods have been developed to better utilize mRNA expression
data and improve the classification accuracy. However, many of existing studies
focus on specific cancer types, and thus it is needed to explore mechanisms acrossmultiple cancer types. For understanding of such mechanisms, it is crucial to analyze
the topology of biological networks and biochemical progress in cells. To this end,
integrated analysis of omics data and biological networks is required. Although manysuch studies have recently been done, currently available approaches are notsatisfactory. To address these issues, we will develop computational methods by
integrating graph-based and machine learning methodologies. In this year, we focus
on analysis of protein complexes because these play important roles in biologicalnetworks.
Results. We developed graph theory-based methods to predict hot spots from only asingle residue interaction network constructed from three-dimensional protein
complex data, where hot spots are sets of residues contributing most to the binding
energy in protein interfaces. The methods are based on the concept of the densest
subgraph and utilize linear programming and integer linear programming. By
evaluating the results on 67 complexes from a publicly available database (SKEMPI
database), our methods clearly outperform existing graph theory-based methods onrecall and F-score. In particular, the Min-SDS method has an average recall of over
0.665 and an F2-score of over 0.364, while the recall and F2-score of the existing
methods are less than 0.400 and 0.224, respectively.
Publication[1] R. Li, J-Y. Lee, J-M. Yang, T. Akutsu: Densest subgraph-based methods forprotein-protein interaction hot spot prediction, BMC Bioinformatics, vol. 23, Paper
ID. 451, 2023.

－25－

2022-26（国際）
Evolution of giant viruses and relationships with the origin of Life
Morgan Gaïa CEA/Genoscope
Background:
The nucleocytoplasmic large DNA viruses (NCLDVs) form a phylum of related familiesof large and giant DNA viruses, which collectively infect the entire diversity ofeukaryotes. They are abundant, active and diverse in many environments, especially theoceans. Their immense diversity and broad host spectrum are likely the results of theirancestry; they were presumably already diversified before the emergence of the modern
eukaryotes and infected their direct ancestors. Considering the large amount of genetransfers regularly occurring between cells and these viruses, including from the latter tothe former, the NCLDVs are suspected of having played a major role in the emergenceand early evolution of modern eukaryotes. The evolutionary mechanisms and forces
behind the gigantism of their genomes also remains to be investigated.
Objectives:
1) Robust phylogeny of the NCLDVs (evolutionary backbone);2) Flow of gene transfers from and to the NCLDVs (past interactions);
3) Inferred lifestyle from genomic functions (adaptation);
4) Characterization of the new classes’ specificity (divergence).
Results:
Objective 1 was achieved by identifying unstable branches from the phylogenomic treeof isolated viral genomes. Viruses identified to contribute to the instability of branches
were removed from the dataset to build a robust phylogenomic tree. Objective 2 was
performed by comparing “gene trees” for orthologous gene clusters to the above
mentioned robust phylogenomic tree (“species tree”). We used the amalgamatedlikelihood estimation method to identify gene loss and gene gain events, the latter being
further classified into gene transfers between viruses (T), gene duplications (D), andunknown originations (U). The result indicated that gene gain overwhelmed the gene loss
events, and among different types of gene gains, gene transfers between viruses (T) wererecognized, for the first time, as a quantitatively important evolutionary event. These
results were obtained in a tight and intensive collaboration with a master student, Junyi
Wu, in the partner laboratory at ICR. We also obtained specific results for Objective 3
and 4 (see: doi: https://doi.org/10.1101/2021.12.27.474232).

－26－

2022-27（国際）Revealing marine microbial-viral interactions through community
interactome analyses
Samuel Chaffron CNRS
Background & Objectives:
As opposed to our conventional view on viruses as small particles, viruses of the phyla
Nucleocytoviricota and Mirusviricota possess outsized virions even larger than small cells bacteria.
These giant viruses can infect various eukaryotic hosts, from unicellular eukaryotes to large animals.
The wide host spectrum of giant viruses makes them abundant, active, and ecologically important in
the global ocean. However, known hosts of giant viruses are very poorly characterized due to isolationand technical limitations. Nevertheless, the diversity of giant viruses has been recently expanded
through metagenome-assembled genomes (MAG) reconstructions. MAGs can provide genomic
information to predict and support infection relationships, as for horizontal gene transfers evidence
between hosts and viruses.
In this project, we aimed to improve our knowledge of inter-species interactions between
viruses and eukaryotes and predict hosts of marine viruses using novel computational methods
applied to a recently published Global Ocean Eukaryotic Viral (GOEV) database [1].
Methods & Results:
First, using abundance profiles of the GOEV database and a marine eukaryotic environmental
genomes database, we inferred a marine virus–plankton association network (referred to as aninteractome) at a global scale (Fig.1). We analysed viral community composition and computed
robust temperature optima for viruses and their predicted hosts. We then assessed a clear structurationof this interactome at the temperature-dependent polar/nonpolar boundary. The uniqueness ofpolar/nonpolar interactions likely causes theendemism of polar viral communities.
We then used a phylogeny-guided Taxon
Interaction Mapper (TIM) method to predict hosts
from interactome associations. Consistent with thefindings above, our analyses suggested anunidentified virus–host relationship between polar
diatoms and giant viruses. Taking advantage ofgenomic information, we further identified
potential HGTs and viral insertions in diatom
Fig. 1 Virus‒plankton interactome
genomes to support our findings. Overall, ourgraph-based computational approach has been instrumental to reveal novel marine host-virusinteractions, which will have to be validated in vitro.
Publication: Lingjie M., Delmont T.0., Gaïa M., Pelletier E., Fernàndez-Guerra A., Chaffron S.,
Neches R.Y., Wu J., Kaneko H., Endo H., Ogata H. (2023) Genomic adaptation of giant viruses inpolar oceans. bioRxiv 2023.02.09.527846; doi: https://doi.org/10.1101/2023.02.09.527846－27－2022-28（国際）－28－2022-29
オミクスデータと流束均衡解析に基づく高温適応進化の機序解明
岸本利彦

東邦大学

（目的）我々は、これまでに高温適応進化大腸菌の継代培養を 15 年以上継続して、48℃以上でも安定的に増殖する株を複数培養中である。高温適応進化大腸菌は、元の野生株とは異なる様々な表現型を示すが、その機序はほとんど未解明である。一方、継代培養を続けた株では、細胞増殖や各代謝反応の速度が安定するので、網羅的トランスクリプトーム解析で予測した反応速度分布を用いて、制約モデルによる流束均衡解析シミュレーションが有効である。本研究では、野生株や高温適応進化大腸菌の網羅的トランスクリプトームデータを用いて、流束均衡解析と GPR ネットワークに基づくシミュレーション
を混合整数線形計画法で定式化して、高温適応進化による GPR ネットワークの変異を検出することを目的とした。
（実験方法）解析対象となる大腸菌として、先祖株 と２系統の高温適応進化大腸菌の 45℃、46℃、
47℃、48.1℃、48.3℃、及び系統１の 47.3℃、系統２の 47.4℃、47.9℃適応株を用いた。大腸菌の培養は、mM63 最小培地を用いて行い、対数増殖（OD600<0.4）を維持するように実施した。RNA 抽出は、各株で 3 本の培養から RNAProtect bacteria reagent と RNAeasy (共に QIAGEN)を用いて行なった。
RNAseq は、NEBNext rRNA Depletion Kit (Bacteria) (NEB）、NEBNext Ultra II RNA Library Prep Kit for
Illumina (NEB)、NextSeq 500/550 High Output Kit v2.5 (Illumina)を用いてサンプル調整を行い、NextSeq
500 (Illumina)によりデータを取得した。RNAseq データの TPM データ化には、Kallisto を用いた。
（実験結果）高温適応進化実験により、大腸菌は、２系統とも 48.3℃適応まで達成された。このうち系統２の 48.3℃適応株は、その増殖至適温度が 45℃から 46℃の間に存在することが判明した。高温菌の増殖至適温度が 45℃以上であることから、実験室進化で中温菌である大腸菌を高温菌まで進化させることに成功した。実験室進化で種を超える進化の報告はないため、世界初の例となった可能性が高い。この大腸菌を含む、高温適応進化大腸菌株 12 株と進化の元株の計 13 株について、最小培地
でそれぞれの株の適応最高温度で対数増殖期の RNA を採取した。このサンプルを慶應大学先端生命科学研究所河野先生に送付し、RNAseq 解析を行った。その結果、全てのサンプルで解析に利用可能なレベルのデータが取得された。これにより、GPR ネットワーク解析を実施する準備が整った。現在、共同研究者である田村先生にデータを送付し、3 月以降に解析予定である。
（考察）本 RNAseq データを用いて GPR ネットワーク解析以外にも、高温適応進化により使用頻度が減少したネットワークの検出などにも応用可能である。本研究における高温適応進化は、通常大腸菌の２オーダー高い変異率で生じている。現存生命で維持されている遺伝子数は、ゲノムの変異率と一次の逆相関していることがわかっており、我々の高温適応進化で活用されている有効遺伝子数が減少していることが示されれば、実験的に遺伝子数と変異率の関係を証明できることにもなる。
（成果報告）
1) 岸本利彦、松尾萌、河野暢明、田村 武幸

大腸菌高温適応進化とその生き残り戦略

第１回総合微生物学研究会、ラフォーレ修善寺、2022－29－

2022-30
Control and Analysis of Complex Networks via Probabilistic
Minimum Dominating SetsJose Nacher

Toho University

Objective. Various molecules interact with each other to carry out life activities incells and organisms, and thus it is important to analyze networks formed by theseinteractions to understand life. To this end, we have been conducting studies oncontrollability of various biological networks such as protein interaction networks,
metabolic networks, and ncRNA-protein networks. In recent years, we have been
focusing on controllability studies using the minimum dominating set (MDS),
which is a well-known concept in graph theory. We developed various extensions of
the MDS-based control model. In particular, we developed methods to classify
nodes into critical, intermittent, and redundant based on in occurrence of nodes in
MDS solutions. In this year, we further explore the MDS-based approach to analyze
large-scale directed networks and to perform more detailed classification of nodes.
Results. We developed two graph theory-based methods for MDS-based analysis of
biological networks. One is an efficient method for classifying nodes in large
directed networks into three categories: critical, intermittent, and redundant, byutilizing novel pre-processing methods. The results of preliminary computational
experiments on large-scale protein-protein interaction networks suggest that theidentified critical proteins are associated to important biomedical functions [1]. The
other one is introduction of a new controllability measure, and its associatedefficient algorithm, that quantifies the importance of intermittent nodes in directedbiological networks. The results of preliminary computational experiments
demonstrate the biological importance of the intermittent nodes as well as theirassociations with specific human diseases [2].
Presentations[1] Y. Tokuhara, T. Akutsu, J. C. Nacher: An algorithm for identifying criticalcontrol nodes in probabilistic directed biological networks, IPSJ SIG Technical
Report, vol. 2022-BIO-72, no. 7, 2022.
[2] W. Someya, T. Akutsu, J. C. Nacher: An algorithm for quantifying theimportance of intermittent nodes in controlling biological networks, IPSJ SIG
Technical Report, vol. 2022-BIO-72, no. 8, 2022.

－30－

2022-31
Development of a comprehensive detection method forcoronaviruses originated in wildlife
Tokiko Watanabe Osaka University
Seven types of coronaviruses are currently known to infect humans, all of which originate fromviruses that infect wild animals such as bats and rodents. In this study, we developed a system tocomprehensively detect coronaviruses in environmental samples and applied this system to actual
surveillance with the aim of strengthening surveillance for coronaviruses carried by animals suchas bats. First, we established an RT-PCR method using degenerate primers designed bybioinformatics analysis to detect coronaviruses for divergent bat coronavirus surveillance. We
designed 39 degenerate primer pairs for comprehensive detection of the RNA-dependent RNA
polymerase gene sequences of coronavirus genes in the database. The RT-PCR conditions were
optimized using these primer pairs, leading us to successfully detect RNAs of alpha-, beta-, gamma-,
and deltacoronaviruses. Next, we performed the optimized RT-PCR using RNA extracted fromorgan samples from 26 bats captured in Sierra Leone, West Africa. An amplicon of 400–450 bp
was detected in RNA extracted from the intestinal tract of one of these bats. This RNA sample wasanalyzed by RNA-seq and identified as acoronavirus sequence. Phylogenetic analysis
revealed that this virus clustered with membersof the genus Alphacoronavirus and the sequenceof the ORF1ab genome shared less than 90%
identity with the closest bat alphacoronavirus(Fig 1, magenta). We have thus established an
RT-PCR method that can comprehensively
detect coronaviruses, which will be useful for bat
coronavirus surveillance and proactive measuresagainst future outbreaks of coronavirus infection.

Fig 1. Phylogenetic tree of coronaviruses(ORF1ab gene)－31－2022-32
Microbial ecology in the dark sea
Takashi Yoshida

Kyoto University

Microorganisms account for two-thirds of the biomass in aquatic environments. In
the marine ecosystem, viruses are the most numerous biological entities and can lyse onethird of the host cells daily. The interaction between viruses and microorganisms
contribute to the variability and stability of the global environment, influencing overallbiogeochemical cycling in the ocean. Much previous effort in marine microbiology
focused on the photic zone, which is highly productive and relatively easy to perform
observations. Aphotic zone (at depths below 200 m), accounting for 95% of thehydrosphere, is characterized as a harsher environment, with no light for photosynthesis,
low oxygen concentration, high pressure and a high concentration of inorganic nutrients.
However, the interaction between viruses and microorganisms in this zone is still underinvestigated due to the high difficulty in sampling this zone.
To analyze the community composition, potential hosts and metabolic capacity ofviruses and microorganisms in deep sea, it is a prerequisite to obtain sufficient amount of
DNA and RNA from samples. In this study, a long-term sampling is planned to conduct
at Muroto Deep Seawater Research Institute in Kochi Prefecture. In this institute, deep
seawater (320 m depth) and surface seawater (0.5 m depth) are pumped up from a spot
within a 3 km distance from the coast. Four times of sampling in Muroto have been carriedout from Dec 2021 to Dec 2022 to concept and develop an appropriate sampling system.
In total, about 2,800 L deep seawater and 100 L surface seawater were filtered.
By building different type of filtration systems, including changing the filtration
membrane pore-size, filtration pump type and RNA/DNA extraction methods, a highefficiency sampling protocol was built for obtaining sufficient DNA and RNA finally. In
brief, seawater was prefiltered through 150 µm mesh nylon mesh to remove large
plankton, and then filter by 3 µm pore-size membrane and 0.2 µm sterivex, individually.
Filtration time was strictly limited in 30 min to prevent RNA from degrading. Finally,
nucleic acid yield increased. Especially for the 3-150 µm size particles in deep sea, theRNA amount from one-liter deep sea water increased from under-detection limit to about
4.8 ng. High yields were also achieved by extracting DNA and RNA separately.
In future, metagenome and metatranscriptome sequencing will be performed to probe
microorganism community compositions and viral gene expression level to better
understand the ecology of virus-host system in the deep ocean.

－32－2022-33
効果的な分子ネットワーク解析方法の発展と医学・農学への応用
茅野光範 帯広畜産大学

本研究では、機械学習と統計学を融合させた統計的機械学習の観点から、効果的な分子ネットワーク解析法を提案し、それを用いて医学・農学における問題を解決する。
分子レベルとして、ゲノム・遺伝子・代謝に焦点を当て、遺伝子ネットワークや代謝
ネットワーク（代謝パスウェイ）の推定や、それらのネットワークへのゲノムの影響、
実験条件（健常者と患者等）による違い等を検証するための解析方法を提案する。
我々は、これまで、図 1 に示した分子発現の相関構造の変化を捉える解析手法を提案し、これを改良した提案手法の数値実験による評価、公共の遺伝子発現データ（GeneExpression Omnibus；GEO から入手した延べ約 100 万個の遺伝子群）に提案手法を適用
し、生物学的に意義のある遺伝子群が検出出来ることを確認した。また、先行研究で報告されている、相関ネットワークが変化する遺伝子群の具体例を集めた。さらに、これまでの提案手法をさらに発展させ、グラフネットワーク理論、計算機統計学、ア
ルゴリズムやマイニング理論を駆使した機械学習・統計学的な分子ネットワーク解析法の提案へ向けて検討を重ねている。
今年度は、これらの解析法の医学分野（特に加齢研究）および農学分野（特に農作物）における具体的な生命科学現象への応用を検討し、医学分野として、ヒトと動物の加齢および加齢関連疾患研究、また、農学分野として、農作物のオミックス解析研
究を進めている。

図 1. 2 つの群間（サンプル 1〜50 および 51〜100）で相関構造が変化する 5 つの遺伝
子 A, B, C, D, E のヒートマップ表示（濃いほど発現量が高い）。遺伝子 A-E の中から任意の対をとると、サンプル 1 から 50 の群では相関を持つが、サンプル 51-100 の群
では相関構造が崩れる [Kayano M., Shiga M. and Mamitsuka H., IEEE/ACM Trans. Comp.
Biol. Bioinform., 11(1): 154-167, 2014 より転載]－33－

2022-34（国際）Investigations into Catalytic and Biochemical Behaviors of
Nitrogenase Fe protein using 57Fe labelingMarkus W. Ribbe－34－

University of California, Irvine

2022-35（国際）Precise synthesis and controlling higher-order structureof tadpole-like Janus cellulose nanocrystal
Atsushi GOTO

Nanyang Technological University

Objectives – Cellulose nanocrystal (CNC) is a rod-like nanoparticle with intriguing
properties such as high strength and high stiffness. We focus on the CNC withdifferent polymers (in chemical composition or degree of polymerization) grafted
regioselectively on the reducing end-groups and the lateral hydroxyl groups of CNC(tadpole-like Janus CNC; Figure 1), which could form novel higher-order structuresotherwise impossible. In this study, as a key step of the versatile synthetic route
toward tadpole-like Janus CNC, we have tried to introduce an initiating group of atomtransfer radical polymerization (ATRP) via click reaction.
Cellobiose
2-picolineborane
70 °C, pH 4.5

1

Tadpole-like Janus CNC

CNC
2-picolineborane
70 °C, pH 4.5

２

CuSO4ꞏ5H2O
ascorbic acid３

Figure 1. Schematic illustration of structures of Tadpole-like Janus CNC and CNC and tadpole-like
Janus CNC and Scheme for Chemical modification of reducing end-groups of cellobiose and CNC.

Results and Discussion – To confirm the effectiveness of reductive amination
reaction with azido ethylamine, reductive amination with cellobiose was caried out
according to the reported procedure,1 indicating that hemiacetal structure decreased
by 97% by the bicinchoninic acid assay. Then, we applied the same reaction condition
to CNC and achieved approximately 60% reduction of the hemiacetal structure of
CNC. Thus, we concluded that sufficient reducing end-groups of CNC was
successfully modified with 2-azidoethylamine. As for the succeeding click reaction
toward CNC-3, the peak derived from the azido group despaired in the IR spectrumof the obtained sample, indicating the successful synthesis of CNC with ATRP
initiating groups. We are going to purify the cellobiose derivative 1 and analyze its
structure and hence the detail of the reductive amination reaction with 2azidoethylamine. We are going to carry out the ATRP using CNC-3 to synthesize
tadpole-like Janus CNC forming a novel higher-order structure.
[1] Delepierre, G., et al. Biomacromolecules 2021, 22, 2702−2717－35－2022-36（国際）Exploration of perovskite solar cell composition:correlating device performance and fundamental property
Akinori Saeki Osaka University
Connecting data science (machine learning) withexperimental methods is critical for accelerating
material science research. We report a multivariate
analysis for exploring A-site organic cation mixing in tin
iodide perovskite (ASnI3) solar cells (PSC), which are
the most suitable Pb-free PSC candidates. To address thecommon drawbacks of Sn perovskites (facile oxidationof Sn2+ to Sn4+ and large degree of mixing), we
proposed an efficient experimental screening method
using 133 types of environmentally stable A2Sn(IV)I6
zero-dimensional pseudo-perovskites to predict thepower conversion efficiency (PCE) of ASn(II)I3, in Fig. 1. Exploration of A-site cation of Sn-PSC.
which A is a ternary or quaternary mixed organic cation(namely metylammonium, formamidinium (FA),dimethylammonium, guanidinium, ethylammonium,
acetamidinium, trimethylammonium, imidazolium, or
phenylethylammonium (PEA)). The high correlation
coefficient of our model (0.953) and experimental
validation (0.982) allowed us to identify a new(FA0.92IM0.08)0.9PEA0.1SnI3 Sn-PSC with a PCE of
Fig. 2. Anisotropic photoconductivity of
7.22%. Our results provide a basis for exploring A-site 2D-PSC.
cation mixing in Sn-PSCs for improving theirperformance.
Two-dimensional pseudo (quasi) perovskites, such as Ruddlesden–Popper (RP) and Dion–
Jacobson (DJ) perovskites, have garnered significant attention. Controlling the orientation of
their layered crystallites is key to vertical charge transport in two-dimensional (2D) PSCs;
however, their detailed electronic properties are yet to be fully understood. We investigated theeffect of processing additives (ammonium salts: NH4Cl, NH4Br, NH4Cl, NH4SCN, andCH3NH3SCN with/without alkali metal salts (NaCl, KCl, RbCl, and CsCl) in water) on the
crystallographic nature and anisotropic microwave photoconductivity of RP and DJ perovskites.
Importantly, a strong correlation (r = 0.882) was observed between the power conversion
efficiencies (1–11%) of inverted PSCs and anisotropic (both out-of-plane and in-plane to thesubstrate) photoconductivities for the 34 compositions of additives analyzed herein. These
results underscore the importance of anisotropic mobility in 2D PSCs and could serve as
guidelines for their further development.
[1] E. Nakanishi, R. Nishikubo, F. Ishiwari, T. Nakamura, A. Wakamiya, A. Saeki, ACS
Materials Lett. 2022, 4, 1124.
[2] R. Shimono, R. Nishikubo, F. Ishiwari, A. Saeki, J. Phys. Chem. C 2022, 126, 17894.

－36－2022-37（国際）－37－2022-38（国際）－38－2022-39（国際）Synthesis of Novel Nanotube Molecules with Different Hole Directions
by Introducing a Double Heptalene Structure
Chaolumen Inner Mongolia University
Exploring efficient synthesis and novel properties of polycyclic aromatics with pentagons are
significantly important for developing new optoelectronic materials. In 2015, we found that 5,11diphenyltetracene can smoothly undergo an oxidative coupling under the Scholl cyclization conditions
to give tetrabenzo-fused pyracylene (TBP), which can further react with n-BuLi and n-BuI to give a
1,4-adduct (1) with unique emissive properties in a solid state (Scheme 1).

In this project, we focus on synthesis and properties of novel molecular nanocarbons containing
non-hexagonal rings. The research outcomes are shown below.
Although 5,11-diphenyltetracene can proceed effecient cyclization under the Scholl conditions
with an excellent yield, 5,11-dinaphthyltetracene (2) afforded an unexpected product 3 with a very
low yield of 4%. The X-ray diffraction analysis disclosed that one naphthyl group migrated during theoxidative cyclization. Delightfully, a newly proposed precursor, i.e., 5,12-dinaphthyltetracene (4), canreadily give 3 with an excellent yield of 90%. The synthesis of the related aromatic compounds withextended π-conjugation motifs is currently ongoing. We believe that this strategy opens a new window
for us to explore various molecular nanocarbons containing non-hexagonal rings.
As mentioned in Scheme 1, although the 1,4-adduct of TBP exhibited intriguing emissive
properties, the synthesis of TBP is expensive and further functionalization of 1 is rather difficult.
During the course of this project, we found that indeno[1,2,3-cd]fluoranthene also can undergo thesimilar 1,4-addition to give dialkylindeno[1,2,3-cd]fluoranthene 5. The X-ray crystallographic
analysis revealed that 5 contains an isolated C=C bond, which is expected to be further functionalized
toward the synthesis of new optoelectronic materials. Accumulating these findings, we are planningto construct novel nanocarbons such as tubular molecules containing non-hexagonal rings. In thisresearch, all of X-ray crystallographic analysis were performed by Dr. Hashikawa at Institute for
Chemical Research, Kyoto University.

－39－

2022-40
金属酵素化学モデルの創製と材料・医化学への応用
太田雄大 山口東京理科大学

目的
小分子活性化を高効率に行う金属酵素化学モデルを開発し、構造化学的研究と触媒材料または薬剤としての応用に向けた基礎研究を行う。金属ポルフィリン二量体および酸化還元活性なヒドロキ
ノン-N4 配位子からなる新規錯体を合成し、各種研究を行う。
実験方法
各種金属ポルフィリン二量体の合成を行い、酸素還元反応と二酸化炭素還元反応について調べた。
酸素還元反応では分子触媒とカーボンナノチューブ（CNT）からなる複合体を電極触媒として調製し、回転リングディスク電極を用いて実験した。また分子触媒による二酸化炭素還元反応は、サイクリックボルタンメトリーで分析した。さらに、ヒドロキノン-N4 型の新規配位子からなる各種金属錯体を調製して、抗酸化活性について WST-1 法で評価した。
結果と考察
X 線結晶構造解析により各種金属錯体の分子構造を決定した。酸素還元反応の研究では、多核化したポルフィリン錯体において単量体と比べて過電圧の抑制と酸素の四電子還元選択性の向上が見られた。今後さらに CNT 上の修飾密度を上げることで高効率な酸素還元触媒になることが期待される。また、二酸化炭素還元反応において、過電圧および反応速度において単量体と比べて著しく反応性を高めた錯体の合成に成功した。今後、ファラデー効率の見積もりが必要になる。抗酸化活性の評価においては、鉄および銅錯体において高い活性（IC50〜2 M）であることを明らかにした。

図 1 ポルフィリン二量体(A)とヒドロキノンN4 錯体(B)

学会発表
1. 見鳥茉実, 脇岡正幸, 大木靖弘, Roger E. Cramer, 太田雄大，”亜鉛ポルフィリン二量体による低過電圧での二酸化炭素還元反応”，日本化学会中国四国大会広島大会 (広島大学, 東広島市)， 講演
番号: 2B-04, 2022 年 11 月
2. 好川大智, 脇岡正幸, 檜垣達也, 大木靖弘, 太田雄大, “ヒドロキノン-N4 型配位子を含む鉄錯体の合成と反応性”, 日本化学会中国四国支部大会広島大会 (広島大学, 東広島市), 講演番号: 1PA-10,
2022 年 11 月
3. M. Mitori, M. Wakioka, Y. Ohki, R. E. Cramer, and T. Ohta, “Electrocatalytic CO2 Reduction with a
Cofacial Zinc Porphyrin Dimer”, 10th Asian Biological Inorganic Chemistry Conference (Kobe International
Conference Center, Kobe), Program No. P-119, Nov 2022．
4. T. Yoshikawa, M. Wakioka, T. Higaki, Y. Ohki, R. E. Cramer, and T. Ohta, “Synthesis, Structure, andReactivity of Iron( Ⅲ ) Complexes with Hydroquinone-N4 Ligands”, 10th Asian Biological Inorganic
Chemistry Conference (Kobe International Conference Center, Kobe), Program No. P-42, Nov 2022.

－40－

2022-41
Dinitrogen Fixation Based on
Nickel→Z-type (-Electron Acceptor) Ligand
Hajime Kameo

Osaka Metropolitan University

PurposeNickelhas

beenconsidered unsuitable as acatalyst for the reduction ofdinitrogen due to its low
nitrogen affinity and low
reduction potential. On theother hand, its characteristics

Figure 1 N2 uptake and multi-electron transfer to N2 ligand.

are potentially able to create energy-saving catalysts that work with only a small amount of overvoltage. I
considered the possibility that the σ-electron-accepting (Z-type) ligand could enhance the electrophilicity of
the Ni center via the Ni→Z bond, facilitating the uptake of dinitrogen (Figure 1). In addition, the flexible
Ni→Z bond interaction was expected to induce the multi-electron transfer necessary for the reduction ofdinitrogen. Previously, Group 13 element-based multidentate ligand 1Z (E = B, Al, Ga) was developed, andNi(0) complexes bearing 1Z were found to afford rare nickel dinitrogen complex 2Z. The present study aims
to achieve the transformation of dinitrogen using nickel complexes 2Z under mild reaction conditions as isdone by enzymes.
Experimental Methods and Results

Cyclic voltammetry measurements were performedon complexes 2Z for developing the reduction ofdinitrogen on the Ni center. A reversible redox wave
based on one-electron oxidation Ni(0/I) was observed
in 2Z (Figure 2). Interestingly, the redox waves (E1/2)

Figure 2 Cyclic Voltammetry of 2Z (in THF).

shifted to higher potentials in the order 1Al (24 mV) < 1Ga (172 mV) < 1B (347 mV), suggesting that the borane
ligand enhanced the electrophilicity of the Ni center most efficiently. Importantly, a reversible redox wave
based on one-electron reduction Ni(–I/0) was also observed in the Ga system (2Ga: –1426 mV), despite of theNi(0) states of 2Ga. Although some attempts to isolate the reduction products of 2Ga were unsuccessful at thisstage, it is worth noting the possibility of the reduction of theN2 ligand. Also, catalytic dinitrogen silylation wasinvestigated using 2Z as catalysts, but the reproducibility
could not be guaranteed. Hence, Co analogs 3Z (E = B, Ga)
of 2Z were prepared and employed as catalysts (Figure 3).
Here, good catalytic activities were observed (TON: 52 for 3B,
Figure 3 Catalytic silylation of N2.

71 for 3Ga). Manuscript is in preparation for reporting theresults described here.
－41－2022-42
キラルシリカの構造と分子認識との相関解明
平井智康 大阪工業大学

キラルシリカは他の有機物と比較して耐熱性，機械的強度に優れていることから，次世代キラル
分離剤としての期待が集まっている。キラルシリカを効率よく調製する手法としてらせん状に配列させたミセルを鋳型としてエトキシシラン誘導体を用いるアプローチが幅広く展開されている。一
方，報告者のグループでは，シロキサン含有高分子のらせん構造を制御することで，キラルシリカ
を調製するアプローチを提案してきた。本年度は線状シロキサンのらせん構造制御に取り組んだ。
PDMS を始めとする線状シロキサンの分子鎖凝集構造に関する議論が X 線回折測定法に基づき行
われ，数多くのモデルが提唱されている。しかしながら，線状シロキサンの主鎖を一方方向に巻き方向を制御したらせん構造はこれまでに成し遂げられていない。そこで報告者らはビニル基を側鎖に有する線状シロキサン(PVMS)を開環アニオン重合法に基づき調製し，さらに側鎖基にとして嵩高く，不斉中心を有するシステイン誘導体をエンーチオール反応に基づき導入することで PVMSCys を調製した。
Figure 1a は調製した PVMS-Cys 膜の円二色性分光光度計(VCD)測定結果である。1100~1000 cm-1の Si-O-Si の伸縮振動に帰属されるピーク上において分裂型のコットン効果が観測され，さらに Lおよび D システインの間において鏡像関係が観測された。この結果より，PVMS 中の線状シロキサ
ン成分は一方方向に巻き方向が制御されたらせん構造を形成していると結論付けた。PVMS-Cys の機能評価を行うために，シンジオタクチック PMMA(st-PMMA)と混合した。WAXD および DSC に基づく評価より，PVMS-Cys は st-PMMA が形成するらせん空孔内に取り込まれ包摂錯体を形成することを見出した。Figure 1b は包摂錯体の VCD 測定の結果である。st-PMMA のエステル基の伸縮
振 動 に 帰 属 さ れ る 1300-1150
cm-1 のピーク上において分裂型のコットン効果が観測されており，さらにそのコットン効
果は PVMS-Cys の L と D の間
で鏡像関係を示した。この結果
は，PVMS-Cys が st-PMMA のらせん構造の巻方向を誘起していることを示しているものである(Figure 1c)。
1. Hirai et al., Chem. Lett., 2022, 51,
781.

Figure 1. VCD spectra of a)PVMS-Cys and b)st-PMMA/PVMSCys inclusion complex. c) Schematic illustration for this work.

2. Hirai et al., J. Polym. Sci., 2022, 60, 766.

－42－

2022-43
フロー合成法を用いた官能性ビニルテルリド合成法
永木愛一郎

北海道大学

ビアリールの合成は極めて重要な分子骨格形成反応の一つであるが，様々なクロスカッ
プリング反応がこれまで開発されてきたにも関わらず，立体障害の大きい基質に対しては依然として多くの課題を抱えている．そこで本研究では高反応性活性種を介する炭素−炭素
結合形成反応を主軸とする合成化学を展開する共同研究者の協力を得て，熱的に不安定なジアリールクプラート中間体を鍵とする酸化的カップリングにより，立体障害の大きなビアリールを選択的に合成する手法の開発を目指して検討を行った．ただし中間体のクプ
ラートは熱的に極めて不安定であり，通常のバッチ反応条件での制御は困難である．そこ
で申請者が得意とするフローマイクロリアクターを用いた反応の精密制御によって反応条件をコントロールすることが不可欠である．そこでまず，有機溶媒に可溶な銅塩溶液としてシアン化銅錯塩を用い，低温で対応するハロゲン化アリールとブチルリチウムから高速
混合にてアリールリチウムを発生させ，続いて別途バッチ容器にて発生させたアリールク
プラートを反応させることでヘテロジアリールクプラートを発生させ，最後に quinone を用いたフロー中での速やかな酸化的カップリング反応により，目的とするヘテロビアリー
ルの生成が確認された．ホモカップリング体の副生は流速などの混合条件の精査と，試薬の当量関係を制御することで抑制される可能性があるため，今後の研究においてさらなるフロー条件の検討で高選択性を得ることを目的として研究を行う予定である．
cooling bathBrAr1aryl halide

mixer M1

Ar1

microreactor

Cu(CN)Li

R1
Ar2

n-BuLi
M2
Ar2

Cu(CN)Li

R2
M3

R3

Ar1

Ar2

Ar1

Ar1

arylcuprate
Me
Me

O
O

Me
Me

Ar2

oxidant－43－

Ar2

cross-couplingproduct

homocouplingproducts

2022-44
環状ヘキサ-2,7-アントリレンエチニレン誘導体と環状パラフェニレンとのホスト-ゲスト化学に基づく複合化
小林健二 静岡大学

我々は、環状ヘキサ-2,7-(4,5-ジアリール)アントリレンエチニレン誘導体 1a の合成に成功し、環状体 1a は-スタック自己会合せず、また、1a の環の内孔サイズに適合した環状 p-フェニレン 9 量体[9]CPP をサイズ特異的に包接することを見出している(図 1)。また、昨年度本申請課題において、
1a の 6 つのアセチレン結合のうち対角位置の２箇所をブタジイン結合で置換した環状体 2a、および、1a に比べ側鎖の嵩高さが若干小さい環状体 1b を合成し(図 1)、単量体として振る舞う 2a は環内孔サイズ特異的に[10]CPP を包接すること、1b は CDCl3 中で単量体と-スタック自己会合二量体(1b)2 の平衡混合物として存在し、1b と(1b)2 共に[9]CPP を包接して４つの平衡状態をとることを見出している。今回、2a および 1b のさらなる会合特性を明らかにしたので報告する。
山子先生らは[10]CPP がフラーレン C60 を包接することを見出している(C60@[10]CPP の形成)。今回、C60 を包接した[10]CPP をさらに環状体 2a が包接する二重包接体 C60@[10]CPP@2a の形成を見出した(図 2)。3 者が溶解する 10% CDCl3–90% CS2 中 298 K で会合状態を 1H NMR にて解析した。
C60@[10]CPP の形成の会合定数は Ka = 107,000 M–1 と算出された。[10]CPP@2a の形成は、CDCl3 中
Ka = 3,170 M–1 に対し、10% CDCl3–90% CS2 中では Ka = 4,250 M–1 に増加した。10% CDCl3–90% CS2
中で C60@[10]CPP の形成を 100%と仮定すると、2a と C60@[10]CPP との包接会合定数は Ka = 5,590
M–1 と算出され、[10]CPP@2a 形成の Ka より増加することがわかった。また、サイズが適合しない
ため C60 を包接できない 2a は 10% CDCl3–90% CS2 中室温にて徐々に C60 と Diels–Alder 反応するのに対し、二重包接体 C60@[10]CPP@2a は殆ど Diels–Alder 反応を起こさないことがわかった。
環状体 1b は CDCl3 中で単量体と-スタック自己会合二量体(1b)2 の平衡混合物として存在する(図 3, Ka = 3,560 M–1 in CDCl3 at 298 K)。単量体 1b と会合二量体(1b)2 の 1H NMR シグナルは平均化
せず独立して観測される。今回、環状体 1b はシクロヘキサン-d12 中で定量的に-スタック自己会合
二量体(1b)2 を形成することを見出した。CDCl3–c-C6D12 混合溶媒中 c-C6D12 の割合が増加するに連れて(1b)2 形成の Ka は増加し(Ka = 8,360 M–1 in 10% c-C6D12, Ka = 63,300 M–1 in 30% c-C6D12)、50% cC6D12 中では(1b)2 の 1H NMR シグナルのみが観測された。また、318 K における(1b)2 の[9]CPP 包接は CDCl3 中 Ka = 9,440 M–1 に対し、70% c-C6D12 中では Ka = 13,200 M–1 に増加することがわかった。

－44－2022-45超分岐構造高分子の滑剤作用の解明と最適化
髙橋裕 東北大学【目的】一般的に潤滑油の特性を表すストライベック曲線は、その摩擦係数と粘度、速度、荷重の関係で示される。ストライベック曲線の流体潤滑において、低粘度油を用いることは摩擦を低減させることができる。しかしながら、低粘度油では境界潤滑において摩擦を増加させる。潤滑油の添加剤として超分岐構造高分子（Fig. 1）を用いることは、摩擦増加の抑制が期待される。そこで本研究でH

は、潤滑油の基油に対する添加剤としての超分岐構造高分

H
H

子の摩擦特性を明らかにすることを目的とした。

H
H【方法】超分岐構造高分子は制御されたラジカル重合によH
Hって合成された（共同研究者の登阪准教授の担当）。潤滑基油として PAO401 を用いた。潤滑油の摩擦評価は、種々の回転速度 (V) および荷重 (L) の条件でボールオンディス

H

Fig. 1 超分岐構造高分子の模式図

ク法による摩擦試験機によって行った。
【結果】合成した超分岐構造高分子の PAO401 に対する溶解性を紫外可視分光光度計を用いて評価した。超分岐構造高分子は、室温では溶解しなかったが、40 ℃以上で完全に溶解した。
Fig. 2 は、40 ℃における超分岐構造高分子を溶解させた潤滑油の摩擦試験の結果を示している。超分岐構造高分子の潤滑油の摩擦係数は，ストライベック曲線の流体潤滑（300 < V/L < 3,000）領域において，基油である PAO401 とほとんど同じであった。
流体潤滑における摩擦係数は溶液粘度に依存するため、超分岐構造高分子の潤滑油の溶液粘度は PAO401 とほぼ同じであることが分かった。この結果は、超微量粘度計による粘度測定
結果とよく一致していた。一方で、境界潤滑（0.003< V/L < 0.03）における摩擦係数は、超分岐構造高分子の添加により著しく減少した。このことから、本研究でのマクロスケールにおける摩擦試験は、
超分岐構造高分子が高い潤滑性を有していることを示す。また、この結果はこれまでに検討してきたナノスケールのおける共振ずり測定の結果とよく一致していた。

Fig. 2 PAO401 と超分岐構造高分子(HBP) の潤滑油のストライベック曲線。

【学会発表】Y. Takahashi, M. Mizukami, Y. He, M. Tosaka, S. Yamago, K. Kurihara, 71st SPSJ
Annual Meeting, 3J07.

－45－

2022-46
Synthesis of Highly Strained Macrocyclic π-Conjugated Molecules via aMultinuclear Au(I)-Pt(II) complex
Yoshitaka Tsuchido Tokyo University of Science[n]Cycloparaphenylenes ([n]CPPs, where n is the number of phenylene groups), consisting of 1,4-linked
phenylene unit, are macrocyclic organic molecules, which have attracted much attention due to their unique πconjugated structures and physical properties. We have developed a new CPP synthesis method via a macrocyclic
gold complex and have succeeded in synthesizing [n]CPPs containing phenylene groups with multiples of three (n= 6, 9, 12, 15) within short reaction steps and in high yields. A notable feature of this method is that the formationof macrocyclic gold complexes, proceeds with extremely high efficiency. We found from our kinetic experimentswith acyclic dinuclear gold biaryl complexes that the Au-C bonds are exchanged rapidly between the complexes,
thus causing the macrocyclization to proceed efficiently. In this study, we developed a new CPP synthesis method
utilizing the Au-C bonds, a new dynamic covalent bond that we discovered. Mixing two macrocyclic goldcomplexes with terphenylene or quarterphenylene linkers at 50 oC, followed by the reductive elimination upon
addition of PhICl2, resulted in the selective formation of four [n]CPPs (n = 9, 10, 11, and 12) (Figure 1a). The
presence of the gold complexes bearing two different phenylene linkers were experimentally confirmed by Fouriertransform ion cyclotron resonance (FT-ICR) MALDI-TOF MS measurement of the crude products after mixing at
50 oC (Figure 1b). These results indicate that macrocyclic gold complexes are reorganized by intermolecular Au-C
bond exchanges. This synthetic method is applicable not only to oligophenylene linkers but also to various arylene
linkers containing such as fused aromatic rings, and various nanohoops have also been successfully synthesized.
(a)Figure 1. (a) Synthesis of [n]CPPs (n = 9, 10, 11, and 12) via reorganization of macrocyclic Au complexes. (b) FTICR MALDI-TOF MS spectrum of the reaction mixture of two different complexes after mixing at 50 oC.
【成果報告】[1] Y. Yoshigoe, Y. Tanji, Y. Hata, K. Osakada, S. Saito, E. Kayahara, S. Yamago, Y. Tsuchido, H. Kawai, JACS
Au 2022, 2, 1857–1868.
[2] 丹治洋平, 畑優成, 吉越裕介, 斎藤慎一, 茅原栄一, 山子茂, 小坂田耕太郎, 土戸良高, 河合英敏，第32 回基礎有機化学討論会，2021 年 9 月 22 日，3A05．
[3] 平田沙弥，森隆博，茅原栄一，土戸良高，河合英敏，山子茂，第 32 回基礎有機化学討論会，2021
年 9 月 22 日，3A06．

－46－

2022-47
有機電子材料を指向したアザアズレン３量体の合成と応用
黒飛敬

久留米工業高等専門学校

今日、π共役系分子がもつ様々な機能は有機電子材料や医薬品などに広く応用されており、新たな機能性分子を探索する意義は大きい。青色の天然色素であるアズレンはナフタレンの構造異性体であるが、その物性は極めて特異的である。例えば、アズレンは 1.0 D の双極子モーメントを持ち、S2 発光を示し、アズレンの最長波長部の吸収末端は 700 nm に及ぶ。そこで、我々は新たな π 共役
系創出の基本分子としてこのアズレンユニットを用いた機能性分子の設計を試みている。また、近年、我々はアズレン類（含窒素複素環を含む）のオリゴマー合成について幾つかの有効な知見を得ている。これら一連の合成法の研究は、アズレン類特有の反応性の活用方法を開拓することによって進められてきた。一方、国内でも直線形のターアズレンの有機電子デバイスへの応用などの報告があり、アズレンの電子材料への応用も徐々に注目されつつある。本研究では、有機電子材料への応用を目指し、アズレンの 5 員環部へ窒素原子を導入した 1-アザアズレンおよび 1,3-ジアザアズレ
ン誘導体の直線型ならびに環状型のオリゴマーとして 3 量体合成を検討したので報告する。
実験方法は、まず直線型オリゴマーの原料として 1,3-ジアザアズレンの 2,6-ジハロゲン体の合成
方法の検討および環状型オリゴマーの原料として 3-アルキル-1-アザアズレンの 2,8-ジハロゲン体の合成方法の検討をそれぞれ行なった。その後、いくつかのカップリング反応の条件を検討した。
1,3-ジアザアズレンのハロゲン化について
は種々の臭素化試薬によって 2-アミノ体 1 に対する直接の臭素化を試みた。その結果、NBSを用いることでアミノ基の誘起効果による 4,6
位の位置選択的臭素化が進行し、6-ブロモ体 3
が収率 23%で得られた。しかし、その溶解性は非常に低く、次のステップであるアミノ基の官能基変換およびカップリング反応の進行が困難であった。一方、3-アルキル-1-アザアズレンの 2,8-ジハロゲン体の合成については、アルキル基について種々検討した結果、今回、メチル基を導入した誘導体で 2,8-ジブロモ体 5 に成功した。これは環状オリゴマーの安定性と溶解性について検討した結果である。続くNi(cod)を用いたカップリング反応によるオリゴマー合成では酢酸亜鉛を共存させることでテンプレート効果を試みた結果、オリゴマー6 が得られた。マススペクトル及び吸収スペク
トルより環状 3 量体の他に多数のオリゴマーとの混合物であり、更なる精査を検討する予定である。
－47－

2022-48
Development of Organometallic n-Type Materials with High Electrical
Conductivity
Michihisa Murata

Osaka Institute of Technology

Introduction
n-Type semiconducting films are indispensable in organic (opto)electronic devices. The synthesis of solutionprocessable n-type organic materials has been attracting growing interest for quite some time, whereby a recent
focus has been placed on their application in flexible thermoelectric generators, which can convert waste heat
into electricity. However, n-type solution-processed films based on organic materials have exhibited serious
issues associated with their instability toward atmospheric oxidation and their low electrical conductivity(generally < 10 S cm−1). Recently, Guo and Facchetti have reported very high conductivity in an n-typesemiconducting polymer (> 100 S cm−1 under N2) by developing a transition-metal-catalyzed n-doping
process.1
Results and Discussion
In this study, we have designed a concise syntheticroute to the n-type nickel coordination complex
NiT2TT, which contains a thieno[3,2-b]thiophene
unit in the ligand. An air-stable n-type composite
film of NiT2TT and PVDF fabricated using a solution process revealed excellent electrical conductivity (>200 S cm−1), which is, to the best of our knowledge, the highest value hitherto reported for solution-processedn-type films of organic or organometallic compounds and polymers.2,3 A grazing-incidence wide-angle X-ray
diffraction (GIWAXD) analysis of the NiT2TT/PVDF film revealed, for the first time, that the orientation of
the nickel coordination complexes in such films can be controlled by the molecular design of the π-conjugatedligand. In these films, NiT2TT exhibits a π-stacked structure in predominantly the in-plane direction (edgeon), which stands in contrast to the standard NiETT, in which the π-stacking occurs mainly in the verticaldirection (face-on) along the film. The edge-on orientation of NiT2TT should contribute to the enhanced
conductivity and reasonable n-type thermoelectric properties in the in-plane direction.
References:
1) H. Guo, C.-Y. Yang, X. Zhang, A. Motta, K. Feng, Y. Xia, Y. Shi, Z. Wu, K. Yang, J. Chen, Q. Liao, Y. Tang,
H. Sun, H. Y. Woo, S. Fabiano, A. Facchetti, X. Guo, Nature 2021, 599, 67−73.
2) 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.
3) K. Ueda, R. Fukuzaki, T. Ito, N. Toyama, M. Muraoka, T. Terao, K. Manabe, T. Hirai, C.-J. Wu, S.-C.
Chuang, S. Kawano, M. Murata, J. Am. Chem. Soc. 2022, 144, 18744−18749.
－48－

2022-49
未踏超不安定構造の単離および物性解明による新概念材料設計指針の創出
上野裕 東北大学【目的】分子が定常的に存在するには，それぞれの物質固有の安定性を揺るがす “刺激”がない環境に置かれている必要がある。極めて安定性の低い分子・構造体は，大気下室温どころか，それ以上に温和な条件でも容易に反応・分解し，そのため、物性や物性の起源となる構造情報などの基
礎的な性質を解明することすら困難である。本研究では，有機合成，およびプラズマを用いたフラーレン内部への原子・分子挿入法を段階的に併用することで，超不活性空間として知られるフラーレ
ン内部における未踏不安定化学種のその場構築によって構造・物性を定常化させ，未知の構造・物性相関を発見・理解・応用することを目的とした．
【実験手法】村田（ICR）らにより報告された有機合成による水分子挿入法，および代表者らが研究対象とするプラズマを用いたフラーレンへのイオン挿入法を段階的に駆使することで，『一分子の水で水和されたリチウムイオン』を内包した C60（Li+-H2O@C60）の合成を試みた。得られた試料をイオン交換カラムクロマトグラフィーおよび電解質添加 HPLC により精製し，NMR および X 線
構造解析による構造解析を実施した。
【結果・考察】各種 NMR スペクトルを Figure 1 に示した。7Li NMR スペクトルでは，−7.8 ppm 付
近にトリプレットシグナルが見られ，これは水分子の二つのプロトンとのカップリングによる分裂に帰属される。また，1H NMR スペクトルでは，−2.1 ppm 付近にシグナルが観測され，7Li の核スピン（3/2）により 4 本に分裂している。
これらのシグナルは，デカップリン
グ測定によりシングレットシグナルとなったことから，Li+と H2O の相関によるものと結論された。NMR に
よって 7Li と 1H のカップリングが明確に観測された例は少なく，隔離空間に閉じ込められることで相関が観測された例として重要な成果となった。単結晶 X 線構造解析についても実施済みであり，目的化合物の完全構造同定を達成している。本研
究により，有機合成による C60 内部へ

Figure 1. 7Li, 1H, 7Li{1H} and 1H{7Li} NMR spectra of thepurified product in CD2Cl2 at RT. LiCl/D2O (0 ppm) was used
as an external standard for 7Li NMR measurements.aの小分子配置，およびこれに続くプラズマによるイオン挿入反応によって C60 内部における不安定
化学種のその場構築が可能であることを実証した．今後，得られた化合物の物性評価や，当該手法を活用した新規分子の合成について継続的に実験を推進し，未踏不安定化学種の物性を活用した新しい材料科学を発展させていく。
－49－

2022-50（国際）Non-linear viscoelasticity of unentangled polymers
Giovanni Ianniruberto Università degli Studi di Napoli “Federico II”
While extensive studies reveal that the linear rheological properties of unentangled polymers canbe well reproduced by the Rouse model, there are still lots of unsettled problems on nonlinear
rheological properties. In the Rouse model, a polymer chain is modeled by consecutive beads
connected by Hookean springs. To reproduce the unentangled polymer dynamics, this model considers
three forces, i.e., the spring, frictional, and Brownian forces. We can naively expect that the Rousemodel can be used to predict the nonlinear rheological properties. However, by construction, thismodel does not exhibit any nonlinear viscoelastic behavior such as viscosity thinning under shear flow.
Thus, several nonlinear rheological models based on the Rouse model have been proposed. For
example, if the Hookean spring considered in the original Rouse model is replaced with the finitely
extensible nonlinear spring, the modified model predicts shear-rate dependent viscosities, which is inqualitative agreement with experimental observations. Nevertheless, there are still several
discrepancies between existing theories and experimental results, especially under extensional flow.
In this research project, we planned to develop a molecular-based model for nonlinear rheologicalproperties of unentangled polymers under both shear and extensional flow. For such a purpose, it might
be required to consider nonlinear factors that characterize the above three forces in the Rouse model.
The team members have been separately developing mesoscopic models and attained success to
reproduce (some) rheological properties. For example, GI developed a Brownian dynamics (BD)simulation method for the nonlinear rheology of unentangled polymers and considered the change ofmonomeric friction accompanied by segmental orientation [1]. TS and his group members at the ICR
have formulated the nonlinear effects associated with the above three forces [2].
Our group and the molecular rheology group at the ICR independently conducted the research
activity while sharing information via several online meetings this year. We have discussed the BD
simulation method with the effects of the finite extensibility, the friction reduction, and the Brownianforce intensity variation. While it is possible to develop a simulation code at the BD level, the difficultylies in how to validate the simulation results. Currently, the molecular rheology group is conducting
combined rheological and dielectric measurements to provide the detailed dynamical properties ofunentangled polymers. Moreover, TS has started molecular dynamics simulations to obtainmicroscopic structures under flow. In the future, we hope to unify these experimental and numericalresults for a further understanding of the rheology of unentangled and even entangled polymers.
References:[1] G. Ianniruberto and G. Marrucci, Macromolecules, 53, 1338 (2020).
[2] T. Sato, Y. Kwon, Y. Matsumiya, and H. Watanabe, Phys. Fluids, 33, 063106 (2021).

－50－

2022-51（国際）Nonlinear Extensional Rheology of Entangled Poly(n-alkyl methacrylate)
Melts with Fixed Number of Entanglements and Kuhn Segments per Chain
Shilong Wu Chinese Academy of Sciences
Understanding of the non-linear rheology of polymer melts is essential in optimizing their processing conditions,particularly in fiber spinning and membrane blowing processes where elongational flow is dominant. Although structureand dynamics of polymer melts have been extensively studied in the past half century, studies of their nonlinear rheologicalbehavior, in particular the elongational behavior under fast flow, are still quite limited. Thus, we have collaborated with
Profs. Watanabe, with a support from the collaborative research program of ICR, Kyoto University in 2022 (Grant No.
2022-51), to examine characteristic elongational features of polymer melts.
In this study, we investigated the effect(s) of side chain length distribution on the transient elongational hardening behaviorof polymer melts. For either entangled or unentangled system, we successfully prepared three polymers, poly(butyl
methacrylate), poly(methyl methacrylate-co-hexyl methacrylate), and poly(methyl methacrylate-co-lauryl methacrylate),abbreviated as PBMA, P(MMA-co-HMA), and P(MMA-co-LMA). These samples exhibited a similarity of their linear
viscoelastic behavior.
For nonlinear extensional rheology, as shown in Figure right, the transient
strain hardening is enhanced on an increase of the side chain length
distribution Those differences are most clearly noted in the top panel of Fig.
3, where ηE+ is directly compared for the three samples (Vader 1000).
namely, in the order of PBMA < P(MMA-co-HMA) < P(MMA-co-LMA):
The side chain would have behaved as a “solvent” to weaken the frictional
reduction and enhance the hardening. For PBMA, the short monodisperse
side chains as a whole always stay near the backbone, thus they should
exhibit a stronger orientational correlation with the backbone thereby
suppressing the strain hardening. In contrast, for P(MMA-co-HMA) andP(MMA-co-LMA), the outer part of the long side chains is located far away from the backbone and would have a rather
isotropic conformation not correlated with the backbone. For this case, the outer part of the side chains should behave as thesolvent to enhance the hardening, in particular for P(MMA-co-LMA) having the largest fraction of that part.

Shilong Wu, Hiroshi Watanabe, Quan Chen, Side-Chain Length Distribution Promotes Transient Elongational Hardening ofPolymer Melts, Physical Review Letters, under review.

－51－

2022-52（国際）Trace metal elemental and isotopic composition in the North Pacific Ocean:sources and internal cycling (3)Tung-Yuan Ho

Academia Sinica

Objectives:
The major objective of this extended joint study is to investigate the sources and internal cyclingof dissolved and particulate trace metals in the water column of the Northwestern and subarctic
Pacific Ocean and to evaluate the impacts of lithogenic and anthropogenic aerosols on thecycling processes. Prof. Yoshiki Sohrin is my host at ICR, Kyoto University.
Methods:
We have joined two Japanese GEOTRACES cruises, KH11-7 and KH15-3, with Prof. Yoshiki
Sohrin’s and other Japanese research groups in the subarctic North Pacific Ocean. We havecollected seawater and particulate samples in the oceanic regions during the cruises. Bothdissolved and suspended particulate samples were collected for trace metal elemental andisotopic composition analysis. Elemental and isotopic composition of trace metals have been
determined by my Ph.D. students (W.-H. Liao and C.-C. Hsieh) by using HR-ICPMS and MCICPMS. The detailed information of the sampling and pretreatment are described in our previous
two published papers.
Result and Discussions:
The details of the results and discussions are under preparation. Chih-Chiang Hsieh, my current
Ph.D. student, has finished the measurement of Fe isotopic composition in the samples and iswriting the manuscript. We found that the quantitative contribution of lithogenic aerosols stillplay a dominant role for the deposition fluxes of dissolvable aerosol Fe in the studied region due
to their high mass fraction and deposition rates (Hsieh et al. in prep).
Publications:
In spite of the limitation of Covid-19 pandemics on in person visit, Prof. Sohrin’s and mylaboratory members have still kept close interaction in the research topics proposed. In 2022, wehave published a paper in Marine Chemistry. Two other collaborative papers are underpreparation. I am also deeply honored to receive the 2022 Oceanochemistry Award, partiallyattributed to my close collaboration with many renowned Japanese chemical oceanographers.
Takano, S., W.-H. Liao, T.-Y. Ho, and Y. Sohrin (2022) Isotopic evolution of dissolved Ni, Cu,
and Zn along the Kuroshio through the East China Sea. Marine Chemistry doi.org/10.1016/
j.marchem. 2022.104135.
Ho, T.-Y. (2022) Multidisciplinary study of trace metal biogeochemistry in the ocean.
Transactions of The Research Institute of Oceanochemistry 35:2, 85-98.
－52－

2022-53（国際）Resolving the structure-dynamics-property relationship in polymer
nanocomposites under uniaxial stretching-II
Tadanori Koga Stony Brook University

g2 (t)

g2 (t)

Objective. The addition of nanoparticles (NPs) to a polymer matrix is a simple route to improving the mechanicalproperty and designing next-generation polymer nanocomposites (PNCs). The key role in this phenomenon is
ascribed to polymer chains (physically) adsorbed on the NP surface (“bound polymer”) that act as tight polymermediated bridges between neighboring NPs at high NP loadings above the percolation threshold, leading to a
network-like microstructure that reinforces the PNCs. However, a comprehensive understanding of the complex
role of polymer bridges in reinforcement under deformation remains unsolved due to the lack of experimental tools
capable of providing structural and dynamic information at the relevant length and time scales. Here we tackle thechallenge to probe the collective motions of NPs associated with bridging network formation under oscillatory
tensile deformation using speckle echo X-ray photon correlation spectroscopy (XPCS).
Experimental. The so-called speckle echo XPCS technique under oscillatory shear allows us to capture theirreversible nanoscopic rearrangements of NPs associated with the yielding of a material1. Calcium carbonate (thesize of 30 nm, the filler loading (x) =20%, which is above the gel point (xc � 16 vol%)) filled cross-linked silicone
elastomer was used. XPCS probes the dynamics over a wide range of timescales (10-3 < t < 103 seconds that iscommensurate with the time window for rheology). When the structure andcorresponding dynamics of NPs change (“out-of-equilibrium”) on the time(a)scale of experiments, a one-time correlation function, g2, which describes
the equilibrium dynamics of NPs, does not correctly describe such aphenomenon. Therefore, a two-time correlation function is necessary,
which defines the intensity-intensity autocorrelation for any respective
Reversible elastic deformation
times t1 and t2 in the time series. The details have been described(b)elsewhere.2 The samples were subjected to oscillatory tensile deformation
at room temperature.
Results. We captured speckle patterns and compared them at a given strain
amplitude and oscillation frequency (Fig. 1a) from which g2 was
0
25
50
75
100
125
150
Time (s)determined in the directions parallel and perpendicular to the stretching
Irreversible plastic deformation
direction. g2 displays periodic peaks corresponding to “echoes” in the(c)elastic
speckle patterns (Fig. 1b). The change in strain between extrema leads togradients in the particle displacements that significantly alter the speckle
pattern even for modest strain values. Thus, g2 ≈ 1 at t = (n + 1/2)T (Fig.
1b), where n is an integer (periods of oscillation), and T is a repeat time for
0
25
50
75
100
125
150
the strain (~ 15 s for the test). On the other hand, at t = nT, the strain returns,
Time (s)and the speckle pattern is recovered, causing g2 to increase above one (Fig.
Fig. 1. (a) Schematic of a strain profile1b). If the deformation is linear and reversible, echoes follow theusing the tensible stage. The strain isequilibrium static dynamics (indicated by the dotted line in Fig. 1b).
ramped back and forth between 0%
Instead, if the deformation is not linear, echoes peaks are reduced (Fig. 1c).
and a given value and held constant at
This attenuation provides a measure of the “nanoscopic” irreversibility ofeach extreme for about 5s during
filler rearrangements. Hence, the results clearly indicate that deformation
which an X-ray exposure wasplays no role in the decorrelation at this strain amplitude, while theobtained. Representative echoes in theg2 functions for cross-linked calcium
significant irreversible rearrangements of NPs occur in the parallel
carbonate filled silicone measured at
direction even when the macroscopic response is still in the linear responseroom temperature are shown: (b) in theregime. The XPCS data will be correlated with the macroscopic
vertical direction and (c) in the parallelmechanical properties which will be measured ex-situ by using a
direction during application of quasirheometer. These studies will shed light on a connection between nanooscillatory strain with 𝛾𝛾=0.5% at q =irreversibility and macroscopic nonlinear deformation, ultimately allowing
0.023 nm-1. The degree of the
us to establish the microscopic criteria for measuring the degree of internalcorrelation of echoes reflects how
material failure non-destructively.
similar the nanoscale structure is
References
between two strain plateaus (e.g.,
1. Rogers, M. C.; Chen, K.; Andrzejewski, L.; Narayanan, S.;strain plateaus (“0” and “2”) and (“0”and “4”) shown in (b) and “0”Ramakrishnan, S.; Leheny, R. L.; Harden, J. L., Echoes in x-ray speckles
corresponding to the initial state of the
track nanometer-scale plastic events in colloidal gels under shear, Phys.
sample).
Rev. E, 90, 062310, 2014.
2. Yavitt, B. M.; Wiegart, L.; Salatto, D.; Huang, Z.; Endoh, M.
K.; Poeller, S.; Petrash, S.; Koga, T., Structural dynamics in UV curable resins resolved by in situ 3D printing
X-ray photon correlation spectroscopy, ACS Appl. Polym. Mater., 2, 4096-4108, 2020.

－53－

2022-54（国際）High Frequency Response of Polymeric Liquids:
Rheology and Dielectric Relaxation
Sathish K. Sukumaran Yamagata University
Experiments performed under isothermal conditions are typically used to investigate theresponse of polymeric liquids to imposed fields. Needless to add, the interpretation of theexperimental results relies on the assumption that the system temperature is not altered by theimposed field and remains uniform throughout the system. Therefore, the isothermal response
functions are appropriate descriptor for any quantitative analysis of the system. However, if theexperimental time scale is shorter than the thermal equilibration time scale, the assumptions ofconstant and uniform temperature are likely to become invalid. An experimentally relevantcase is the response at high frequencies/short times where, adiabatic response functions might
be more appropriate. To investigate this, the theoretical and experimental expertise of ICR(Sato), and the computational, theoretical and experimental expertise of international (Chen,
Watanabe; Changchun) and domestic (Masubuchi; Nagoya) researchers were combined to forma collaboration between ICR and several international and domestic research partners.
The effect of imposing isothermal and adiabatic conditions on the linear dynamics andviscoelasticity of an unentangled polymer melt was investigated. The polymer chains weremodelled as Lennard-Jones beads connected by finitely extensible nonlinear elastic springs andthe motion of the beads were simulated using molecular dynamics (Kremer-Grest model).
Isothermal conditions (NVT ensemble) were simulated by using a Langevin thermostat tocontrol and maintain the temperature. In the adiabatic simulations, the system was decoupledfrom the thermostat thereby preventing energy exchange and thermal equilibration. Oscillatory
shear deformation of sufficiently small amplitude (linear regime) was imposed at several
frequencies and the storage modulus, G’, and the loss modulus, G’’, were determined.
Negligible difference was found between the isothermal and the adiabatic G’ and G’’. Thisimplied that, at least in the linear regime investigated here, the imposed conditions had
negligible effect on the relaxation times or equivalently, the dynamics of the polymer chains.
Under adiabatic conditions however, the system temperature progressively increased with time
and the temperature increase under high frequency oscillatory shear deformation was
significantly larger than under low frequencies. Needless to add, the increase in temperature
under adiabatic conditions cannot be sustained indefinitely without affecting both the state of
the system and its response to the external field and therefore, clearly unphysical. We are
currently investigating the response when the shear (oscillatory and step) is applied for longer
times. Based on these results, we plan to investigate the more interesting but significantly moredifficult nonlinear response regime in the future.
－54－

2022-55（国際）Control of Mechanical Properties in Polymer Blend Materials by Hydrogen
Bonding Interaction
Osamu Urakawa

Osaka University

It has long been known that introducing specific attractive interactions, such as hydrogenbonding, into a compatible polymer blend can enhance its thermal and mechanical properties1.
However, the quantitative relationship between the strength of the interaction and the rheologicalproperties has not yet been established especially for the entangled systems. In this study we
examined rheological behaviors for miscible polymer blends, poly(2-vinyl pyridine) / poly(4-vinyl
phenol) (2VPy/VPh), in which intermolecular hydrogen bonds play an important role2. The
molecular weight of the 2VPy (2VPy182) was Mw=1.82×105, higher than the entanglementmolecular-weight Me, while those of VPhs were Mw=1.9×103 (VPh2) and Mw=4.5×103 (VPh5),
both lower than Me. In the mixture of 2VPy/VPh, only the 2VPy chains entangle each other, andthe low molecular weight VPh can be regarded as a diluent.
We found that the time-temperature superposition principle approximately holds, andcomposite curves of the complex moduli could be constructed. WLF equation with a single
parameter set (c1 and c2) could represent their shift factors by setting the reference temperatures Tr*
to be Tg+64°C, where Tg is the glass transition temperature of each blend. Figure 1 shows thecomposite curves of storage moduli G′ at Tr* for 2VPy182/VPh5 blends with several compositions.
The rubbery plateau modulus GN observed in the frequency between 10-1 s-1 and 102 s-1 decreased
with decreasing the 2VPy concentration (the weight fraction w2VPy ~ volume fraction φ was varied
from 1 to 0), according to the following relationship: GN ~ w2VPy2. This means that the entanglement
density decreases simply by the dilution effect, even though hydrogen bonds between VPh and
2VPy exist. Contrary, the zero shear viscosity η0 and the cross point relaxation time τx (determinedfrom the frequency at which G′ = G″) show weaker concentration dependence than polymer /diluent systems. As shown in Figure 2, the following relations were confirmed: η0~ w2VPy1.8 and τx~
w2VPy0.53. These exponents are smaller than the ordinary solution values3: η0~ φ3.6 and τ~ φ1.3,
suggesting that the terminal flow of the 2VPy/VPh blends is affected by the hydrogen-bonded
associates.
6.5

τx (2VPy182/VPh5)
τx (2VPy182/VPh2)

η0
η0

5.5
5.0

2.0
1.5

slope 1.8

4.5
4.0

0.1

Figure 1 Composite curves of G′ for 2VPy182 blendswith several compositions.

1.0

slope 0.53
2

0.5
3

4

w2VPy

6

7 8 9

1

0.0

Figure 2 Dependence of η0 and τx on the
2VPy concentration.

1 Z. Yang, and C.D. Han, Macromolecules. 49, 153 (2021).
2 O. Urakawa, et al., Nihon Reoroji Gakkaishi (J Soc Rheo Jpn). 49, 155 (2021).
3 R.H. Colby et al., Macromolecules. 24, 3873 (1991).

－55－

5

log (τ / s )log (G' / Pa)log (η0 / Pa s )6.0

2022-56
Analyzing Structural Fluctuation in Thermally Activated Delayed
Fluorescence Materials with Ultralow-Frequency Raman Spectroscopy
Hikaru Sotome

Osaka University

Thermally activated delayed fluorescent (TADF) materials are luminescent materials that can achieve
an internal quantum efficiency of 100% by utilizing the triplet state produced by charge recombination. The
key to this high emission quantum yield is the reverse intersystem crossing (RISC) from the triplet state (T1state) to the fluorescent singlet state (S1 state). Recent studies suggest that not only the energy gap between
the S1 and T1 states but also dynamic structural fluctuation contributes to the high RISC efficiency. Such
dynamic structural changes correspond to low-frequency vibrational modes involving the overall molecular
framework, but conventional vibration spectroscopy has difficulty in visualizing the above nuclear
displacements due to the limited detection wavenumber region. In the present work, to elucidate the role oflow-frequency vibrational modes in the RISC process we have analyzed such vibrational modes using Raman
spectroscopy in the ultralow-frequency region down to 5 cm-1.
We first measured Raman spectra of powder MA-TA (Figure 1a), which is a blue emissive TADF
molecule recently developed in Kaji group (Kyoto Univ., ICR), and compared with those obtained fromquantum chemical calculation. Figure 1b shows experimental and calculated Raman spectra of MA-TA. Five
low-frequency modes were observed at 18, 46, 66, 81 and 122 cm-1, and this spectral pattern was well
reproduced by calculated one of a single MA-TA molecule. This result indicates that we can analyze the lowfrequency modes involved in the overall molecular skeleton free from lattice phonon modes. To identify thevibrational modes assisting RISC, we calculated nuclear displacement vector in the conversion from the T1state to the S1 state. The magnitudes are plotted as a function of normal mode frequencies, as shown in Figure
1c. Two modes at 13 and 16 cm-1, which correspond to the experimentally observed mode at 18 cm-1, showprominent amplitude. These vibrational modes are ascribable to relative rotation between MA and TA units. A
series of the results show that this rotational motion promotes the efficient T1-S1 conversion and a key nuclear
displacement in the RISC process.

Figure 1. (a) Chemical structure of MA-TA. (b) Experimental and calculated (scaled by 1.2) Raman spectra.
(c) Magnitude of nuclear displacement vectors in RISC. The vibrational modes at 13 and 16 cm-1 are depicted.

－56－

2022-57
Effect of microplastics on the distribution of trace heavy metals in seawater
Yuzuru Nakaguchi

Kindai University

Purpose) Trace metals were play an important role in marine biogeochemistry. These elements exist as thedissolved state (dMs) and labile particulate (lpMs) in seawater. The particulate matter in seawater includes metaloxides, hydroxides, sulfates, carbonate compounds, mineral particles, and biological particles. In recent years,
microplastics produced by UV degradation and weathering have been added to particulate matter in seawater.
However, the detail relationship between trace metals and microplastics remain unknown. In this research, In
this study, we targeted Osaka Bay, Yodo River and Yamato River, which is greatly affected by human activities.
In order to clarify the relationship between the trace metal speciation and microplastics, we determined trace
metals and microplastics in seawater.
Experimental) Sea water samples were collected by Niskin sampler in September. 28 in 2022 and February 1 in
2023. River water samples were collected at the Yodo and Yamato River in June, August and October in 2022.
All sea water samples were transferred to precleaned LDPE Nalgene bottles. Unfiltered samples were directlycollected from Niskin bottles to determine the concentrations of total dissolvable trace metals (tdMs). Someportions of samples were filtered through PTFE membrane filters with pore size 0.22 µm to determine theconcentrations of dissolved trace metals (dMs). All the filtered and unfiltered samples for trace metals wereacidified with 20% HCl (Tamapure AA-10) to achieve a final HCl concentration of 0.010 mol/kg (pH ~2.2).
Nutrients were determined by autoanalyzer. Chlorophyll a was determined by high performance liquid
chromatography. The trace metals were preconcentrated using a chelating resin which ethylenediaminetriacetic
and iminodiacetic acids were immobilized. Trace metals are determined by a high-resolution ICP-MS (HR-ICPMS) equipped with a magnetic sector mass spectrometer. The sample solutions for microplastics were filteredby PTFE membrane filters with pore size 5.0 µm. After filtration, the samples with filters transferred toseparatory funnel. A saturated NaI solution was added to the separating funnel, and the microplastics wereseparated by the difference of density. After separation, the organic matters remaining in the sample were
decomposed by mixed acid (HNO3+HClO4+HF). Microplastics were identified by Microscopic Raman
photoluminescence system.
Results and discussions) The load of MP which supplied from the Yodo River to Osaka Bay was estimated. The
weight of MP were measured by size as MPfine (particle size <100 µm), MPcoarse (particle size from 100 µm
to 4.75 mm). The average loads of MP were calculated to be 43.0 ton/year for MPfine and 13.2 ton/year for
MPcoarse from the concentration of MP and the river discharge of the Yodo River.
Achievement report) Nakaguchi, Y., Sakamoto, A., Asatani, T., Minami, T., Shitashima,K., Sohrine, Y.
Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the Seas of Japan and Okhotsk. Mar.
Chem. 241, 104108, doi.org/10.1016/j.marchem. 2022.104108 (2022)－57－

2022-58
Exploration of liquid membrane transportation of metal ions with a polymer
membrane containing ionic liquid by use of electric field response of ions
Hiroshi Mukai[Introduction]

Kyoto University of Education

Liquid-liquid extraction is one of the useful methods for metal recycling which is getting

more important for sustainable use of metal resources. Hence, liquid membrane transportation of metal ionsusing a thin layer of a liquid membrane (LM) instead of an organic solvent is an alternative method of liquidliquid extraction which use a large amount of harmful organic solvents and valuable carrier molecules. ThisLM method is expected to reduce these risks and costs. In our previous work, an almost quantitativetransportation of copper (II) ions using polyvinyl chloride (PVC) membrane containing ionic liquid (IL) was
achieved. However, the flow rate of metal ions was not sufficient for practical use. In order to improve theflow rate, the use of electric field response of the ions in IL was attempted. Week alternating current by ionic
conduction of IL was generated through a LM by two mesh electrodes located at both sides of the LM. This
electric field response of IL ions in a LM was expected to stir the LM phase and to promote the diffusion of
metal species transported. The influence of the electric field response to metal transportations was examined.
[Experimental](1) Preparation of membranes: 1-Phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP) was

dissolved in 1-butyl-3-dodecylimidazolium bis(trifluoromethanesulfonyl)imide ([C4C12im][Tf2N]) at theconcentration of 0.005 mol kg-1. This solution of 1.0 g and PVC of 0.1 g was dissolved in tetrahydrofuran of
5 g in the glass petri dish of 49 mm inner diameter and were dried. (2) LM transportation: The membrane (38.5mm in diameter) was fixed at the center of a U-shaped reaction tube of PVC. The 30 cm3 of aqueous supplying
phase ([Fe(NO3)3] = 2.0×10-5 mol dm-3, [CH3COONa] = 0.01 mol dm-3, [NaClO4] = 0.1 mol dm-3, pH 5.0)
and the 30 cm3 of aqueous receiving phase ([CH3COONa] = 0.01 mol dm-3, [NaClO4] = 0.1 mol dm-3, [HNO3]= 0.1 M, pH 1) were poured into each part of the reaction tube separated by the membrane, which was put
between copper mesh electrodes (32 mm in diameter) with 0.5 V alternating voltage. 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 fresh mesh electrodes made of copper wires were gradually dissolved in acidic
aqueous media. To prevent the dissolution of copper, the electrodes were used once in the reaction tube underalternating voltage of 0.5 V before LM transportation of metals. Because of the influence of the dissolution ofcopper in the aqueous phases, LM transportation experiments were carried out for iron (III) ions. The
transportation rates of Fe (III) ions after 24 hours under alternating voltage of 0 V and 0.5 V are 0.18 and 0,
respectively, and the removal rates from the receiving phase are 0.81 and 0.56, respectively. Contrary of
expectations, the both of the rates decreased under electric tension probably because of electrode reactions.
The removal of iron (III) ions in the supplying phase by reduction to metal on the electrode and the depletionof protons on the surface of LM in the receiving phase by reduction to hydrogen are considered as reasons.
[Outcome report]

1. H. Mukai, S. Miyamoto, A. Nishimura, R. Konishi, Y. Sohrin, 71st JSAC annual

meeting abstracts, PA3025 (2022).
－58－2022-59
硫黄ポリマー材料におけるナノ構造不均一評価
藤原明比古

関西学院大学1. 緒言 : X 線小角散乱（SAXS）-CT 法では、材料内部のナノスケールの構造分布を非破壊で観測することが可能である。本法は、各投影角で走査しながら SAXS 測定を行うことで、得られた散乱像のシグナルから CT 像を再構成する手法である。このシグナルは、ナノスケールの構造情報に起因しているため、対応する構造情報の分布が CT 像より明らかにできる。しかしながら、測定時間
が 2-3 時間程度有するため、計測の短時間化が大きな課題である。これまで、共同研究者の竹中・小川らとともに、計測については投影角度を間引くことで測定を短時間し、得られた再構成画像をトータルバリエーション（TV）正則化により画像回復を実現した。しかしながら、依然として測定には 1-2 時間程度を有している。硫黄ポリマー材料等への応用にはさらなる測定の短時間化が必要であるため、ビームを複数方向(マルチビーム)から入射する SAXSCT 法の開発研究を始めた。
2. 実験 : マルチビーム SAXSCT 法に向けて、従来の 1 ビームからマルチビーム化を実現する必要がある。まずは 2 ビーム化の方法に関する基礎的な検証を、大型放射光施設 SPring-8 の BL03XU において実施した。
3. 結果 : 2 ビーム化の検討を進め、同時に、2 ビームに対していかに効率よく試料全面をスキャンするかについても検討を行った。2 ビーム化には、大きく分けて波面分割（例えば図 1（案 1）：結晶の Bragg 反射（2 回反射）を利用）、振幅分割（例えば図 1（案 2）：結晶の Bragg 反射（1 回反射を利用）、図 1（案 3）：結晶による多波同時 Bragg 反射（2 回反射）+ ダイレクトビーム利用）の 3 種類が考えられる。案 1
及び 2 については、試料後に散乱した X 線を検出するための
図 1：2 ビーム化に向けた光学系案。

真空パスや検出器などの設置に大幅な改良が必要であり、実現するには膨大なコストがかかってしまう。本計測を効率的に実施するため案 3 を候補として絞り、その結果、案として、結晶による多波同時 Bragg 反射（2 回反射）+ ダイレクトビーム利用）について検討した。1 ビーム目に対して最も条件が厳しい 90 度で入射可能な最適条件と、それを実現するための光学素子の設計を進めた。その結果、X 線のエネルギーを 7.51keV を選

図 2：本研究で成功した 2 ビーム化の概要と各ビーム
プロファイル。

択し、図 1 に示すような三つの結晶系(第一結晶:Si(111)面、第二、三結晶:Si(311)面)で反射することで、90 度の入射が可能であることがわかった(図 2)。

－59－2022-60－60－

2022-61
プラズモニック合金ナノ粒子を設計するための理論的指針の構築
飯田健二 北海道大学

周期表 11 族の単金属(Cu，[目的] 可視域に局在表面プラズモン共鳴(LSPR)吸収を示す材料としては，
Ag，Au)のみが使われてきた。しかし近年，B2(塩化セシウム)型や C1 型の合金ナノ粒子が可視域に
LSPR 吸収を示すことが京大化研寺西研究室にて見いだされた。我々は，合金ナノ粒子の設計に資する知見を得るべく理論計算研究を進めてきた。2022 年度は，C1 型構造を持つ PtIn2 に着目して，光励起の機構を解析した。

[計算手法] 高い並列化効率を有する第一原理計算プログラム SALMON を用いた大規模計算によって，直径数 nm のナノ粒子の光励起電子ダイナミクスをシ
ミュレーションした。結晶構造から直径約 3 nm の Pt249In432 合金ナノ粒子(図1)を切り出して計算した。また，光触媒や光電極の研究へと展開していくため，溶液中のナノ粒子や固液界面の光や電圧に対する応答を計算することが出来

図 1. 対 象 と し た
Pt249In432 ナノ粒子。

1,2
るようにプログラムを拡張した。

[結果と考察] 光励起の機構を明らかにするべく，2.8 eV で 20 fs のパルス光を照射したときの電子占有数の変化を解析した。光照射中の 10 fs の時に比べると，光照射後の 20 fs では占有数が全体的に大きく変化していた。これは光の照射にともない電子遷移が進んだことを示す。さらに遷移強度の軌道エネル
ギーに対する依存性を比較したところ，10 fs ではフェルミレベル(0 eV)近傍の−1 ~ 1 eV で大きく変化していた一方で，20 fs では−3 ~ −2 eV および 2 ~ 3 eV で大きく変化していた。金ナノ粒子では，フェルミレベル近傍の自由電子のバンド内遷移が d 電子のバンド間遷移を誘起することが知られている。
Pt249In432 に対する本計算結果は，−1 eV から 1 eV にある電子が光応答して，その後に−3 ~ −2 eV の電子がバンド間遷移することを示す。PtIn2 ナノ粒子の光励起について，LSPR に起因するキャリア生成の機構が発現していることが分かった。

[論文(謝辞あり)][1] K. Iida, J. Phys. Chem. C, 126, 7492-7499 (2022).
[2] K. Iida, J. Phys. Chem. C, 126, 9466-9474 (2022).

[学会発表(招待講演)][3] K. Iida, "Theoretical Study on Heterogeneous Interface under Light and Voltage Bias" IMS-ICAT Joint
Symposium of Surface Science for Catalysis, Hokkaido University., Oct. 11, 2022.
[4] K. Iida "Theoretical and Computational Study on Nanostructures under Light and Voltage Bias" ICAT-FHI
Symposium: New Dimension of Catalytic Surface Study, Hokkaido University., Sep. 16, 2022.

－61－

2022-62
新規ハイブリッド型部分フッ素化リン脂質二分子膜の構造・物性の解析
園山正史

【目的】

群馬大学

私たちはこれまで，膜タンパク質研究に資する部分フッ素化リン脂質の設計指針を得るための物理化学的な研究により，リン脂質 Dimyristoylphosphatidylcholine（DMPC）の 2 本の疎水鎖の末端にパーフルオロアルキル基(Rf, CnF2n+1)を部分的に導入したアナログ分子群 Fn-DMPC（n = 2, 4, 6, 8）は，Rf 鎖長依存的な際だった膜物性を示すこと等を明らかにして来た。本研究では，DMPC の一方の疎水鎖の末端を部分フッ素化した新規 Hybrid 脂質シリーズ Fn-Hybrid を新たに合成し，膜物性および分子構造を調べることにより，膜タンパク質研究への応用の可能性を探ることを目的とした。
【方法】

これまでの方法に準じて合成した新規 Hybrid 脂質 Fn-Hybrid（n = 4, 8）を用いて，示差走査熱量測定（DSC）により脂質膜の熱物性を調べた。また，水面上単分子膜の表面圧−面積（π−A）等温曲線を 25℃において測定した。さらに水面上単分
子膜を金基板に転写し，赤外反射吸収（RAS）スペクトルを測定した。
【結果と考察】Fn-Hybrid 懸濁液の DSC 測定を行ったところ，F4-Hybrid は 0.97 ℃に主転移と考えられる吸熱ピークを示したが，F8-Hybrid では
0 ℃以上に明確なピークが観測されなかった。したがって F8-Hybrid の主転移温度は氷点下と考えられ，DMPC の 24.4 ℃に比べて F8-DMPC の主転移温度が約 40 ℃上昇することと対照的であった。
25 ℃ に お い て 測 定 し た F4-Hybrid お よ び
F8-Hybrid の水面上単分子膜のπ−A 曲線を DMPCとともに右図に示す。F4-Hybrid では F4-DMPC より低面積側で気体膜が現れた。これは，Rf 基とア

図． Fn-Hybrid（ n = 4,8） およ びD M PC水面上
単分子膜の表面圧ｰ面積等温曲線（ 25 ℃）

ルキル基の異なる占有面積が原因と考えられる。F8-Hybrid は，DMPC よりも高面積側に先ず液体膨張膜を形成した。これも Rf 基の占有面積がアルキル基よりも大きいことに由来すると考えられる。興味深いことに，2 本の疎水鎖に Rf 基を導入した F8-DMPCに比べ，F8-Hybrid の液体膨張膜は高面積側に現れた。これは，両方の疎水鎖に Rf 基が導入された F8-DMPC は，Rf 基間の強い相互作用により分子が密に凝集した膜を形成するのに対し，一方の疎水鎖のみ Rf 基を導入した F8-Hybrid では分子間相互作用が抑制されているためと考えられる。RAS スペクトルで観測された CF2 対称伸縮振動バ
ンドも，分子パッキングに関する本考察を支持している。
【成果報告】
中川原ら，1 本の疎水鎖末端をフッ素化した新規 Hybrid 脂質シリーズの水面上単分子膜の特性評価，日本化学会第 103 春季年会（2023 年 3 月 22 日（予定）），他 2 件。
－62－2022-63
Identification of active gibberellins in the basal land plant
Marchantia polymorpha
Takayuki Kohchi

Kyoto University

Active gibberellins (GAs) are important plant hormones that regulate plant growth anddevelopment. A number of GA-related factors, including biosynthetic enzymes and receptors, havebeen identified, and the physiological functions of GAs have been elucidated mainly from
Arabidopsis and rice plants. To systematically understand the origin of GAs and the molecular
evolution of their signaling pathways, we focused on the liverwort, Marchantia polymorpha.
Phylogenetic analysis has shown that M. polymorpha is located at the basal land plant lineage, andis an excellent model with basic genetic information and technologies. From our previous
experiments, we found that GA signaling factors found in vascular plants are partially present in M.

polymorpha. To identify the active GA, we developed a bioassay of M. polymorpha. Since GA
biosynthetic mutants of M. polymorpha showed the delayed sexual organ formation, we preparedfractionated samples from extracts of according to the two-phase partitioning method, and conducteda bioassay using the timing of sexual organ formation as an indicator in collaboration with Dr.
Shinjiro Yamaguchi (co-researcher) and Dr. Kiyoshi Mashiguchi (research collaborator) of theInstitute for Chemical Research, Kyoto University. We found that the fraction in which low polar
acidic substances accumulated showed the activities of restoring the delayed sexual organ formationof GA biosynthesis mutants. We further analyzed this fraction using HPLC and reverse-phasecolumns, and identified a specific subfraction that affected sexual organ formation. We are planningto determine the structure of the active GA by combining mass spectrometry and NMR. We are also
searching for potential GA receptors by genetic approaches. Mutants of MpSABATH2, which
possibly encodes an inactivating enzyme of GA, showed severe phenotypes such as dwarfism andgrowth inhibition. In order to obtain mutants that suppress these phenotypes, we conducted an EMS
mediated mutant screen. As a result, we could obtain five independent mutants. NGS analysis
revealed a candidate transcription factor (TF), which was considered to be the causal gene of all themutants. Complementation test confirmed that this TF as the causal gene. We plan to investigate
the possibility of the TF as a receptor in the future.

Conference reports
Okabe et al. (2022), Exploration of gibberellin related compounds in liverworts Marchantia polymorpha. The
86th Annual Meeting of the Botanical Society of Japan
Shimokawa et al. (2022), Screen for mutants affecting methyltransferase function related to gibberellins inMarchantia polymorpha. The 86th Annual Meeting of the Botanical Society of Japan
Shimokawa et al. (2023), Exploration for a novel signaling factor of gibberellin in Marchantia polymorpha. The
64th Annual Meeting of the Japanese Society of Plant Physiologists－63－2022-64（国際）Characteristics of quantum magnon in magnetic insulators
Kab-Jin Kim

KAISTObjective:
The aim of the research is to study the characteristic properties of magnon in magnetic
insulators.
Experimental methods:
We measured magnon propagation in YIG (Yttrium iron garnet), which is a magnetic
insulator, in the frequency/time domain using micro-patterned coplanar waveguide
antennae and a 25 GHz vector network analyzer. We observed the effect of heavy-metal(HM) distributed Bragg reflector (DBR) on the magnon propagation. We also measured
the magnon excitation mode in the vicinity of the microwave resonator, to investigate
the magnon-photon coupling phenomena. For that, microwave transmission at the YIG
sphere mounted at the center of a ring-shaped NbN-based superconducting microwave
resonator is measured using a VNA and the real-time oscilloscope.
Experimental results:
The magnon spectrum in YIG film shows a distinct magneto-static surface wave
characteristic. By altering its period, we observed the impact of the magnonic DBR
effect on magnonic transmission dispersion. Injection of current through the magnonic
DBR, which applies spin-orbit torques in the YIG layer, suppressed magnon modes that
did not match the period of the HM grating. During the magnon-photon coupling
experiment, we observed a prominent anti-crossing between the magnon and microwave
photon bands, and the Rabi-like oscillation between two coupled magnon modes in YIG
spheres.
Discussion:
The magnonic gating effect plays a crucial role in regulating magnon transport for
future quantum magnonic technology. Using the DBR effect to selectively control
magnon modes opens the possibility of single magnon qubit processing, such as amagnonic Hadamard gate. The magnon-photon coupling phenomenon and Rabi-likeoscillation between two magnon modes offer potential applications in hybrid quantum
magnonic devices, serving as a quantum interface for future quantum computers.

－64－2022-65（国際）Observation of orbital Hall effect in transition metal dichalcogenides
Sanghoon Kim

University of Ulsan

Next-generation memories called as non-volatile RAMs (NVRAM) are demanded toovercome the speed of DRAM, and storage density of the NAND flash memory.
Magnetoresistive random access memory (MRAM) is a representative next-generation nonvolatile memory and has been successfully commercialized as an embedded type by Samsung
Electronics and TSMC. The MRAM consists of nanometer-sized magnets, and storesinformation by using a phenomenon in which a resistance difference occurs depending on the
direction of magnetization directions. In order to increase the energy efficiency of the MRAM,a high conversion rate from charge to spin current is required. Here, spin current can be
defined as a flow of electronsʼ spin angular momentum. The memory using this phenomenon
is called spin-orbit torque (SOT) MRAM because it simultaneously utilizes spin and orbital,
which are the rotational motion and the orbital motion of electrons, respectively. The SOTMRAM is considered as the next-generation technology of currently commercialized MRAM,
so research is being focused around the world.
The key to improving the efficiency of spin-orbit torque (SOT) MRAM technology is togenerate a sufficient amount of spin current. Recently proposed orbital-Hall-induced torque(OHT) can be a candidate to enhance the efficiency because the orbital current jorbital, as aresult of the orbital Hall effect (OHE), has been expected to be quite larger than the jspin insome elements.
A research team led by Professor Sanghoon Kim from the Department of Physics at the
University of Ulsan has conducted an international joint research program with Professor
Teruo Ono group at Kyoto University. Using atomic-level thin film deposition technology,
the team fabricated a W/Co/Pt asymmetric artificial superlattice and observed that thegenerated spin current was more than 300% higher than that of Pt, an element that has beenstudied as important in existing SOT-MRAM. We found that this result is attributed to theorbital structure of the superlattice. Our result can be a standard approach to observe theorbital Hall effect in transition metal dichalcogenides. Details can be found in our recent
paper; Adv. Sci. (2023) 2206800.

－65－2022-66（国際）Investigation on high efficient spin-orbit torque effect in multilayerswith combine anisotropy and DMI
Alexey Ognev

Far Eastern Federal University

Epitaxial [Pd/Co/CoO]n superlattices were grown on the single crystal Si(111)substrates by the molecular beam epitaxy technique. The samples were grown in an ultrahighvacuum chamber (Omicron Nanotechnologies) with pressure P ≈ 10-10 Torr. Si(111)substrates were prepared by chemical cleaning before loading into the chamber. Eachferromagnetic layer (Co) was oxidized for 3 minutes in a dry oxygen atmosphere in theseparated chamber which equipped with a gas flow system. The deposition of each following
layer was controlled by recording the RHEED. The magnetic parameters of the samples werestudied using a vibrating sample magnetometer (LakeShore VSM 7410). The study of thedomain structure was carried out using a magneto-optical Kerr microscope (MOKE, Evico
Magnetics) and a magnetic force microscope (MFM, Ntegra Aura) allowing the manipulationof the magnetic structure by high coercivity magnetic probes.
In epitaxial [Pd/Co/CoO]n superlattices the perpendicular magnetic anisotropy isobserved. The curvature of the loops at values of the applied magnetic field (H) close tosaturation indicates the manifestation of the dipole-dipole interaction between magnetic
layers. The partial oxidation of the Co layer broke the structural inversion symmetry of thesystem promoting the existence of the interfacial Dzyaloshinskii-Moriya interaction. The
competitive contributions of the i-DMI, PMA and interlayer dipole-dipole interaction create
conditions favorable for the origin of chiral domains (labyrinth ordering of domain walls).
Magnetic force microscopy is used forformation the skyrmion lattices from the labyrinth
structure of [Pd/Co/CoO/Pd]n samples, where n =7 and n = 10 . We demonstrated that of the two-passscan by the MFM probe led to the complete
formation of the skyrmion lattice as shown in theright figures. The size and density of skyrmionsdepended on the periodicity of the labyrinth domain
structure and on the distance between two adjacentscanning lines. These results can be used to create anovel type of magnetic memory based on skyrmions,which will allow significantly improve the speed ofreading/writing of information.

－66－

2022-67（国際）Research on the efficiency enhancement of the NV centers creation in
nanodiamond
Takuya F. Segawa ETH Zürich
For the life science application, the NV centers in nanodiamonds are significantly interested asa nanoscale probe for dynamics, magnetic field, electric field, temperature, and pH in a living cell.
Yet, knowledge regarding the formation mechanism in very small particles is still limited. Half-fieldsignals in electron paramagnetic resonance (EPR) spectroscopy are recorded as a reliable method toquantify NV- centers in nanodiamonds. Enhancing the efficiency of creating the NV centers in
nanodiamonds is required for a higher sensitivity of the NV sensor. The investigation of themechanism is very important for elucidation and improvement of it.
We measured the EPR spectrum of the NV center in nanodiamonds, which were produced byvarious methods. One of the main targets in the project is detonation nanodiamonds (DND), which
our collaborators produced. In Figure 1, halffield EPR spectra (= 9.87 GHz) of electron
irradiated DNDs with 2 MeV electrons (darkgreen) and 1 MeV electrons (light green) at afluence of 5×1018 e-/cm2 are shown and arereported in [1]. The spectra shown werebackground corrected. In addition, we measured
TEM (Transmission Electron Microscopy) andDLS (Dynamic Light Scattering) to estimate thesize of nanodiamonds. We discussed andanalyzed the EPR spectra and enhancement of
the efficiency of creation of the NV centers in
nanodiamond.

Theobtained

results

andinformation are important for higher sensitivity
and the life science application of the NV
sensor.

Figure 1. Half-field EPR spectra (= 9.87 GHz)of electron irradiated DNDs with 2 MeV
electrons (dark green) and 1 MeV electrons (lightgreen) at a fluence of 5×1018 e-/cm2. The spectra
shown were background corrected. [1]Published papers[1] F. T.-K. So, A. I. Shames, D. Terada, T. Genjo, H. Morishita, I. Ohki, T. Ohshima, S. Onoda, H.
Takahsima, S. Takeuchi, N. Mizuochi, R. Igarashi, M. Shirakawa, T. F. Segawa, The Journal of
Physical Chemistry C, 126 (11), 5206-5217 (2022).
[2] D. Terada, F. T. K. So, B. Hattemdorf, T. Yanagi, E. O̅ sawa, N. Mizuochi, M. Shirakawa, R.
Igarashi, T. F. Segawa, Nanoscale Advances 4, 2268 (2022).

－67－2022-68（国際）Research toward stable NV centers at shallow region and spin dynamics indiamond
Gopalakrishnan Balasubramanian Helmholtz-Zentrum Dresden-Rossendorf
Recently, NV centers in diamond have been significantly interested as a candidate for a
resource for quantum sensing with nanoscale spatial resolution and ultra-high sensitivity. It is because
single spins can be coherently controlled, and the spin coherence times are significantly long even atroom temperature (RT) in the NV center. By utilizing nanoscale shallow NV centers, applications fornanoscale imaging and nanoscale nuclear magnetic resonance were demonstrated.
Toward these issues, Kyoto University group synthesized Phosphorus doped n-type diamond [1].
To make stable NV centers at shallow regions, the n-type diamond plays important roles in the longspin-coherence time (T2), the stabilization of the charge state, and an improvement of the creation
yield of NV centers formed by the ion-implantation technique [2]. The n-type diamond samples weresynthesized by CVD using tert-butylphosphine,which is much less toxic than phosphine. Hallmeasurements confirmed n-type conduction inmeasured samples prepared under different
growth conditions. The highest measured Hall
mobility at room temperature was 422
cm2/(Vs). The T2 was increased to 1.62 ± 0.10
ms in the sample with the lowest nitrogenconcentration. Optically detected magnetic
resonance spectra indicated that all measured
NV centers were aligned along the [111]direction. This study provides appropriate CVD

Fig. 1, Hahn-echo signal of the NV center inconditions for growing phosphorus-doped n-diamond (data with black dots, exponential-

type diamonds with perfectly aligned NV

decay fit with red line, T2 = 1.62 ± 0.1 ms). The

centers exhibiting long spin coherence times,

dashed black line at 0 corresponds to the statespaving the way to developing and applying

being populated equally. To remove common-

diamond quantum sensing devices.

mode noise, two results were subtracted andPublished paper

normalized [1].

[1] R. Kawase, H. Kawashima, H. Kato, N. Tokuda, S. Yamasaki, M. Ogura, T. Makino, N.
Mizuochi, Journal of Applied Physics, 132, 174504 (2022).
[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).

－68－2022-69
Demonstration of topological phase control in chalcogenide superlattice
Misako Morota AIST
Purpose: This study aims to create a variety of topological materials by simply changing the combination of
thickness, number of layers, repeat counts of multilayers consisting of a few types of chalcogenide materials and todemonstrate new topological properties, and this is a continuing project from the previous year. Topologicalinsulators are anticipated to exhibit highly efficient spin-charge current conversion due to surface states caused bystrong spin-orbit coupling. In the previous year, we measured spin-torque ferromagnetic resonance (ST-FMR) using
Sb2Te3/ferromagnetic metal bilayers, as a result, we succeeded in obtaining a frequency-dependent ST-FMR signal.
However, the signal intensity is too weak for detailed measurements because of its the high resistivity around 1000
Ohm. In this year, we tried to measure ST-FMR superimposed with ferromagnetic resonance due to an induced
magnetic field by adding a metallic layer to the Sb2Te3/ferromagnetic metal bilayer film.
Experimental: First, multilayer films of Sb2Te3/NiFe/Ru were deposited on thermally oxidized silicon substratesby RF sputtering without breaking the vacuum at AIST. Next, device processing and ST-FMR measurements were
performed at Institute for Chemical Research, Kyoto University. The NiFe and Ru layer thicknesses were fixed forall samples at 5 nm and 10 nm, respectively, and the Sb2Te3 layers were crystalline highly oriented crystalline film
and prepared at three different thicknesses of 4, 5, and 10 nm.
Results and Discussion:
Figure shows the ST-FMR voltage for the
Sb2Te3 5nm/NiFe 5nm/Ru 10nm sample ateach frequency. These signals of thesample were about 5 times stronger thanthat of the previous sample with the same
thickness of Sb2Te3 and ferromagnetic
bilayer. In addition, the asymmetry ofthesesignalsalso

evidencesthat

ferromagnetic resonance is caused by the

Figure. Signal of ST-FMR on a Sb2Te3 5nm/NiFe 5nm/Ru 10nm

induced magnetic field of the current

sample measured under frequencies of 2-8 GHz. The inset isflowing across the Ru layer. In the future,

direction of the applied external field to the sample.

this sample structure will be optimized forfurther detailed measurements by using
ST-FMR.

－69－

2022-70
人工反強磁性体のマグノンを用いた量子情報演算素子の基盤技術開発
石橋未央 東京大学

本研究では、人工反強磁性面内磁化膜において観測された音響モードと光学モードのマグノン結合[1]を利用した新しい情報素子開発を目的として、マイクロマグネティックシミュレーション[2]を用いて、マグノン結合した人工反強磁性面内磁化膜に外部からギャップ周波数に対応した交流磁場を印加することで、マグノン結合状態の制御を試みた。図(a)に示すように、音響モードと光学モードが最も強く結合する、マグノンの伝播方向に対して 45 度だけ傾けた方向に面内磁場を印加した人工反強磁性面内磁化膜を再現する。理論計算から、この系は 10.2 GHz と 11.2 GHz の共鳴周波数を有している。低い方の共鳴周波数である 10.2 GHz のマグノンをアンテナによって励起する。
アンテナの中心部から 10 μm だけ離れた位置の幅 2 μm の領域に、ギャップ周波数に対応した 1
GHz（11.2 GHz と 10.2 GHz の差分）の交流磁場を印加する。この 1GHz の交流磁場を印加した領域の通過前と通過後の位置での z 方向の磁化の時間変化をフーリエ変換することで、伝播するマグノンの共鳴周波数が得られる。図（b）、（c）は、1 GHz の交流磁場を 45 度の外部磁場に平行に印加した場合と、直交して印加した場合の 11.2 GHz の共鳴ピークの大きさの交流磁場の振幅依存性である。交流磁場を外部磁場と平行に印加した場合（図（b））、通過後、11.2 GHz の共鳴周波数のマグノンが通過前よりも多く伝播していることがわかる。本研究結果より、ギャップ周波数の交流
磁場の印加によって伝播するマグノンのモード遷移を確認できたと考えられる。

（a）

（b）

図(a)

（c）

シミュレーション設定。
（b）、(c) シミュレーションによって得られた磁化の振動を解析した結果。

[1] Y. Shiota et al., Phys. Rev. Lett. 125, 017203 (2020). [2] A. Vansteenkiste et al., AIP Advances 4, 107133 (2014).

－70－

2022-71
ダイヤモンド量子情報素子のための表面状態研究
徳田規夫 金沢大学【緒言・目的】ダイヤモンド中の NV 中心は、超高感度量子センサとして幅広い分野での応用が期待される。特に、表面からナノレベルの深さに存在する NV 中心は、高い空間分解能を実現することが期待されるが、表面付近ではスピンコヒーレンス時間（T2）が短くなって感度が低下することや、電荷状態の不安定化が知られていた。近年、リンドープダイヤモンドにイオン注入法により作製したナノレベルの深さに存在する NV 中心では、T2 の長時間化と電荷の安定性向上が報告されていた[1]。このことから、
ダイヤモンドへのリンドーピングの重要性が高まっている。従来、化学気相成長(CVD)法によるダイヤ
モンドへのリンドーピングではホスフィンが用いられてきたが、ホスフィンは毒性及び爆発性が高く、合成作業に危険が伴い、無毒化のために高額な装置を導入しなくてはならないという問題点があった。
本研究課題では、ホスフィンと比較して格段に爆発性・毒性が低いターシャリーブチルホスフィン(TBP)[2]を用いてリンドープダイヤモンドを合成した。

【実験と結果】リンドープダイヤモンドは、原料ガスに水素で希釈した高純度 12C メタンを用いて、
ARIOS 社製のマイクロ波プラズマ CVD 装置によって、Ib(111)基板上に合成した。二次イオン質量分析法により不純物濃度を測定した。ホール測定から、n 型伝導性を示すことを確認した。今回、ダイヤ
モンド試料中の不純物を、微量のリンが取り込まれつつ、窒素混入を抑制できたことを確認した。T2 の測定は、室温下で自作の共焦点顕微鏡を用いたハーン・エコー法で行い、NV 軸の方向は光検出磁気共鳴測定により確認した[2]。更に、最適化した条件での合成試料で、長い T2 を有する単一
NV 中心が生成していることを確認した（図 1）。これは T2を短くする不純物を抑制できたことを示していると考えられる。更に、NV 軸の配向性についても、[111]方向への高い配向性を確認した。また、新たな量子センシング手法を考案

図１ コヒーレンス時間（T2）をし、実証した[3]。これらの成果は、今後の量子センシング

ハーン・エコー法によって室温で測定

応用研究にとって重要な結果である。

した結果．

【参考文献】[1] A. Watanabe, T. Nishikawa, H. Kato, M. Fujie, M. Fujiwara, T. Makino, S. Yamasaki, E. D. Herbschleb,
N. Mizuochi, "Shallow NV centers augmented by exploiting n-type diamond", Carbon, 178, 294 (2021).

【成果報告】[2] R. Kawase, H. Kawashima, H. Kato, N. Tokuda, S. Yamasaki, M. Ogura, T. Makino, N. Mizuochi,"n-Type diamond synthesized with tert-butylphosphine for long spin coherence times of perfectly aligned NV
centers", Journal of Applied Physics, 132, 174504 (2022).
[3] H. Tabuchi, Y. Matsuzaki, N. Furuya, Y. Nakano, H. Watanabe, N. Tokuda, N. Mizuochi, J. Ishi-Hayase,"Temperature Sensing with RF-Dressed States of Nitrogen-Vacancy Centers in Diamond", Journal of Applied
Physics, 133, 024401 (2023).
－71－2022-72
量子センサの高感度化に向けたリンドープダイヤモンド合成と量子科学技術研究牧野俊晴

産業技術総合研究所【緒言・目的】ダイヤモンド中の NV 中心は、量子科学技術分野において精力的に研究され、特に固体中のスピンとしては群を抜く長いスピンコヒーレンス時間を持つことにより、高い量子センサ感度が実現し、磁場、電場、温度、圧力、pH などの高感度センサとして幅広い分野での応用が期待される。今後の社会への波及効果を考える際、スピンの電気的制御・検出や、センサ手法開発が重要で、本研究課題
ではそれらに取り組んだ。
【実験と結果】以前、我々は pin 構造を持つダイヤモ
ンドダイオード素子を作製し、電気的に単一光子を室温で発生させることに世界で初めて成功していた[1]。
この時は、NV 中心の中性状態を単一光子源としていたが、センサなどへの応用には負電荷状態からの発光が望まれていた。今回、産総研グループが p+-i(n-)-n+ 構造を有する作製したダイヤモンドダイオード素子を用いることにより、負電荷の NV 中心からのエレクトロ
ルミネッセンスと考えられる発光を観測することができた（図１、[2]）。今後の量子情報応用研究にとって重要な結果である。

図１

観測された NV 中心のエレクトロルミ

ネッセンス（EL）スペクトル．青色、水色がそれ
ぞれ 50 V, 30 V を印加したときに得られた EL ス
ペクトル．赤がそれぞれの差から得られたスペク

また我々は、低周波数の交流磁場を高感度に、且つ高周波数分解で計測できる新たな量子センシング手法を考案し、実証した。この手法を用い、これまで NV 量

トル．黒が NV 中心の負電荷状態のフォトルミ
ネッセンススペクトル.

子センサを用いて計測した NMR 信号の線幅としては世界最小線幅（1.6 Hz）を実証した[3]。更に、高品質で優れたスピン特性を有するリンドープ n 型ダイヤモンドの合成に成功した[4]。
【参考文献】[1] N. Mizuochi, T. Makino, H. Kato, D. Takeuchi, M. Ogura, H. Okushi, M. Nothaft, P. Neumann,
A. Gali, F. Jelezko, J. Wrachtrup, S. Yamasaki, "Electrically driven single photon source at room temperature
in diamond", Nature Photonics, 6, 299 (2012).
【成果報告】[2] M. Haruyama, H. Kato, M. Ogura, Y. Kato, D. Takeuchi, S. Yamasaki, T. Iwasaki, H. Morishita,
M. Fujiwara, N. Mizuochi, T. Makino, “Electroluminescence of negatively charged single NV centers indiamond”, Applied Physics Letters, 122, 072101 (2023).
[3] E. D. Herbschleb, Y. Ohki, K. Morita, Y. Yoshii, H. Kato, T. Makino, S. Yamasaki, N. Mizuochi, “Low-frequency
quantum sensing”, Physical Review Applied, 18, 034058 (2022). (Editor’s suggestion)[4] R. Kawase, H. Kawashima, H. Kato, N. Tokuda, S. Yamasaki, M. Ogura, T. Makino, N. Mizuochi, "n-Typediamond synthesized with tert-butylphosphine for long spin coherence times of perfectly aligned NV centers",
Journal of Applied Physics, 132, 174504 (2022).
－72－2022-73（国際）Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune
Therapy
Yan-mei Li Tsinghua University
The development of synthetic cancer vaccine adjuvants has been an area of active
research. One promising class of small-molecule anti-cancer adjuvants are agonists of
TLR7/8 that usually sense viral single-stranded RNA to elicit a Th1-type cellular innate
immune response. In this collaborative research with ICR, we extended ICR’s previous
discovery of a self-assembling vaccine adjuvant named cholicamide, with the goal ofidentifying a potent cancer vaccine adjuvant with an improved safety profile. Our
collaboration resulted in a cholicamide derivative (cholicamide β) as a non-cytotoxic
small-molecule cancer vaccine adjuvant that stimulates antigen-presenting cells to induce
antigen-specific T-cell activation.
To prepare a series of cholicamide derivatives, the Uessugi group of ICR replaced
deoxycholic acid with four other bile acids (cholic acid, lithocholic acid, chenocholic acid,and ursodeoxycholic acid) or changed the length of the diamine linker. To assess theirability to stimulate the immune response, we treated bone marrow-derived dendritic cells(BMDCs) with the cholicamide derivatives and measured the production of IL-6, acytokine typical for activation of antigen-presenting cells. Two compounds exerted morepotent activity than cholicamide at 100 µM. When we examined their effects on the cell
viability, compound 6 showed essentially no cytotoxicity up to 80 µM. We named thismolecule (6) as cholicamide β.
The non-cytotoxic characteristics of cholicamide β (6) prompted us to use it as acancer vaccine adjuvant. Our lab in Beijing examined whether cholicamide β (6)combined with an OVA antigen inhibits tumor growth in a B16-OVA melanoma model.
C57BL/6 mice were inoculated on day 0 with 1.5 × 105 B16-OVA melanoma cells by
subcutaneous injection. Cholicamide β (6) combined with the OVA antigen significantly
reduced tumor proliferation with negligible body weight. Cholicamide β (6) may serve asa starting point of small-molecule cancer vaccine adjuvant.
Publication
Self‐assembling small‐molecule adjuvants as antigen nano‐carriersJin, S., Zhuo, S., Takemoto, Y., Li, Y., Uesugi, M.
Chem. Comm. 58, 12228–12231 (2022)－73－2022-74（国際）Evaluation of CaCO3 dissolution rates in deep-sea sediments by a novel
tracer method
Cai Pinghe Xiamen University
Objectives: By working with Prof. Yoshiki Sohrin at ICR, this project aims to 1)
quantify CaCO3 dissolution rates and 2) examine what controls CaCO3 dissolution
rates in the Pacific Ocean floor.
Experimental methods: Sediment and porewater samples were collected along atransect in the North Pacific Ocean between mid-September and late October, 2021
(Figure 1). Radium-226 (226Ra) andthorium-230 (230Th) in sediment andporewater were measured using a highsensitivity ICP-MS. Porewater profiles ofdissolved inorganic carbon (DIC) was
determined by Apollo Dissolved Inorganic
CarbonAnalyzer.

concentrationsin

Calcium(Ca2+)

porewater

weredetermined using an ICP-OES.
Figure 1. Sampling stations in the North Pacific Ocean
Experimental results: Despite continuous flushing of the upper layer of the ocean
floor, all pore water profiles consistently manifest a marked depletion of Ca2+.
Strikingly, pore water profiles show a concomitant depletion of DIC relative to bottom
seawater.
Discussion: The results suggest that in contrary to the dissolution theory, authigenic
CaCO3 is forming in the upper sediment column of the Pacific Ocean floor lying below
the compensation depth. The reaction can be expressed as:
Ca2++HCO3- +OH-  CaCO3 (authigenic calcite) + H2O
By use of the 226Ra/230Th disequilibrium approach, we estimate a range of 12 to 120
mmol m-2 yr-1 (average: 60 mmol m-2 yr-1) for the rate of authigenic CaCO3 formation.
However, it is still unclear what reactions can produce OH- in sediment porewaters
Outcome report : Not yet available.

－74－2022-75（国際）Advanced Oxygen – mediated Flow ChemistryThomas Wirth

Cardiff University

Molecular oxygen is the most appealing reagent to perform oxidation reactions. Yet, lower
reactivity of molecular oxygen from its ground state (triplet oxygen, 3O2) generally requires
high pressure and temperatures for oxidation reactions. In contrast, the excited singlet oxygen(1O2) is highly reactive with different organic molecules even under very mild conditions.
Recently, Nakamura, Isozaki (the ICR collaborating researchers on this project) andcoworkers have synthesized gold nanoclusters (AuNCs) and utilized those AuNCs as efficientphotocatalysts for oxidative cyclization of amino alcohols to generate oxazolidine cores (ACS

Catal. 2021, 11, 13180-13187). Generation of singlet oxygen by the photoexcited AuNCs was
proposed as the key intermediate in the mechanism. To investigate if the AuNPs only
generate the singlet oxygen responsible for the subsequent reaction steps, treatment of 1 withsinglet oxygen was initially performed in the absence of AuNPs. The generation of “darksinglet oxygen” was confirmed from the quantitative formation of ascaridole from α-

terpinene (Chem. Eur. J. 2019, 25, 12486-12490). In all cases, 3 was found as the major
product with traces of 4 in some cases as indicated in the Scheme below.

We introduced the AuNPs under identical reaction conditions to investigate if the Au
nanoclusters could provide the cyclized product with pre-generated singlet oxygen in theabsence of light. However, even in the presence of AuNPs, no trace of the cyclized product 2
was observed, although the formation of 3 was slightly improved (38-62%). The formation of
4 was not observed in the presence of AuNPs. From many experiments we concluded that thelight and photoexcited AuNPs are involved in more than one step in the formation of final
cyclized product 2 rather than just generating singlet oxygen.
Our numerous efforts to cyclize 1 to 2 using “dark singlet oxygen” were not yet unsuccessful.
We now propose employing alternative singlet oxygen sources (photochemical approaches,use of endo-peroxides) to effect the transformation, also investigating modified starting
materials and include solvent modifications in the experiments.

－75－

2022-76（国際）Novel strategy for intracellular delivery of nanomedicines
Sílvia PUJALSInstitute for Advanced Chemistry of Catalonia

Nanomedicine arose 20 years ago with the promise of selectively deliveringdrugs to target 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 of them 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
have strong background of nanomaterials characterization and intracellular behavior
using various microscopic techniques (including electron microscopy and superresolution microscopy). On the other hand, Prof. Futaki at ICR, Kyoto University is
an expert on intracellular delivery of nanomedicines. This joint research aims toestablish novel approaches for stimulating cellular uptake of nanomedicines createdby Pujals group (IQAC) with the know-hows of Futaki group at ICR, Kyoto
University.
Our group has formulated few batches of Poly(D,L-lactide-co-glycolide)(PLGA) nanoparticles. They are around 200 nm and have DiI (excitation at 550 nm)
or DiO (excitation at 484 nm) for visualization of their methods of cellularinternalization. PLGA-based nanoparticles are biodegradable and widely employedin drug delivery systems in various medical applications. In addition to discussions
via e-mail, Prof. Futaki visited Barcelona in the August of 2022 and made detailed
planning of our studies. Methods in cellular uptake of these particles are now
understudy in Futaki laboratory. Pujals is planning to visit ICR in the fiscal year of2023 to extend the collaboration.

－76－

2022-77（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 forthe formation of clathrin-coated pits during endocytosis. Modulating the structuraldynamics of biomembranes by inducing bilayer curvature and lipid packing defects has
been highlighted as a 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 already shown that the N-terminus 18-residue peptide of epsin-1(EpN18) possess curvature inducing abilities of the parent protein.
The method of curvature induction by EpN18 is thought by way of shallow insertionof its hydrophobic face into the lipid bilayer. Possible steric hindrance among the lipids
by the insertion of helix leads to increase in surface area of outer leaflet of the membranes,
yielding curvature in the cell membranes. Through the functional refinement of EpN18,
the ability of membrane structural alteration may be more enhance and utilized for
artificially controlling cellular phenomena involving membrane structural alteration. We
therefore aimed to elucidate the important structural factors of the helical segment for thecurvature induction for the better understanding of curvature inducing mechanisms andfuture design of more effective means of curvature control.
The structural factors of amphiphilic helical peptides include hydrophobicity, helicity(α-helix content), charges, amphiphilicity balance (hydrophobic surface area), andpeptide length. We thus synthesized structurally simplified peptides and see the effects on
the curvature inducibility through physicochemical and cell biological evaluations. As aresult, we found a positive correlation between hydrophobicity/helicity and the abilitiesof curvature induction and lipid-packing loosening. The report on these results is now
under consideration for publication.

－77－2022-78（国際）－78－2022-79（国際）Intracellular delivery of biofunctional proteins using artificial protein
nanocages
Yusuke Azuma

Jagiellonian University

Proteins that self-assemble into hollow, cage-like structures present an attractive platform todevelop nanocarriers for intracellular delivery of intact cargo molecules in vivo. To achieve this,efficient methods for guest encapsulation and its release in recipient cells are needed. One of theapplicants (Azuma) holds expertise in protein cage engineering, devising strategies forencapsulation of cargo molecules, such as other proteins, in the lumen as well as control of cageassembly-disassembly by an external stimulus. The Futaki laboratory (the host at ICR) is
developing peptidyl tools for intracellular delivery of biofunctional proteins including antibodies.
By combining the specialties of both groups, this project aimed to develop novel intracellulardelivery systems for biofunctional proteins that are potentially applicable to clinical study.
Expected outcomes of this project included: (i) obtaining insight into the effect ofnanocage/peptide structures on their cellular uptake efficacy; (ii) establishing the approaches fordesign of protein nanocage capable of delivering biofunctional protein cargoes into cells; (iii)
providing guidelines for designing effective delivery systems for nanomedicines; and (iv)strengthening research exchange between Jagiellonian University and ICR.
As the first step, we discussed the possible candidates of protein nanocages via e-mailand planned experiments for production of protein cages encapsulating model guest proteins.
Meanwhile, we realized that improvement on delivery peptides is likely a priority objective toattain delivery of protein nanocages with satisfactory efficacy, the knowledge being obtained
through a Futaki group’s work on the development of a nanocage delivery system using a delivery
peptide called HAad (Angew. Chem. Int. Ed. Engl. 59, 19990-19998 (2020)). Prior to thiscollaboration work, Azuma and Futaki have reported a cationic lytic peptide that markedly
promotes the endosomal escape of biomacromolecules (Angew. Chem. Int. Ed. Engl. 57, 1277112774 (2018)). However, metal ions employed in this preliminary study may prohibit theapplication in vivo. Based on this design concept, the Futaki group lately developed new delivery
peptides without the need for metal ions. One of the designed peptides exhibited a marked activity,
successfully delivering a large protein, antibody (150 kDa), into various types of cells without
significant cytotoxicity. We anticipate that applying our latest peptide to protein cages will provide
a versatile nanocarrier system for efficient intracellular cargo delivery.

－79－2022-80
Real-Time Visualization of Cellular Phase-Separating Proteins
Kazuya Kikuchi

Osaka University

Objectives
A growing number of proteins contain disordered regions of low-sequence complexity
which induces protein condensation via liquid-liquid phase separation (LLPS). Althoughthese protein condensates initially have liquid-like properties, they can also age into more
solid-like states leading to many diseases. The goal of the present collaboration is todevelop a new chemical technique that allows us to monitor the transition of liquid-liquid
phase separation into the more solid or viscous state in live cells.
Results
Together with the Uesugi group of ICR, we designed and experimentally tested a newchemical technique that detects the status of protein condensates. This fluorescence-based
technique uses a unique protein labeling method (PYP method) that has been developedby our group in Osaka. The PYP method takes advantage of the relatively small size of
PYP protein for visualizing proteins of interest fused with PYP. First, HEK293 and U2OS
cells were transfected with each of 18 plasmids that encode a PYP protein fused to 18
different phase-separating proteins. The addition of a PYP ligand fluorescent probe into
the culture medium permitted the detection of the 18 PYP fused phase-separating proteinsin live cells under a confocal microscope. To monitor the formation of solid-likecondensates, we performed pulse-chase analysis, in which PYP ligand probes withdifferent colors were added at different time points (Orange probe first and Far-red probe
later). We hypothesized that solidified protein condensates would only be labeled byOrange probe. Newly formed liquid protein condensates would only be marked by Farred probe, and the remaining liquid protein condensates would be double-labeled withboth Orange and Far-red probes. The results suggest that this is in fact the case, although
the conclusion needs to be confirmed by other techniques in the future.
Future plan
We plan to establish the proposed method to analyze solid aggregates and liquidcondensates quantitatively. Sorting of the cells harboring those proteins by a FACS
machine would facilitate ranking the 18 phase-separating proteins to identify the highly
aggregating protein under different conditions. In addition, sorted cells will be subjected
to RNA sequencing and proteomic analysis to identify genes and proteins involved in thecondensate solidification process.

－80－2022-81
合成小分子化合物による細胞の遠隔操作
西川元也

東京理科大学●研究目的 細胞の中には多くの自己集合体が存在する。これらの自己集合体はマテリアルと生命体を分ける境界をなす。細胞内で最もマテリアルに近い自己集合体はメラニンだろう。この黒色の集合体はメラニン産生細胞の細胞小器官であるメラノソーム内で生合成される。メラノソーム内のチロシナーゼが出発物質のチロシンを認識し、酸化重合を引き起こすことでメラニンが生成する。
本研究では、合成小分子化合物による細胞内メラニンの化学的加工を試みる。究極的な目標は、非天然の機能性が付与された人工メラニンを利用した生細胞の遠隔操作である。
●背景

京都大学化学研究所の上杉グループでは、チロシン誘導体によりメラニンの生合成メカニ

ズムをハイジャックし、細胞内メラニンを化学的に加工する手法を開発している。この手法の応用
例として、常磁性チロシン誘導体による細胞内メラニンへの磁気応答性の付与と細胞の磁気制御が2022 年の Journal of the American Chemical Society に報告されている 1)。本論文は、メラニンの自己集合性を磁気応答性マテリアルの合成に応用した初めての報告例である。磁気応答性メラニンは、常磁性の鉄錯体が結合したチロシン誘導体を細胞内チロシナーゼで酸化重合することにより生合成される。磁気応答性メラニンを生合成した細胞に外部磁場を印加すると磁気配列させることが可能である。細胞内自己集合性分子と磁性学を融合した新たな生理活性化合物の概念を提案した。
●実験方法 共同研究では、磁気応答性が付与されたメラノーマ細胞の磁気制御をマウス体内で検討した。メラノーマ細胞をマウスに静脈注射すると肺転移することが知られている。肺移行性を磁場で遠隔操作できるかを西川グループで調べた。初めに、上杉グループで確立した手法を元に
B16F10 メラノーマ細胞内で磁気応答性メラニンを生合成した。この磁性化メラノーマ細胞を DiRにより蛍光標識した後、尾静脈注射し、マウスの胸部にネオジム磁石を配置した。静注 3 時間後、肺を摘出し、DiR 由来の蛍光強度を測定することで肺移行性を評価した。磁性化メラノーマ細胞は外部磁場に引き寄せられ、肺転移が増進すると予想した。
●結果と考察

磁性化メラノーマ細胞の肺移行性は外部磁場存在下で顕著な増進が見られなかった。マウス体内で磁気制御できるほどの磁性が人工メラニンに備わっていなかったことが原因として考えられる。磁気特性を増強する必要がある。磁性材料の磁気特性に大きな影響を与える要素は、その材料を構成する常磁性分子の集合様式である。磁気応答性メラニンは常磁性鉄錯体とチロシンを含むペプチドのハイブリッド化合物が重合し、高度に自己集合することで合成される。ペプチド部位のアミノ酸をチューニングすることで磁気応答性メラニンの集合性を調節し、磁気特性を改善できる余地がある。現在、上杉グループで新たな磁性チロシン誘導体の開発を進めている。

1) K. Nishio, K. Toh, A. Perron, M. Goto, M. Abo, Y. Shimakawa, M. Uesugi, Magnetic Control of Cells by
Chemical Fabrication of Melanin, J. Am. Chem. Soc. 2022, 144, 16720.

－81－2022-82
有機合成・単分子測定・計算化学の協同による
2 次元ドナー・アクセプター分子系の構築
木村謙介

理化学研究所

ドナー・アクセプター(DA)分子界面における励起子の挙動は、電荷分離、熱活性化遅延蛍光、
光化学反応といった分子が有する様々な光化学機能の根源である。このような励起子の挙動は、
DA 分子がナノメートルスケールで近接した際に起こる現象であることから、DA 分子間の空間的な配置を決定したうえで光学測定を行うことが重要である。本研究では、共同研究者である梶教授らにより化学研究所のスーパーコンピュータシステムを用いた量子化学計算により表面上に 2
次元 DA 分子系を形成する最適な組み合わせを見出したのち、研究代表者らを中心に理化学研究所の Kim 研究室に設置されている走査トンネル顕微鏡(STM)をベースとした単一分子発光測定手法を用いて、2 次元平面上にモデル DA 分子系を構築し、その光学特性の評価を行った。
計算化学を用いたスクリーニングにより、Mg フタロシアニン(MgPc)を D 分子、HAT-CN を A分子として用いて近接させたとき DA 二量体からの電荷分離発光が期待されることを見出した(図1a)。そこで、これらの分子を自作した 2 源蒸着器を用いて NaCl 超薄膜を成長させた Au(111)表面に吸着させ、STM 探針を用いた分子移動技術を用いて近接させた。図 1b は MgPc(左)と HATCN(右)を 1.06 nm の距離まで近接させたときの STM 像であり、分子の最低空軌道(LUMO)が可視化されている。図 1c は作成した DA 二量体に対してSTM 発光を測定した結果である。図 1(b)中の赤点の位置に STM 探針を置いて電荷注入をしたとき、659.5 nm に発光ピークが観られ (図 1c 赤線)、MgPc
モノマーの発光波長は 656.5 nm であることから、3nm ほど長波長化している。次に、青点に STM 探針を置いて発光測定を行うと発光ピークが分裂する現象を観測した。このように励起位置により発光スペ
クトルの形状が変化した現象は、4 回対称の MgPc に対して HAT-CN が近接することで対称性が崩れたことに起因すると考えられる。現在、STM によって決定した DA 分子の配置に基づいて二量体の励起状態計算を行うことにより、スペクトル変化の詳細な起源を調べている。
本研究に関しての具体的な成果報告は未だ行えていないが、次年度は学会発表および論文化を目指して、引き続き研究を進めていく。

－82－2022-83
両親媒性希土類錯体を利用した薄膜発光体の作製
三枝栄子 大阪公立大学【背景・目的】
3 価のランタノイドイオンの発光は、長寿命でスペクトルの線幅が狭いことが特徴であり、この発光特性を利用してレーザーやバイオセンサーなどに応用されている。我々は、環状ポリアミンにコレステリル基を導入した両親媒性キレート配位子を開発し、様々なランタノイド錯体を報告している。
この錯体は水溶液中で自己会合コロイドを形成し、疎水場の効果によりランタノイドイオンの長寿命発光を実現した。これまでの成果より、配位子 L およびユウロピウ
ム錯体 EuL の単分子膜を LB 法により作製することに成功した。pMAIRS (偏光多角入射分解分光) 法を用いた赤外分光分析を行い、膜中の微細構造を明らかにした。EuL
積層膜の発光スペクトルから Eu3+由来の微弱な発光を観測したが、膜厚と発光強度の定量評価には至らなかった。

Fig.1 Structures of [EuL]･3Cl and sensitizer (HABA).

また先行研究において、EuL コロイドに増感剤を添加すると強い増感発光が得られ、溶液中のアニオン交換で消光することが見出されている 1)。本研究では、これを薄膜に拡張し固体センサーとして利用できるか検証することを目的とし、EuL の積層膜作製および増感剤を添加した場合の膜構造変化と発光特性について検討した。
【実験方法】
LB 法により Si 基板上に EuL の積層膜と、増感剤 (HABA, Fig.1) を 1 当量添加した積層膜 (EuLHABA) を作製し、pMAIRS 法を用いた赤外分光分析により膜構造解析を行った。それぞれの発光ス
ペクトルを測定し、薄膜中の増感効果について評価した。
【結果・考察】EuL および EuL-HABA の水面上単分子膜の-A 曲線を Fig.2に示す。EuL の単分子膜は、これまでの結果をよく再現した。
EuL-HABA の-A 曲線は、EuL 単独の膜に比べて極限面積はほとんど変わらないが表面圧の立ち上がりが大きくなった。
HABA が錯体同士を引き付ける働きをする可能性が示唆された。この成膜条件で作製した EuL 積層膜の pMAIRS スペクト
ルから、1627 cm-1 に C=O 伸縮、1574 cm-1 に NH 変角の吸収がFig.2 -A curve of EuL w/o HABA

観測されたが、面内・面外の配向性は見られなかった。EuL-HABA 積層膜も同様に評価を行ったが、増感剤がどのように存在しているか詳細な解析に至らなかった。発光スペクトル測定から、EuLHABA 積層膜は EuL 積層膜に比べて強い発光を示し、膜中の増感効果を確認することができた。
【文献】1) T. Sagami et al., Chem. Commun., 2017, 53, 3967.

－83－2022-84
フッ素系樹脂の摩擦界面における分子挙動の解明
粕谷素洋

公立小松大学

フッ素樹脂は優れた自己潤滑性を示すため，固体潤滑剤として自動車や船のエンジン内ピストン
摺動部等に用いられている．一方で，フッ素樹脂は耐摩耗が課題となっており，フィラー等の添加による改善が行われてきたが，そもそも摩擦・摩耗中の高分子鎖挙動やフィラーの役割について，
分子レベルでは分かっておらず，さらなる摩耗特性の改善にはその化学的過程の理解が必要な状況である．
申請者はこれまでシリコン系水潤滑材料やゴム-氷間における摩擦挙動を含む界面分子挙動を精密摩擦試験と分光手法を組み合わせて評価することで，新規な分子レベルの摩擦・潤滑機構を解明してきた（例： J. Phys. Chem. 2013, Soft Matter 2019, 光化学 2021）．現在，同様の手法を医療用高分子材料やフッ素樹脂等，摩擦分野で重要な他の樹脂に展開すべく，研究を進めている．
これらの研究を通して，申請者は真に摩擦を分子レベルで理解するためには，① 分子数の少ない界面層を検出可能な感度の高さ，② 分子情報，特に配向を直接観測可能，という２点を兼ね備えた分光手法が必要，という着想を得て，本申請の共同研究者である京大化研長谷川教授の開発した多角入射分解赤外分光法(IR-MAIRS)を摩擦界面の評価法として展開することを着想した．
本研究では，IR-MAIRS 法によりフッ素樹脂の摩擦・摩耗に伴う分子構造変化を捉え，摩擦機構の分子レベルでの解明に利用可能であることを示すことを目的とした． 実験としては，シリコン
ウェハにスピンコート法により成膜したフッ素樹脂薄膜（ポリ（フルオロアルキル
アクリレート）をもう一枚のシリコン基板 と 接 触 ・ せ ん 断 さ せ ， 前 後 で の IRMAIRS スペクトル変化を比較した結果を右図に示す．1300 cm-1 周辺の CF3 伸縮振動 に由来するピークには面内/面外の比率に変化がないのに対して，1200 cm-1 周
辺のフォノンバンドには大きな変化が観測された．これはパーフルオロアルキル
鎖の配向は変化せず，集合構造は変化す

図

フッ素樹脂薄膜の摩擦に伴う面内および面外の赤外スペクトル変化ることを示している．
以上の結果より，

法が摩擦による分子構造変化の評価に適用可能であることを示すことができた．これらの成果の一部については，日本化学会第トライボロジー会議

春 東京にて発表予定である．

－84－

春季年会

年

月 ，および2022-85
エクソソームの細胞内への送達設計
中瀬生彦

大阪公立大学

生体における殆ど全ての細胞は小胞を絶えず分泌しているが、例えば直径が約 30~200 nm のエク
ソソームは、分泌時に microRNA や酵素といった生理活性分子を内包し、それらの「メッセージ」
を離れた細胞に送ることで細胞間情報伝達を行なっている。近年では、がんを含む疾患進展にエク
ソソームが影響を及ぼすことが明らかにされ、がんの転移を誘導するエクソソームや、エクソソー
ムを化学的にブロックすることで転移を抑制する技術構築も進められている。一方でエクソソーム
は、薬学的な観点から（1）免疫制御が可能、（2）毒性が低い、（3）遺伝子発現による膜タンパク質の人工化（配向性制御）、（4）活性分子カクテルの天然・人工内包、（5）細胞間コミュニケーション
経路の利用等の高い優位性より、次世代の薬物運搬体として大きく期待されており、国内は遅れているものの世界的に臨床研究も盛んに進められている。研究代表者は、これまでにエクソソームの細胞内移行におけるマクロピノサイトーシス経路の重要性を世界に先駆けて報告し、がん受容体（EGFR や CXCR4）の活性化や K-Ras 変異体発現でのマクロピノサイトーシス誘導促進によるエクソソームを介した細胞間コミュニケーションの増強や、それを逆手にとるマクロピノサイトーシス誘導型エクソソームを基盤とした drug delivery system（DDS）の構築を展開してきた[1, 2]。本研
究は、研究代表者がこれまでに開発してきたエクソソームを含む細胞外小胞の機能化において、特にがん細胞への高い標的性とサイトゾル送達性を兼ね添えたエクソソーム DDS の技術構築を目指
すことを目的としている。これまで、研究代表者はポリアルギニンや、抗菌タンパク質由来新規細胞内送達ペプチド修飾によるエクソソームの細胞内取込促進を達成している[3,4]。本研究プロジェ
クトでは、さらに超音波を新たに用いることで、効率的な機能性ペプチド修飾技術を構築しつつある。これまでのペプチド修飾技術では、エクソソーム膜へ目的ペプチドを結合させるために 30 分
以上反応させる必要があったが、見出した超音波を新たに用いる手法では数十秒といった短時間で、エクソソーム膜への十分なペプチドの結合性、及び、例えばマクロピノサイトーシスを誘導するペプチドを用いた場合では、がん細胞内への取り込み量の顕著な上昇が確認されている。現在、本手法で適用できる機能性ペプチドの種類や、化学結合様式、エクソソーム物性の評価を中心に、さらなる研究展開を続けており、生体から単離したエクソソームを如何に早く機能化できるかといった重要な課題の中で、本基盤技術・知見は DDS 技術構築に大きく貢献できることが強く考えられる。
本研究課題を通して、医療応用を見据えたさらなる技術構築が達成できるように研究を一層進展させる。

＜参考文献＞[1] Nakase, I. et al. Sci. Rep. 5, 10300 (2015), [2] Nakase, I. Processes 9, 224 (2021), [3] Noguchi, K., Nakase,
I. et al. Mol. Pharm. 18, 3290-3301 (2021), [4] Hirase, S., Nakase, I. et al. Mol. Pharm. 19, 1135-1145 (2022)－85－

2022-86
細胞外小胞の標的細胞への移行メカニズムの解明
江口暁子

三重大学

【目的】
研究代表者は、慢性肝疾患の病態進行過程において、障害肝細胞由来細胞外小胞(障害 HC-EV)と正常肝細胞由来細胞外小胞（正常 HC-EV）による標的細胞の活性化には、違いがあることを明らかにしている。しかし、障害 HC-EV と正常 HC-EV の標的細胞への取り込み量や取り込み経路の違いについては、全く解明できていない。そこで、障害 HC-EV が細細胞間情報伝搬経路としてマ
クロピノサイトーシスを介して各種標的細胞へ取り込まれる機構を解明し、障害 HC-EV に特異的な取り込み経路を同定することを目的とする。この研究過程において、取り込み量の測定や取り込み経路の可視化等、様々な化学的な実験要素が必須となるため、化学研究所・二木史朗博士が開発した実験系を利用するために共同研究を実施する。研究代表者である江口は、共同研究者である二木史朗博士が開発した「細胞外小胞の細胞内動態検出系」を活用して、障害 HC-EV と正常
HC-EV の各種標的細胞への移行量を定量し、障害 HC-EV と正常 HC-EV 間の移行量の違いや標的細胞間における移行量の違いを明らかにする。
【実験方法】
共同研究者である二木史朗博士がこれまでの研究で培ったマクロピノサイトーシス等の細胞への取り込み経路の実験条件を利用して、各種阻害剤を用いて細胞内移行経路に関して検討することで、障害 HC-EV と正常 HC-EV の標的細胞への取り込み経路を明らかにする。なお、フローサ
イトメトリーや共焦点レーザー顕微鏡や標的細胞における遺伝子発現レベルを用いて、取り込み経路を評価する。
【実験結果】
様々な阻害剤を用いた検討から、障害 HC-EV と正常 HC-EV の標的細胞への取り込みは、マクロピノサイトーシスを始めとする様々な経路を介して行われていることや、標的細胞により取り込みの経路は異なることが明らかとなった。さらに２つの標的細胞を用いた比較実験から、障害
HC-EV や正常 HC-EV の取り込み経路の優位性は、標的細胞により異なる可能性があることが示唆された。現段階において、障害 HC-EV と正常 HC-EV の取り込み経路に大きな差異はないと思われるが、阻害剤を用いた検討で HC-EV の取り込み阻害が強くかからない標的細胞もあり、異なる
取り込み経路の検討が必要である。
【考察】
標的細胞によって HC-EV の取り込み経路が異なることが明らかとなったが、阻害剤で取り込みが完全に抑制できない標的細胞もあることから、阻害剤以外の取り込み経路についても検討する必要がある。さらに、HC-EV が取り込まれる他の標的細胞についても検討をすすめる。
【成果報告】
特になし－86－2022-87（国際）Role of PIP5K Genes in Pollen Tube Development
Li-Jia Qu

Peking University

Objectives: Phosphatidylinositol (4,5)-bisphosphate [PtdIns(4,5)P2], one of phosphoinositides
serving as lipid signals on eukaryotic membranes, modulates various cellular processes
including cytoskeletal organization, membrane trafficking, and signal transduction for gene
expression. PtdIns(4,5)P2 localizes mainly to the plasma membrane or its membrane
subdomains, and physically interacts with various regulatory proteins. The spatiotemporal
existence of PtdIns(4,5)P2 is critical for its signaling function, and established basically via its
metabolization. Although the metabolic pathways of phosphoinositides are elaborately linked
to one another, phosphatidylinositol 4-phosphate 5-kinase (PIP5K), which produces
PtdIns(4,5)P2 by phosphorylating PtdIns(4)P, is thought to be a key enzyme responsible for the
spatiotemporal pattern of PtdIns(4,5)P2 in higher plant cells, where some of thephosphoinositide metabolic pathways found in animal or fungal cells are missing. In plants,
PtdIns(4,5)P2 has been studied especially for its involvement in root hair and pollen tube
growth mainly using the Arabidopsis system. We have identified a set of PIP5K genes thecomplete loss of functions of which caused male sterility. Pollens with the multiple mutations
were found to be defective of pollen tube development. In this study, an essential role of
PIP5K in pollen germination was investigated.
Experimental Methods: T-DNA or transposon tagging mutant lines of the PIP5K4, PIP5K5,
and PIP5K6 genes were obtained from public organizations for biological resources.
Loss-of-function mutant lines for the genes were established, and crossed with one another toobtain multiple mutant lines. Single and multiple mutant lines of the PIP5K4 6 genes were
examined for their phenotypes in pollen development and germination by microscopic
observation.
Results and Discussion: We investigate processes of the pollen development and germination
by detailed microscopic observation. Using the double mutants pip5k4pip5k5, pip5k4pip5k6,
and pip5k5pip5k6, we found that the PIP5K4 6 genes redundantly function in pollen
germination as well as pollen tube growth. The pip5k4pip5k5pip5k6 triple mutant pollen grains,which were obtained from heterozygous triple mutants, were apparently normal in theirmorphology. However, they couldn't germinate under germination conditions while some ofthem swelled and ruptured their cell wall. Phylogenetic analysis of type-B PIP5Ks revealed
that four clades, which contain PIP5K1 3, PIP5K4 6, PIP5K7 8, PIP5K9, respectively, areconserved in angiosperms, while gymnosperms have type-B PIP5Ks only in the parent clade
containing the PIP5K7 8 and PIP5K9 clades. We hypothesize that a common ancestor of the
PIP5K4 6 genes evolutionally differentiated to function in the pollen germination, a criticalprocess for the elaborate angiosperm pollen system.
－87－2022-88（国際）Construction of heterologous protein secretion system at low
temperatures by using cold-adapted microorganisms
Xianzhu Dai

Southwest University[Background and Objectives] Shewanella vesiculosa HM13, a psychrotrophic
bacterium isolated by the group of the ICR partner researcher (Prof. Tatsuo Kurihara)from fish intestine, secretes a large number of spherical particles called extracellular
membrane vesicles (EMVs) at low temperatures. These vesicles carry an S-layer proteinlike protein, P49, as a single major cargo protein. P49 is translocated across the inner
membrane from the cytoplasm to the periplasmic space by the Sec translocon and thentranslocated across the outer membrane to be secreted to the extracellular space by a type
II secretion system (T2SS)-like apparatus. P49 is predicted to bind to capsularpolysaccharide on the surface of the cells and EMVs. This cargo transportation
mechanism is expected to be useful for vesiculation-mediated heterologous protein
production. In the previous study, green fluorescent protein fused to P49 was detected in
the cellular and EMV fractions, suggesting that P49 can transport its fusion partner to
EMVs. However, the fusion of heterologous proteins was found to reduce the efficiencyof transport of the fused P49 to EMVs. In this study, we evaluated the effects of the fusionof various peptide tags to N- and C-terminal regions of P49 on its transport to EMVs.
[Results and Discussion] When StrepII tag was inserted downstream of the P49 secretion
signal for the Sec translocon, the tagged protein was not detected in both the cellular andextracellular fractions. This suggests that insertion of the tag to the immediate
downstream region of the secretion signal affected the efficiency of translocation of P49
across the inner membrane by the Sec translocon and that the fusion protein was degradedin the cells. When StrepII, G11, and SpyT tags were introduced into the C-terminal regionof P49, the tagged proteins were detected only in the cell fraction and not detected in theextracellular space. This suggests that the C-terminal tag insertion interfered with theinteraction of P49 with the T2SS-like apparatus and inhibited the translocation of thefusion proteins across the outer membrane, resulting in their accumulation in the
periplasmic space. Although the mechanism of the substrate recognition of this secretion
apparatus is unknown, the C-terminal region of P49 might be involved in its interaction
with this apparatus. For surface modification of EMVs by modification of P49, it isimportant to introduce a fusion partner without disturbing the translocation of P49 acrossboth the inner and outer membranes. The type of tag sequence and insertion sites that do
not interfere with the translocation of the fusion protein should be explored in futurestudies.

－88－2022-89（国際）Structural and functional analysis of the surface polysaccharides of outermembrane vesicles released by bacteria
Maria Michela Corsaro University of Naples Federico II
Objectives:
The aim of this research has been the characterization of the capsular polysaccharides (CPS)
isolated from the cells of the nfnB mutant of Shewanella vesiculosa HM13. Previous studies
suggested that the affinity between CPS and P49 is reduced in the mutant that lacks nfnB, a genein the close vicinity of the P49 gene. Therefore, we have been focused on the structural analysisof polysaccharides isolated from this mutant. The group of the ICR partner researcher (Prof.
Tatsuo Kurihara) has furnished the samples, and the characterization has been performed by
NMR spectroscopy.
Experimental:
Dried cells (1.9 g) of nfnB mutant from S. vesiculosa HM13 were extracted with either
phenol/chloroform/light petroleum (PCP) or hot phenol/water methods (Galanos et al 1969), andthe crude lipooligosaccharide (LOS) was precipitated as already reported (Di Guida et al. 2020).
The extracts were dialyzed against water (cut-off 3500 Da) and lyophilized. The samples weretreated with 1% CH3COOH (100 °C, 3 h) and, after centrifugation, the supernatants werefractionated on a Bio-Gel P-10 column (Sigma, 90 × 0.75 cm, flow rate 12.0 mL/h, fraction
volume 2.5 mL) eluted with water. Two fractions were obtained and analysed.
Results:
The glycosyl GC-MS analysis, performed on the first fraction, disclosed the presence ofrhamnose (Rha), glucose (Glc), and 2-amino-2-deoxy-glucose (GlcN), as already reported(Casillo et al., 2022). In addition, this fraction was analysed by 1H NMR. The spectrum confirmed
the presence of the same CPS already characterized from the wild-type cells. Furthermore, the1

H NMR spectrum of the second fraction isolated from the water/phenol extract revealed the

production of an additional CPS. The latter will be characterized by means of chemical analyses
and 2D NMR experiments.

Casillo, A. et al. Marine Drugs (2019), 17, 34.
Di Guida et al. Marine Drugs (2020), 18, 231.
Casillo et al., Carbohydrate Polymers (2022), 297, 120036.

－89－2022-90（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 tetracyclic diterpenoid carboxylic acids. They act
as plant hormones that control diverse developmental processes. Bioactive GAs play criticalroles in promoting growth, including internode (stem) elongation of rice. The elongateduppermost internode 2 (eui2) mutant of rice shows a tall phenotype due to its elongateduppermost internode. Because of this reason, this mutant has been utilized in hybrid rice breedingin order to eliminate panicle enclosure in male sterile parents. Previously, we have shown by
map-based cloning that EUI2 is a functionally-uncharacterized protein that belongs to the ,fold hydrolase superfamily. In collaboration with Shinjiro Yamaguchi’s group, we havepreviously characterized the rice eui mutant and found that EUI encodes a cytochrome P450
enzyme that deactivates GAs via 16,17-epoxidation. Based on these results, we speculated that
EUI2 might act as an epoxy hydrolase and further deactivate epoxidated GAs in the uppermost
internode of rice. In fact, our collaboration showed that EUI2 protein could hydrolyze epoxy
GAs in vitro. In addition, we determined the levels of endogenous 16,17-epoxy GAs in wild
type and the eui2 mutant by LC-MS/MS analysis.
Experimental methods: Various 16,17-modified GA derivatives were chemically synthesized,
and their biological activities were determined using GA-deficient rice seedlings. Endogenouslevels of epoxy GAs in another genetic background of WT and eui2 mutant rice plants were
determined by LC-MS/MS using deuterium labeled epoxy GAs as internal standards.
Experimental results: We chemically synthesized 16,17-modified GA4 derivatives and foundthat many of them are weakly, but significantly active in promoting the second leaf sheaths ofrice seedlings. In addition, our data also showed that the biological activity of the hydrolyzed
product (16,17-dihydroxy GA4) was significantly weaker. This finding suggests that EUI2 plays
a role in further deactivating epoxy GA4. Previous X-ray crystallographic analysis of the GA4GID1 complex suggested that C-17 plays an important role in closing the lid of the GID1 receptor
through hydrophobic interaction. Therefore, the introduction of a hydroxyl group at C-17 may
inhibit this hydrophobic interaction. This would explain why 16,17-dihydroxy GA4 (EUI2
product) is nearly inactive. To confirm the results obtained before, we analyzed endogenous
epoxy GAs in another genetic background of WT and eui2 mutant rice plants. Consistent withthe previous data, the eui2 mutant accumulated epoxy GAs at much higher levels than does WT.
Publications: In preparation.

－90－2022-91（国際）Analysis of novel transporters for strigolactones or their biosynthetic
intermediates
Yunde Zhao

University of California San Diego

Objectives: Strigolactones (SLs) are carotenoid-derived plant hormones that regulate various
processes of plant growth and development. They are also secreted from plant roots into therhizosphere and function as allelochemicals for symbiosis with arbuscular mycorrhizal fungi andfor stimulating seed germination of parasitic plants. Classical grafting studies have suggested
that SL and/or its biosynthetic intermediate(s) can move from roots to shoots, but much has notbeen fully elucidated about SL transport. Previously, we likely have identified novel transporters
for SLs or intermediates for SL biosynthesis in rice. The knockout mutants of the transporters
increased tiller numbers, which are phenotypically very similar to those well-characterized SL
biosynthesis mutants and signaling mutants. The physiological and biochemical roles of theidentified transporters need to be experimentally demonstrated.
Experimental methods:
Our group• Phenotypic and genetic interaction studies of the mutants whose ability to transport SLs or SL
biosynthetic intermediates have potentially been compromised.
• Generation of additional mutants using CRISPR/Cas9 gene-editing technology.
ICR partner researchers (Dr. Kiyoshi Mashiguchi, Prof. Shinjiro Yamaguchi)• Analysis of the endogenous levels of SLs and SL biosynthetic intermediates by LC-MS/MS tofind transporters' substrate(s).
• Elucidation of SLs and SL biosynthetic intermediates that can move from roots to shoots• Evaluation of transporters' export/import activity toward the candidate compound(s).
Experimental results: This year, we further conducted genetic studies on the putative SLtransporters. Moreover, ICR partner researchers discovered that two SL biosynthetic
intermediates, carlactone and carlactonoic acid, can move from roots to shoots in Arabidopsis.
Furthermore, they also showed that methyl carlactonoate, a bioactive SL in Arabidopsis, is not
likely mobile. In addition, they found SL-related compounds in xylem sap in Arabidopsis andrice. We are going to analyze the endogenous amounts of SLs and their biosynthetic
intermediates using the knockout mutants of the transporters.
Publications: No publications from the collaboration in FY2022.

－91－2022-92（国際）Phase separation in mixture of nematic liquid crystal and solvent
Ryoko ShimadaJapan Women’s University

Mixtures of liquid crystalline (LC) molecules and ordinary solvents have two order parameters, theconcentration and orientation Q of the LC molecules, that are fluctuating with time in a coupled way.
This study focuses on such a mixture of dimethyl terephthalate (DMT) and 4-cyano-4'-pentylbiphenyl(5CB) to examine their phase diagram shown in Fig.1. (This diagram was obtained from FTIR analysisof aliquots taken from the phase-separated DMT/5CB mixture.)
The previous study1) combined the Flory-Huggins (FH) and Landau–de Gennes2) (LdG) theories toformulate a model describing the phase behavior in the absence of crystalline.

This study extends

the model to allow coexistence of the isotropic or nematic phase with the DMT crystalline phase. For
example, the extended model expresses the free energies G of the nematic and crystalline phases asnematic phase:G[ nem]

RT

[nem]

[nem]

total
5CB

n
crystalline phase:

G

total

[nem]

total [ nem]

 nDMT ln DMT  n5CB ln 5CB   Nn5CB DMT

[ cry]

RT

total



[nem]

nDMT

 A T  T  Q  BQ  CQ   RT 
**

[nem]

nDMT  nDMT
RT

2

3

4

(1)
[liq]
DMT

(2)

[ cry]

 DMT

where RT is the thermal energy, ni[ ] and i[ ] denote the mole number and volume fraction of thetotal
in the total mole number of 5CB, N ( 2) is the molar volume ratio
component i in the phase , n5CB
[liq]
[cry]
and  DMT
are the chemical potential of DMT in the dissolved liquidof 5CB to DMT, and  DMT

state and undissolved crystalline state, respectively. A, B, C, and T** are the LdG parameters
introduced previously1). For adequately tuned LdG parameters, minimization of the total free energy[nem] G [cry] gives  DMT. The result is shown in Fig.1 with the blue curve. The green and red[iso]
curves show  DMT in the isotropic phase coexisting with the nematic (DMT/5CB) and crystalline[iso](DMT) phases. This  DMT
is obtained from[ nem][cry]
and/or G
combined withG
[iso](expressed in a way similar to eq. (1)G
but with Q = 0).
These curves welldescribe the experimental phase boundaries(black circles), and suggest an apparent
triple point (green circle) at a given pressure.
It is of interest to compare the fluctuationofand Q deduced from the model and thatobtained in future experiments.

G[ nem]

1) Shimada, Urakawa, Inoue, and Watanabe, Soft
Matter, 17, 6259-6272 (2021).
2) de Gennes and Prost, The Physics of Liquid
Crystals, Clarendon Press, Oxford, 1993.

Fig. 1－92－

Phase diagram of DMT/5CB mixture2022-93（国際）Chromatin, epigenetic and proteolytic regulation of RNA processing inplant morphogenesis
Vicente RUBIO

National Center of Biotechnology

Objectives: We focus to understand molecular mechanisms bridging proteolysis to mRNA
processing in environmental adaptation. Arabidopsis was used as a model to investigate
CRLs, DCAFs, CSN and their binding factors, that are highly conserved among kingdoms.
To date, plants have utilized these protein complexes in adaptation to light environmental
changes. CFI (cleavage factor I) is a complex that binds CSN in mammals and plants, andis involved in processing 3' UTR ends of pre mRNAs. In my group at CNB-CSIC, taking
advantage of “tandem affinity purification” and “protein detection” system, CFIinteracting proteins has been analyzed using different bait and environmental conditions.
The results are being cross-examined against the DCAF list that we have. Preliminary
results suggested promising overlaps in certain proteins categories of each list.
Experimental results: Through complementary collaboration with Dr. Tsuge's group at
ICR, numerous proteins have been listed up as interacting partners for CRLs, DCAFs,
CSN and their binding factors. However, it remains unclear which network is the key
network linking proteolysis to mRNA processing regulation. We revealed that
Arabidopsis CFI 25a subunit interacts with CFI 25a, CFI 59, and CFI 68, confirming thatan intact CFI complex could be formed in plants. Six out of 8 subunits composing the
CSN protein complex was also identified. The two smaller subunits might have not been
identified due to the resolution of the experimental setup. We also observed an
overrepresentation of proteins involved in proteolysis. This led us to believe that CSNCFI interaction could be a key link between proteolysis and mRNA processing regulation.
Discussion: These unique results were outcome of taking advantage of the plant system
as a model to comprehend a universal regulatory system. We favor our hypothesis thatdiverse yet temporal-regulated transcript usages are key to respond to specificenvironmental stimuli. Further collaboration will gain understanding of the key generalplatform for gene expression regulation via proteolysis and transcriptional regulation.
Publications: Zhang X, Nomoto M, Garcia-León M, Takahashi N, Kato M, Yura K,
Umeda M, Rubio V, Tada Y, Furumoto T, Aoyama T, Tsuge T. (2022) CFI 25 Subunit ofCleavage Factor I is Important for Maintaining the Diversity of 3' UTR Lengths in
Arabidopsis thaliana (L.) Heynh. Plant Cell Physiol. 63:369-383. doi:
10.1093/pcp/pcac002.
In preparation, " Plant Cleavage Factor I complex regulates cleavage and polyadenylationof its own subunit mRNAs"－93－

2022-94（国際）Site-Selective Protein Acetylation and Phosphorylation by Small
Molecules
Lu Zhou Fudan University
Post-translational modifications (PTMs) play essential roles in regulating a myriad ofcellular processes in mammalian cells, including signal transduction, metabolism, and genetranscription. Dysregulation of protein modifications causes metabolic diseases, immune
diseases and cancers. Among protein modifications, acetylation and phosphorylation
represents the most critical PTM. In FY2022, we collaborated with the Uesugi researchgroup of ICR to develop small molecules that specifically acetylate cellular proteins tocontrol human immune responses.
The presence of DNA in the cytoplasm is normally a sign of microbial infections andis quickly detected by cyclic GMP‐AMP synthase (cGAS) to elicit anti‐infection
immune responses. It has been reported that Lys acetylation of cGAS inhibits its
activation to impair cGAS‐mediated immune responses. To discover a small moleculethat selectively acetylates cGAS, we exploited the structure of RU521, a known cGAS
inhibitor, as a starting point. The introduction of an acetyl ester group to the structure
at varied positions led to a series of candidate cGAS‐acetylation compounds. In
FY2022, we found that one of these compounds, CCY‐G208, acetylated cGAS in vitro
and in cells. In line with its ability to acetylate cGAS, CCY‐G208 reduced the protein
expression level of IFNβ1, a representative cGAS‐responsive interferon, in human
THP‐1 immune cells. Consistent with this, other biological assays conducted in our
Fudan lab also showed that CCY‐G208 inhibits phosphorylation of IFR3, a downstream
event of cGAS, to decrease the promoter activity of the IFNβ1 gene.
In a separate project, we collaborated with the Uesugi group of ICR to develop non‐cysteine‐targeting covalent inhibitors. Our collaboration was published in ACS Chem.
Biol. in 2022.
Publication
Jung Y, Noda N, Takaya J, Abo M, Toh K, Tajiri K, Cui C, Zhou L, Sato S, Uesugi M.
Discovery of Non‐Cysteine‐Targeting Covalent Inhibitors by Activity‐Based Proteomic
Screening with a Cysteine‐Reactive Probe.
ACS Chem. Biol. 17, 340‐347 (2022).

－94－2022-95（国際）Developments of highly efficient and high color purity organic
electroluminescent devices based on thermally activated delayed fluorescentmaterials exhibiting ultrafast reverse intersystem crossing process
Lian Duan Tsinghua University
This project focused on the thermally activated delayed fluorescence (TADF) sensitizedfluorescent (TSF) systems, which realize high efficiency and high color purity simultaneously onorganic light-emitting diodes. The systems generally consist of a host, a TADF sensitizer, and afluorescent terminal emitter (TE). Hosts can affect photophysical properties of TADF molecules,
which may further influence the performance of TSF systems. However, most reported TSF systems
focused on TADF sensitizers and TEs, and there have been rare investigations about the host effects
on the TSF systems.
We prepared and conducted the photophysicalcharacterizations of solution- processed 0.5 wt%
tPhBODIPY: 20 wt% MCz-TXO: CzSi/PPF TSF
systems. Here, MCz-TXO reported by Kaji’s group
was used as the TADF sensitizer because of its verylarge rate constant of reverse intersystem crossing(RISC), kRISC, ~108 s−1[1]; tPhBODIPY reported byour group was used as the TE owing to its narrow
emission and high photoluminescence quantum
yield
[2];
9-(4-(tert-butyl)phenyl)-3,6bis(triphenylsilyl)-9H-carbazole(CzSi)
ordibenzo[b,d]furan-2,8-diylbis(diphenylphosphineoxide) (PPF) was adopted as the host to investigate
the host effects.
Experimentally, both TSF systems showed fast
Figure. 1. The excitons transfer processes in the
FRET from MCz-TXO to tPhBODIPY. However,solution-processed 0.5 wt% tPhBODIPY: 20
the PPF-host TSF system is expected to show a
wt% MCz-TXO: (a) CzSi/ (b) PPF,
much more effective FRET. At first, the rate
respectively.
constant of FRET, kFRET, (5.1 × 108 s−1) in PPF islarger than the kFRET (2.3 × 108 s−1) in CzSi; second, the kFRET is larger than the rate constant ofintersystem crossing (kISC) in PPF while the kFRET is smaller than the kISC in CzSi. Therefore, more
excitons can be transferred to tPhBODIPY for narrow emission in the PPF-host TSF system than the
CzSi-host one. Dexter energy transfer (DET) behaviors were also investigated. Experimentally, DET
was successfully inhibited in the PPF-host system although it occurs in the CzSi-host system. These
investigations experimentally demonstrated the profound impacts of hosts on the FRET and DET in
the TSF systems and also provided a novel strategy for suppressing the undesired DET.
The manuscript highlighting this work will be submitted soon. In addition, another manuscript
closely related to this joint work and also focusing on the host effects in the solution-processed TSF
systems is in preparation.
[1] Y. X. Ren et al., Appl. Phys. Express 14, 071003 (2021). [2] X. Z. Song et al., Adv. Opt. Mater., 8, 2000483 (2020).

－95－2022-96（国際）Fabrication of nanotopographical polymer surfaces for bactericidal
properties-IV
Maya Endoh－96－

Stony Brook University

2022-97（国際）Verification and development of dynamic stiction theory
Ken Nakano

Yokohama National University

Objectives – Since the time of Charles-Augustin de Coulomb (1736–1806), we havebelieved that there exist two types of solid friction: static and kinetic. However, in 2020,
Nakano and Popov published a different friction theory indicating that static friction
might be an illusion made by the rotation of kinetic friction [Nakano & Popov, Phys. Rev.
E 102, 063001 (2020)]. This friction theory, termed the dynamic stiction (DS) theory, isdescribed within a purely mechanical framework by introducing a geometricalmisalignment, the impact of which had been overlooked over two hundred years. In thisstudy, we aimed to verify and develop the DS theory for polymeric materials, including
the unique polymeric swollen materials termed the concentrated polymer brushes (CPBs)
developed by Professor Yoshinobu Tsujii, ICR, Kyoto University.
Results and Discussion – A physical model of sliding friction, termed the viscoelastic
foundation (VEF) model [Nakano & Kono, Front. Mech. Eng. 6, 38 (2020)], wasextended to describe the relationship between the viscoelasticity of CPBs and the DS
theory. A rigid indenter was assumed to slide on an array of single-degree-of-freedom
viscoelastic elements. The standard linear solid model was used as the viscoelastic
element. Analyzing numerical simulation results finds three types of dimensionlessparameters determining the friction coefficient of the VEF model. The master curve offriction is branched by the ratio of the two types of time constants, the retardation timeand relaxation time of the standard linear solid element. However, the master curve has
three types of asymptotes for low-, middle, and high-speed regions, the same as theasymptotes for the Voigt-type VEF model (for low- and middle-speed regions) and theMaxwell-type VEF model (for middle- and high-speed regions). This means that when
we describe the relationship between the viscoelasticity of materials and the DS theory,
the Voigt-type VEF model is sufficient as the DS mode vanishes for the high-speed region.
Outcome reports – [1] K. Nakano, “Contact and Friction of Elastomers”, TTRF-TAIHOInternational Symposium on Automotive Tribology 2022, Online, 14 April 2022 (Invited).
[2] T. Watanabe, S. Hatanaka, K. Nakano, “Description of hysteresis friction by thestandard linear solid model”, JAST Tribology Conference, Fukui, 09 November 2022. [3]K. Nakano, “Virtual damping generated by friction vector rotation”, AsiaBrake 2023
Conference and Exhibition, Bangkok, Thailand, 28 March 2023 (Invited).

－97－2022-98（国際）Synthesis of Polyether Nanocomposite Solid Polymer Electrolytes for
Lithium-Ion Batteries
Robert C. Ferrier, Jr. Michigan State University
Objective: The objective of this work was todevelop novel polyether nanocomposites bycombining the epoxide polymerization techniquesof the PI with the polymer brush synthetic expertiseof Prof. TSUJII at Kyoto University. Experimental
Methods: Initiators were characterized by 1H NMR
spectroscopy. Polymers were characterized by sizeexclusion chromatography (SEC), 1H and 13C NMR
spectroscopy, and differential scanning calorimetry
Silicananoparticles
(NPs)
were
Figure 1. (top) SIP scheme for (DSC).
characterized by scanning electron microscopy andepoxides. (bot.) TGA of grafted NPs.
thermogravimetric analysis (TGA). Outcomes:
Ionic conductivity results showed interesting behavior for high dielectric materials, suchas polyepichlorohydrin (PECH) with a dielectric constant (𝜀𝜀) of ca. 17. We developed asurface-initiated polymerization (SIP) scheme by grafting thiolated silanes to NPs andreacting the thiol with trimethyl aluminum to form an initiator (cf., Figure 1 top). SIP of
ECH produced PECH brush grafted NPs. This is the first time, to our knowledge, SIP of
epoxides has been demonstrated. We further synthesized single ion conductors through
PECH modification, which we will apply to PECH brushes. New initiators weredeveloped from NHS-ester thiols allowing us to graft polymers to aminated surfaces totune membrane interfaces. Analysis: TGA was performed on the synthesized brushgrafted NPs (cf., Figure 1 bottom). The grafting density was calculated to be 0.57 chains/ nm2 based on the targeted molecular weight of 40 kg/mol. FTIR and NMR spectroscopy
were consistent with the presence of grafted brushes. Furthermore, brush grafted NPs
were soluble in organic solvents. Publications: (1) N. Safaie et al., Polymer Chemistry,
2022, 13 (19), pp 2803-2812. (2) Robert C. Ferrier, Jr. “Facile Epoxide Polymerizations
with Sustainable Aluminum Catalysts.” Invited seminar. Kyoto University, January 2023.
(3) Robert C. Ferrier, Jr. “Facile Epoxide Polymerizations with Sustainable Aluminum
Catalysts.” Invited seminar. ACS Mid-Michigan, October 2022. (4) Robert C. Ferrier, Jr.,
Synthesis of (co)poly(thio)ethers using Earth abundant aluminum-based compounds.
Seminar. ACS National Meeting, Chicago, IL, August 2022.

－98－2022-99（国際）Development and characterization of metal oxide nanocrystalline
films for solar water splitting
Yasuhiro Tachibana

RMIT University

Introduction
Photocatalytic water splitting is an attractive technology to produce sustainablehydrogen gas from water using solar energy. To develop such photocatalytic materials, it
is vital to initiate water reduction and oxidation reactions before photogenerated electrons
and holes recombine. It is necessary to form nanocrystalline films to accelerate water
splitting reaction and retard charge recombination reaction.
In this project we have developed oxygen deficient tungsten oxide nanorods using asimple method. Optical properties and photocatalytic performance were characterized by
employing a series of spectroscopies. We have conducted this project with Professor
Teranishi at the ICR.
Experimental
Tungstic acid (1 mmol) was dispersed in 15 mL OLA and 6.5 g ODE. The solution wasdegassed to remove oxygen and water under vacuum at 125℃ for 2 hrs. Subsequently,
the solution was heated to 320 ℃ under nitrogen atmosphere. The solution wasmaintained at 320 ℃ for up to 12 hrs. The synthesized WOx nanorods were purified byadding excess ethanol to remove excess ligands, the unreacted precursors, i.e. tungstic
acid, or by-products. Finally, the precipitated WOx nanorods were re-dispersed in
OA/toluene.
Results and Discussion
While the reaction temperature rises up to 320 ℃, the solution colour was changed fromyellow to green, and finally to navy blue. The final navy blue solution was purified andanalysed using TEM, resulting in WOx nanorods with an average length of 13.5 nm andwidth of 9.4 nm. The synthesized WOx nanorods are highly emissive with the emission
peak around 490 nm, a PL lifetime of around 4 nm and a PLQY of 2.3 %.
In addition to the synthesis and characterisation of WOx nanorods, we are also
successful in synthesizing lead free metal halide perovskite nanocrystals.[1]Outcomes[1] T. Teranishi, Y. Tachibana and co-workers, J. Photopolym. Sci. Technol., Accepted (2022).

－99－2022-100（国際）Interdisciplinary Approach to Nanostructured Materials for Applications
Jean-Pierre Bucher

Université de Strasbourg

We summarize here the progress on two fronts of our interdisciplinary project for which
Professor T. Teranishi is our ICR contact
Structural changes of inorganic nanoparticles (Teranishi, Kyoto) can be characterizedwith much advantage by HR-TEM (Banhart, Strasbourg).
In 2022, Teranishi’s group has achieved the following results:
1) Synthesis of ~3 nm Pd nanoparticles (NPs) capped with 1-dodecanethiol or
triphenylphosphine ligand and confirmation of phase change from Pd to PdSx at around
250 °C by using synchrotron XRD.
2) Synthesis of wurtzite-CoS and spinel-Ni3Se4 NPs larger than 15 nm.
Self-organization of single molecule magnets (SMM’s) by means of macrocycle
networks and LT-STM characterization.
The SMMs were synthezised in Strasbourg (Ruben’s group). This compound has been sent
to Nagoya where it will be incorporated in the synthesis of the 2D-crystal made of properly
functionalized pi-conjugated macrocycles (Tanaka’s group).
Simultaneously Tanaka’s group has undertaken the synthesis of the proper ligand to growthe macrocycle. This optimization process is still ongoing. Next step will consist incharacterizing the crystallized sample, by means of conventional techniques such as X-ray
diffraction and optical techniques, before the drop cast 2D network is examined on Au(111).
Simultaneously M. Boero in Strasbourg, in collaboration with Bucher’s group, undertook
a molecular dynamics calculation to solve a long standing issue on the conformation of selfassembled TbPc2 SMM in a 2D network. The results were compared with the STM data forthe simple case of self-assembled TbPc2 on Au(111). The calculated electron densities of the
TbPc2 molecules compare well with STM results and deepen our knowledge of these doubledecker SMMs in interaction with their environment. In particular, it is found that it is notnecessary to consider an azimuthal angle different from 45° between the two Pc ligands toaccount for the experimental result. A publication is in preparation.

－100－2022-101（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 ω+ω→(2-u)ω+uω is enhanced, where ω is the energy of the creation
laser pulse and uω is the energy of the inducing laser pulse with 0<u<1. The signal photon energy
in this scattering process corresponds to (2-u)ω.
Progress and Achievements
We have extended the search by increasing laser intensity and developing a new method to handle
backgrounds from atomic FWM processes, in particular, from the optical elements included in the
searching system.
We summarize the published papers and a press release relevant to this subject during FY2022
as follows.
Published papers:[1] Search for sub-eV axion-like particles in a stimulated resonant photon-photon collider with two laser beams based on a novel method todiscriminate pressure-independent components, Yuri Kirita, Takumi Hasada, Masaki Hashida, Yusuke Hirahara, Kensuke Homma*, Shunsuke
Inoue, Fumiya Ishibashi, Yoshihide Nakamiya, Liviu Neagu, Akihide Nobuhiro, Takaya Ozaki, Madalin-Mihai Rosu, Shuji Sakabe & Ovidiu
Tesileanu (The SAPPHIRES collaboration), Journal of High Energy Physics volume 2022, Article number: 176 (2022). (acknowledge the support
by ICR)[2] Hunting dark energy with pressure-dependent photon-photon scattering, Taishi Katsuragawa, Shinya Matsuzaki, and Kensuke Homma, Phys.
Rev. D 106, 044011 – Published 3 August 2022. (acknowledge the support by ICR)

[3] Sensitivity to Axion-like Particles with a Three-Beam Stimulated Resonant Photon Collider around the eV Mass Range, Kensuke Homma *,Fumiya Ishibashi, Yuri Kirita and Takumi Hasada, Universe 2023, 9(1), 20. (acknowledge the support by ICR)

Press release:[1] https://www.hiroshima-u.ac.jp/news/72499 (acknowledge the support by ICR)

－101－

2022-102（国際）Tin-perovskite thin film crystallization on new hole-transporting materials
Antonio Abate

Helmholtz-Zentrum Berlin

Perovskites solar cells (PSCs) are bringing third-generation photovoltaic technologies to their goldenage, with power conversion efficiencies (PCE) over 25% and 32% for single junction and tandem
devices, respectively. Among their several advantages, their low cost of manufacturing is particularly
remarkable, opening the door to their implementation in all kind of environments, including theirintegration in buildings and residences. However, the main component of the currently best
performing devices, i.e. lead (Pb), is strongly hindering the potential of this technology for thisapplication. The most promising candidate up to date to replace Pb is tin (Sn), with proven much
lower toxicity and the potential to overcome the PCE of Pb-based solar cells owing to their lower
bandgap. These compositions, while showing encouraging PCE values around 15%, face strong
stability challenges due to their structural and chemical nature. With this work, we aimed to point out
these problems from a critical perspective and propose the directions for the field to achieve efficientand long-term stable lead-free Sn-based perovskite solar cells for the future implementation in all
kind of environments.
First, the composition of the Sn-based perovskite material is critical for its structural and thermal
stability. Using several A-site cations or introducing 2D/3D mixtures can lead to big increases in longterm in-operando stabilities. Here, phenylethylammonium cations have shown a unique ability tolower the density of defects, improve interfaces and blocking water penetration into the materials.
Second, we discussed the charge-selective layers with the strongest potential for Sn perovskites. We
highlighted the wide applicability and opportunities of fullerenes as electron transporting materials
and interface modifiers for p-i-n device architectures, as well as the possibility to optimize PEDOTbased hole selective layer for enhancing charge extraction and stability at the bottom interface. We
pointed out the need for further investigations on the influence of inorganic charge selective layers
on the stability of Sn perovskites. Moreover, Sn(II)-containing materials always face the oxidationdriven degradation. To address it, we proposed the use of DMSO-free solvents, as well as otheradditives such as SnX2 ones or reductive organic materials. We also listed the typically less-discussed
intrinsic factors affecting Sn perovskites stability. Finally, we emphasized encapsulation strategies asa critical step to develop towards the commercialization of lead-free Sn-based perovskite
photovoltaics and optoelectronics.
[1]

E. Aktas, N. Rajamanickam, J. Pascual, S. Hu, M. H. Aldamasy, D. Di Girolamo, W. Li, G.
Nasti, E. Martínez-Ferrero, A. Wakamiya, E Palomares, A. Abate, Commun. Mater. 2022, 3,
104.

－102－

2022-103
Biochemical characterization of aldehyde dehydrogenases involved in thebiosynthesis of plant volatile benzenoids
Takao Koeduka

Yamaguchi University【Research aims】Aromatic compounds, especially volatile benzenoids, derived from natural resources,
including rare plants, are known as functional components showing health-promoting activities and as
signaling molecules for interactions among organisms in ecosystems. Therefore, human being, especially plantbiochemists, are strongly interested in understanding their biosynthesis and regulatory mechanisms. In thisstudy, we aim to understand the formation and control mechanisms of diverse aromatic compounds at themolecular level, and to analyze the function of dehydrogenases that convert benzaldehyde, an importantintermediate for volatile benzenoids, to benzoic acid.
【Method and results】We have succeeded in obtaining comprehensive gene expression data by transcriptome
analysis of the petal limb, flower buds, and leaves of petunia (Petunia hybrida), which nocturnally emits
volatile benzenoids as floral scent. We searched for candidate genes by tBLASTx analysis using aldehyde
dehydrogenase (HcBD) from Hypericum calycinum as a query against the gene expression data of petunia. As
a result, we found a gene (contig_15074) that shows 73% identity at amino acid level with HcBD and was coexpressed with known biosynthetic genes for volatile benzenoid. Next, we extracted total RNA from petunia
petals at different developmental stages of petunia flowers and at different times of the day and night, andperformed qRT-PCR analysis to examine the expression pattern of contig_15074. Then, we found that
contig_15074 was highly expressed post-anthesis and specifically in the evening. Furthermore, we also
expressed the recombinant proteins of contig_15074 in E. coli cells and purified them by Ni-affinity
chromatography. The resulting purified enzymes showed the activity to produce benzoic acid frombenzaldehyde in the presence of NAD+ or NADP+. The high enzymatic activity was found at a wide pH rangeof pH 6.5-10.0 and the purified enzymes displayed apparent Km value of 92.7±6.0 µM for benzaldehyde. These
results suggest that contig_15074 encodes a benzaldehyde dehydrogenase that produces benzoic acid(hereafter referred to as PhBALDH). The substrate specificity of PhBALDH is currently being analyzed.
【Summary】In petunia that attracts nocturnal moths as pollinators, the production of floral scent increases
after flowering at night. The expression pattern of PhBALDH was positively correlated with the production
pattern of petunia floral scent, suggesting that it is responsible for the biosynthesis of floral scent in petals.
This is the first report of benzaldehyde dehydrogenase in Solanaceous plants, and the ability to utilize both
NAD+ and NADP+ as cofactors is the first enzymatic property of this enzyme family. To elucidate thecontribution of PhBALDH in petunia petals, we are now trying to generate transgenic petunias overexpressing
or deleting PhBALDH to examine the effect of benzaldehyde dehydrogenase on the production of floral scent.

－103－2022-104
Regulatory Role of Phytohormone Cytokinin
on Leaf Epidermal Cell Differentiation
Shiori Aki

Nara Institute of Science and Technology

Objectives: The leaf surface is composed of various types of cells including pavement,
trichome, and stomatal cells, all of which differentiate from meristematic cells in the leaf
epidermis concomitantly with leaf development. Although the differentiation of leaf epidermal
cells proceeds basically according to the genetic program, it is greatly influenced byenvironmental conditions and plant growth statuses. Due to the accessibility of the leaf surface
for many purposes, differentiation processes of leaf epidermal cells have been intensively
investigated in genetic and physiological studies. As a result, regulatory factors and their
networks have been clarified to a large extent for leaf epidermal cell differentiation, especiallyfor differentiation of trichomes and stomata in Arabidopsis thaliana. However, regulatory
mechanisms for the transition of leaf epidermal cells from the proliferation state to thedifferentiation state remain relatively unclear. In this study, we focus on cytokinin, aphytohormone involved in the transition from proliferation to differentiation, and geneticallyexamined its involvement in leaf epidermal cells differentiation.
Experimental Methods: The Arabidopsis transposon-tagging mutants SM_3_33583 and
SM_3_38189 for the cytokinin oxidase/dehydrogenase genes CKX4 (AT4G29740) and CKX5(AT1G75450), respectively, were obtained from Arabidopsis Biological Resource Center(ABRC). Their homozygous mutant lines were established and crossed with each other toobtain their double mutant. Single and double mutant lines of the genes were examined fortheir morphological phenotypes in the leaf surface and total plant development.
Results and Discussion: To investigate effects of cytokinin on the cell differentiation of leaf
epidermal cells genetically, we utilized Arabidopsis mutants defective in cytokinin
oxidase/dehydrogenase (CKX), a cytokinin-metabolizing enzyme that irreversibly inactivatesthe endogenous cytokinin trans-zeatin. Among seven Arabidopsis CKX genes, we selected
CKX4 and CKX5, which are expressed at relatively high revels in the shoot apex including theleaf epidermal meristem, and obtained their transposon-tagging mutant lines, SM_3_33583 and
SM_3_38189 (designated as ckx4 and ckx5, respectively) from ABRC. We determined thatboth ckx4 and ckx5 contain the transposon insertion in the first coding exons of their relevant
CKX genes, indicating that they are loss-of-function mutants. We crossed them and obtained
the ckx4ckx5 double mutant in the F2 generation. Neither the single nor double mutants
exhibited obvious phenotypes in the leaf surface. Because environmental stresses greatly
enhanced the expression of those CKX genes, their phenotypes are assumed to appear only
conditionally. Phenotypic analyses under stressed conditions, e.g., treating with exogenous
cytokinin, will be effective for further investigation.
－104－2022-105
Electronic and spintronic properties of multilayer system
including NiCo2O4 and Fe3O4
Taro Nagahama Hokkaido University
Introduction: Oxide magnetic materials are a promising new class of spintronic materials, characterized byadvantageous features such as a high transition temperature and large spin polarization. Furthermore, itsvarious electrical conductivity makes it a crucial component in the semiconductor spintronics, currently facing
material issues. In this investigation, the epitaxial heterojunction of Fe3O4 and NiCo2O4 were evaluated withan aim towards realizing p-n junctions in the future. Fe3O4, a conventional Fe oxide, has been reported to
exhibit n-type semiconductor behavior, while NiCo2O4, a newly-observed oxide magnet attracting muchattention, has reported to have p-type conductivity. Since both are spinel structures, it is expected that epitaxial
growth can be achieved. In this study, Fe3O4/NiCo2O4 bilayer films were prepared by reactive molecular beam
epitaxy and their properties were investigated.
Experiment: Multilayers were prepared on MgO(100) substrates by reactive molecular beam epitaxy methodin the oxygen atmosphere. The layer structure of the MTJs was MgO(100) substrate/MgO buffer (20nm)/NiCo2O4 (24 nm)/MgO (0 or 1 nm)/Fe3O4 (30 nm) /AlOx (5 nm). Epitaxial growth and crystal structure
were investigated by RHEED and XRD.
Results and discussions: In the sample preparations, the order of deposition was an important point. In theorder of the subst./Fe3O4/NiCo2O4, the annealing in high oxygen partial pressure of 300 Pa was necessary togrow epitaxial NiCo2O4 layer, which would bring about excessive oxidation of bottom Fe3O4 layer. On theother hands, for the opposite order, subst./NiCo2O4/Fe3O4, the multilayers were exposed to heat treatment at ahigh temperature of 873K, which would result in the phase separation of NiCo2O4 layer. Adding to that, bottom
interface of Fe3O4 tend to show dense anti-phase boundary. Figure 1 showed RHEED patterns and XRD
profiles of NiCo2O4/Fe3O4 films. The epitaxial growth of each layer was confirmed in the Fig.1. We
investigated the magnetic coupling of bilayer
by insertion of MgO layer of 1 nm. Obvious
direct magnetic coupling was observed in thebilayer without MgO layer.
Publication and Conference: 1, Hara et al.,"Inverse

TunnelMagnetoresistanceofMagnetic Tunnel Junctions with a NiCo2O4
Electrode" AIP Advances accepted. 2,
Nagahama et al., " Observation of thenegative spin polarization of NiCo2O4 bytunnelmagnetoresistance"

Okinawa, July 2022.

ICMSF2022
Fig.1 RHEED patterns and XRD profiles for NiCo2O4/Fe3O4.
－105－2022-106
アルツハイマー病治療に向けたアミロイド光酸素化触媒の構造最適化
金井求

東京大学

アルツハイマー病は進行性の神経変性疾患であり、認知機能の低下を引き起こすため、社会的に大きな問題となっている。アミロイド性タンパク質であるアミロイドベータ(Aβ)はアルツハイマ
ー病の原因物質と考えられており、Aβ の凝集抑制・分解ができればアルツハイマー病の予防・治療につながると期待される。我々は、スイッチ機能を有する光触媒が促進するアミロイド選択的酸素化反応を利用することで、Aβ の凝集性低減・毒性低下・モデルマウス個体内からの除去が実現できることを見出している。現在、大型動物およびヒトでの治験の応用に向けた触媒活性の向上のため、BBB 透過性を持つ分子サイズを保ったまま、長波長光照射における触媒の項間交差効率を上昇させる分子設計を目指している。一方で化学研究所の梶らは、計算化学による項間交差速度の予測に成功している。梶研究室との共同研究により、理論化学と実験化学との融合研究から、アルツ
ハイマー病治療研究のステージを進めるアミロイド光酸素化触媒の創出をおこなうことを本研究の目的とした。
検討の結果、以前までに⾒出しているアゾベンゼンボロン錯体母骨格では大幅な活性向上は困難であることが明らかになった。一方で我々はトリアリールメタン系色素がスイッチ機能を持つ有望な光酸素化触媒になりうることを見出した。本色素は芳香環に共役した C=N 二重結合を有しており、励起状態において項間交差に有利な n-π*性の増大・反応性の向上が期待される。また、本色
素は比較的コンパクトな構造を有するため、BBB 透過性の向上が期待できる上に、置換基を変更することによりその吸収波長を長波長化することができる。種々の検討の結果、最適な触媒としてEV(Ethyl Violet)を得た。595 nm の光にて凝集 Aβ の酸素化反応を検討したところ、反応は Aβ 選
択的に進行し、従来型触媒の約 100 倍の活性を示すことが明らかになった。現在、梶らと共同し、EV の項間交差速度の予測からそのスイッチ機構発現のメカニズムと酸素化効率の向上のメカニズ
ムについて解析を行っている段階である。
さらに我々は EV の高細胞毒性、低 BBB 透過性という問題点を解決するためにプロドラッグ化戦略をとることとした。すなわち、中央のカルボカチオンにヒドリドイオンを結合させ中性種としたロイコ体 LEV(Leuco Ethyl Violet)をプロドラッグとし、酸化刺激によって系中で活性種であるカ
チオン種を遊離させることを目指した。その結果、LEV の細胞毒性は光照射の有無に関わらず大きく低下し、BBB 透過性も約 4 倍向上した。そこでこの触媒を用い、生体マウスでの反応を検討した。アルツハイマー病モデルマウスに触媒投与と頭部への光照射を 2 か月間継続し、マウス脳由来
サンプルをウエスタンブロッティング法にて評価した。その結果、EV, LEV を投与したマウスでは
Aβ 量の減少が確認された。また、LEV で処置したマウスは頭部の外傷が認められなかった。これは BBB 透過性、標的選択性の向上により、頭皮組織での活性酸素生成が抑制されたためであると考えている。

－106－2022-107
動的効果を考慮した熱活性化型遅延蛍光速度論の確立
浦谷浩輝 早稲田大学

有機発光ダイオード（OLED）の発光効率を高める手段として熱活性化型遅延蛍光（TADF）の利用が注目されている。TADF 速度論の理論予測にあたっては、蛍光、無輻射失活、系間交差、逆系間交差のそれぞれに関する速度定数の理論計算が必要となる。従来、これらの計算は単一の分子構造を仮定して行われてきた[1]。しかし現実の OLED においては、発光分子は周辺分子との相互作用を受けて様々な配座をとっており、動的な構造ゆらぎも存在する。本研究は、これらの効果を取り込んだ新たな TADF 速度論の構築を目的とする。
ターゲットとして、ホスト分子に CBP、発光分子に DACT-II を用いた非晶質有機薄膜を選択した。ホスト分子との相互作用による発光分子の配座及び環境のばらつきを再現するため、古典分子動力学計算により凝集構造を作成した。得られた構造から、発光分子と周囲のホスト分子を含むク
ラスターモデルを複数抽出した（Fig. 1）。各モデルに対し、無輻射失活速度定数を支配する因子である振電相互作用強度（|𝑉𝑉� |）を計算した。クラスターモデルは 20 分子程度からなる大規模な系であるため、半経験的量子化学計算手法である密度汎関数強束縛（DFTB）法を用いた。本研究では、
DFTB 法に基づく|𝑉𝑉� |の近似式を導き、計算ルーチンを DCDFTBMD プログラム[2]に実装した。

16 種類のクラスターモデルに対して|𝑉𝑉� |のスペクトル分布を計算した結果を Fig. 2 に示す。比較のため、気相における安定構造の DACT-II に対する計算結果も示す。クラスターモデルにおけるスペクトル分布は、気相中のものと異なるピーク強度を持ち、かつ、ばらつきを持つことがわかる。このことから、非晶質有機薄膜における個々の発光分子の TADF 速度論は、周辺分子との相互作用の影響を強く受けており、気相中分子を仮定して得られる速度論とは異なっていることが示唆される。

Fig. 1. Model construction.
[1] K. Shizu and H. Kaji, J. Phys. Chem. A 125, 9000 (2021).

Fig. 2. Spectral distribution of |𝑉𝑉� |.

[2] Y. Nishimura and H. Nakai, J. Comput. Chem. 40, 1538 (2019).

－107－2022-108
Analysis of the physiological functions of extracellular vesicles produced byintestinal bacteria and their application
Atsushi Kurata

Kindai University

Introduction:
The animal gastrointestinal tract is inhabited by a complex community of bacteria. Gut
bacteria contribute to the maintenance of host physiological functions through the production ofbacterial metabolites. Membrane vesicles (MVs) produced by intestinal bacteria are attracting
the attention as novel bioactive substances. Within this context, the first objective of this study
is to elucidate the physiological effects of enterobacterial MVs on host organisms and the
production mechanisms of MVs from intestinal bacteria. The second objective is to develop thenovel expression systems for heterologous proteins using MVs-producing bacteria.
Results:
1. Properties of MVs produced by intestinal bacteria.
We detected a large amount of MVs in the rat gastrointestinal tract. Lactiplantibacillus
plantarum produces MVs that activate innate and acquired immune responses. L. plantarum
induces an immunostimulation though the Toll-like receptor 2 recognition of the N-acylatedamino acid moiety of lipoprotein in the MVs. Bifidobacterium longum subsp. infantis produces
MVs. Extracellular solute-binding protein in B. infantis MVs is involved in the production of
IgA by acquired immune cells via the production of IL-6 by innate immune cells. These bacterial
strains produce useful MVs. We plan to develop novel strains that produce large amounts of MVs
using the bacterial strains.
On the other hand, abnormal immune responses in the gut causes inflammatory bowel
disease. MVs derived from L. plantarum NBRC 15891 inhibited the lipopolysaccharide-induced
inflammation in HT-29 cells. Additionally, MVs were orally administered to mice with dextran
sodium sulfate-induced colitis, which tended to decrease neutrophil infiltration in the coloniclamina propria and reduced the symptoms of colitis.
2. Function of the major cargo protein of MVs from Shewanella vesiculosa HM13.
S. vesiculosa HM13 isolated from intestinal contents of horse mackerel (Trachurusjaponicus) abundantly produces MVs, which carry a major cargo protein named P49 on theirsurface. By nanoparticle tracking analysis of MVs from a P49-less mutant and its parent strain,
we found that MVs from the mutant were prone to aggregation. We also found that the additionof purified P49 to the P49-free MVs improved their dispersibility. Thus, P49 on the surface ofMVs probably suppresses aggregation of MVs. This function may be beneficial for increasing
the surface area of MVs and for their long-distance delivery.
－108－

2022-109
Analysis of membrane lipid-dependent fermentation stress response
in acetic acid bacteria
Yosuke Toyotake

Ritsumeikan University[Introduction] Acetic acid shows potent antimicrobial activity and inhibits the growth of mostmicroorganisms even at low concentrations. However, acetic acid bacteria (AAB) such as
Acetobacter spp. can produce acetic acid from ethanol and possess extraordinary resistance to acetic
acid. Many researchers have analyzed the mechanism of acetic acid resistance in AAB, but the full
extent of this mechanism has not yet been elucidated. In particular, the contribution of membrane
lipids of AAB to acetic acid tolerance has not been fully understood.
AAB produce phosphatidylcholine (PC) as a membrane phospholipid (PL), constituting the cell
membrane. Although previous studies have suggested that PC is involved in acetic acid tolerance,
the physiological functions of PC in detail remain unknown. To elucidate PC functions in AAB, wepreviously constructed the PC-deficient mutant of A. pasteurianus SKU1108. In this study, we
showed that the loss of PC reduces various stress tolerance in A. pasteurianus SKU1108.
[Results and Discussion] AAB synthesize PC from phosphatidylethanolamine (PE) using PE
N-methyltransferase (PmtA). Thus, we constructed a markerless pmtA-deletion mutant (ΔpmtA)
from the parental strain of A. pasteurianus SKU1108 by homologous recombination. We confirmedthat PC was not produced, but PE was accumulated in ∆pmtA by analyzing the membrane PLs using
thin-layer chromatography. In addition, the introduction of the pmtA-complementation plasmid,
under the control of its native promoter, into ΔpmtA restored the synthesis of PC.
The colony-forming ability of ΔpmtA on agar medium supplemented with acetic acid wascompared with that of the parental strain, and ΔpmtA showed higher sensitivity to acetic acid thanthe parental strain. In addition, ΔpmtA did not grow well on agar medium acidified withhydrochloric acid to pH 3.5 compared with the parental strain. These results indicated that PC isimportant for the growth of this strain both in the presence of acetic acid and in low pH
environments. In addition, we demonstrated that ΔpmtA did not grow well at higher temperatures orunder oxidative stress caused by hydrogen peroxide, suggesting that PC also contributes to thethermotolerance and oxidative tolerance of A. pasteurianus SKU1108.
[Conference]
1. Toyotake Y, Yamamoto S, Hara Y, Tsuji A, Kawamata Y, Matsui D, Wakayama M “Analysis ofphosphatidylcholine-regulated membrane functions of acetic acid bacteria.” Japanese Society for
Extremophiles 2022
2. Yamakawa W, Toyotake Y, Tsuji A, Matsui D, Wakayama M “Physiological function analysis ofsqualene cyclase homologs from acetic acid bacteria” Japanese Society for Extremophiles 2022
－109－

2022-110
擬秩序ガラスの熱伝導
増野敦信

弘前大学

目的：酸化物ガラスは一般に，SiO2 などの網目形成酸化物の四面体ユニットが頂点共有して 3 次元ランダムネットワークを形成しているが，MgO などの修飾酸化物を添加すると，ネットワークが切断され非架橋酸素が生成する．SiO2 が少ない組成ではネッ
トワーク形成が困難になりガラス化できないが，この限界は無容器法を用いることで克服できる．例えば MgO-SiO2 二元系は無容器法によって MgO が多い組成までガラス化範囲を広げられる．これまでの構造解析の研究から，ネットワークの切断が進むほど原子充填密度が増加し，原子配列において結晶のような秩序性があらわれることがわかってきた．このようなネットワーク連結様式の変化，あるいは秩序性の増加は，ガラス中の熱伝導に影響を及ぼすと考えられる．そこで本研究では，MgO-SiO2 二元系
において幅広い組成範囲でガラスを合成し，その熱輸送特性の組成依存性を調べた．
実験と結果：ガス浮遊炉を用いて xMgO–(100−x)SiO2 二元系ガラス（0 ≤ x ≤ 67）を合成した．Raman 散乱スペクトルから，x が 50 を超えるとネットワークの切断が著しく進行し，x = 67 では，孤立した SiO4 や二量体 Si2O7 などが多く存在していることがわかった．ピクノメータによってガラスの密度を計測したところ，MgO 含有量の増加とともに密度と充填密度は増加していた．示差走査熱量測定（DSC）によりガラスの比熱を，
そして温度波法によって熱拡散率を測定した．得られた密度，比熱，熱拡散率から，熱伝導率を算出した．
Figure 1 に，xMgO–(100−x)SiO2 二元系ガラスの熱伝導率を示す．MgO 含有量の増加に伴い熱伝導率は大きくなり，
67MgO–33SiO2 ガラスでは，1.9 W/m·sを超える値を示した．Si–O–Si のネット
ワークが切断されることで熱伝導率は低下する，とした当初の予想とは逆の結果であった．このメカニズムは現時点では不明であるが，Mg–O–Mg の新たなネットワークが形成されたか，あるいは原子配列の秩序性の増大によるものと考Figure 1. xMgO–(100−x)SiO2 ガラスの熱伝導率．

えている．
成果報告：阿保健太，増野敦信，「MgO–SiO2 系ガラスの熱伝導特性」，令和 4 年度日本
セラミックス協会東北北海道支部研究発表，2022.11.10．
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電気化学的プロトン脱挿入を利用した金属酸化物の新奇物性探索土屋敬志 物質・材料研究機構

機能性材料である遷移金属酸化物の構造・物性は遷移金属の価数と密接に関連している。電界を利用して遷移金属の価数を制御することは、酸化物の新奇機能を開発やデバイス応用にも有用である。特に電界で制御できる電気化学的な酸化還元反応を利用した場合には、可逆的に価数を変調できるだけでなく、酸化物中へプロトンなどの余分なイオンを挿入することも可能であり、新しい物質相の発見も期待できる。これまでに我々は、ゲート絶縁体としてプロトン伝導性電解質であるナフィオンを用いたトランジスタ構造デバイスが遷移金属酸化物の電気化学的制御、さらにはプロトン注入による新物質開発に有用であることを明らかにしてきた[1]。本課題では、エピタキシャル
成長技術によって安定化された準安定酸化物に着目し、ナフィオンを利用した電気化学的な物性制
御やプロトン注入を行うことで、新物質相や新奇物性の開発を目指した。
以下に例として TiO2-δ 薄膜に関する実験結果を示す。パルスレーザー堆積法により、(100)LSAT
基板上に蒸着することで準安定構造であるアナターゼ型の結晶構造を有する TiO2-δ エピタキシャル
薄膜を製膜した。作製した薄膜をチャネルとしてプロトン伝導性電解質であるナフィオンをゲート絶縁体としたトランジスタ構造（図 1）を作製し、3 V のゲート電圧 VGS を印加することで電気化学的に水素を薄膜チャネルに注入した。水素注入前後において TiO2-δ 薄膜チャネルの電気抵抗には変化が見られなかった。また薄膜チャネルに対して弾性反跳原子検出法（ERDA）を行った。図 2 に得られた反跳水素のエネルギースペクトルを示す。水素注入を行った薄膜試料では、900 keV 付近における反跳水素に由来するピーク強度がわずかに増加していた。これらの結果は、TiO2-δ 薄膜へ注入した水素の大部分は、薄膜内部には導入されず、蓄積されてていたとしても薄膜表面近傍であることを示す
ものである。このことは薄膜チャネルの抵抗が水素注入前後でほとんど変化しなかった実験結果とも整合する。

収量 (arb. unit)

⽔素注⼊後
⽔素注⼊前

0

図 1. トランジスタ構造の模式図

500

エネルギー (keV)

1000

図 2. アナターゼ TiO2-薄膜の ERDA スペクトル[1] Y. Isoda, et al., Appl. Phys. Lett. 120, 091601 (2022).

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高圧合成による新規フッ化物イオン伝導体の探索
齊藤高志

高エネルギー加速器研究機構

遷移金属イオン（M）が酸素イオン（O）に加え他のアニオン（X）とも結合した複合アニオン化
合物は、結晶構造内において M-O 結合及び M-X 結合からなるネットワークが形成されることで酸化物とは異なる機能・物性を持つことが期待される。本研究では X アニオンとしてフッ化物イオンに着目し、ペロブスカイト構造酸化フッ化物の合成を試みた。フッ化物イオン F−は酸素イオン O2−とイオンサイズが近いため、酸化フッ化物を高温での焼成による通常の固相反応で作製した場合、一般的には F−/O2−が無秩序に入り混じった結晶構造となる。そこで本研究では、ペロブスカイト型
SrFeO3−δ を還元して得られる SrFeO2 の酸素欠損サイトへ F−をカチオンのフレームワークを保ったまま低温でトポタクティックに挿入することにより、F−と O2−が秩序列した酸化フッ化物 SrFeO2Fの合成を試みた。
まず SrCO3 と Fe2O3 の固相反応から得られた SrFeO3−δ を CaH2 で還元することで Fe イオンが酸
素平面 4 配位構造となる SrFeO2 を作製した。続いて、得られた無限層構造酸化物 SrFeO2 を化学研究所が有する高圧合成装置を用いて圧力下において比較的低温で XeF2 と反応させることにより
SrFeO2F を合成した。図 1 に示す X 線回折の結果から、生成物がペロブスカイト型構造を持つことが明らかになった。またメスバウアー分光測定から Fe イオンの価数は 3+であったが、Fe サイトは１種類しかなく、F−/O2−が無秩序配列していることが示唆された。メスバウアー分光測定から Fe イ
オンの価数は 3+であり、フッ素の挿入による Fe2+の酸化が起こったと考えられる。
合成した SrFeO2F のイオン伝導特性に関しては、交流インピーダンス測定法などにより今後詳細に検討を進めていく予定である。

30000

25000

Intensity

20000

15000

10000

5000

0
4

8

12

16

20

24

28

32

36

40

44

2 / 

図１．SrFeO2F の X 線回折パターン

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界面活性剤を利用した溶媒含浸樹脂による金属分離
倉橋健介

大阪公立大学工業高等専門学校

１．目的
固相抽出法による金属の分離は、溶媒抽出法に比べ、人体や環境に有害な揮発性有機溶媒の利用が少ないことから、資源の偏在などよって資源枯渇のリスクを抱える希土類金属元素のリサイクルなどで注目されている。我々の研究グループでは、多孔性樹脂に界面活性剤を含浸させた溶媒含浸
樹脂(SIR)を調製することで、他の抽出剤の助けなしに希土類金属元素を樹脂相へ吸着できることを見出した。溶媒含浸樹脂は簡便な手法で調製が可能であることに加え、抽出剤として用いる界面活性剤も入手が容易であることから、界面活性剤を用いた溶媒含浸樹脂は安価かつ環境に配慮した吸着剤としての用途が期待される。本研究では、この界面活性剤のみを用いた溶媒含浸樹脂による分離法を確立するため、吸着した金属イオンの回収法についての検討を行った。
２．実験方法エタノールで洗浄後、乾燥した多孔性樹脂 Amberlite XAD-7HP 1.0 g に対し、界面活性剤として
Sodium Dodecylsulfate (SDS)を 0.2 mmol 含むエタノール溶液 20 ｍL を加え、1 日含浸させた。溶媒を減圧留去し、50℃で 1 日真空乾燥させ、目的の SIR を調製した。1 ppm の La と緩衝液として 0.1
M クロロ酢酸ナトリウムを含む水溶液 2.5 mL を HCl と NaOH で pH 2.0 に調整し、SIR を 0.1 g 加え、15 分振とうした。振とう後、3000 rpm で 5 分間遠心分離し、水相のみを 2.0 mL 採取した。残った樹脂に、任意の濃度の HCl を加え、15 分振とうした後、遠心分離後の水相を分取することで逆抽出操作とした。得られた水相は Ni を内標準として、誘導結合プラズマ発光分光分析装置(ICPOES)を用いて金属濃度を測定した。
pH 2.0 で La を抽出した樹脂に対し、濃度を 0.1~1.0
M とした HCl を投与し、樹脂からの La の回収を試みた。結果を図 1 に示す。HCl 濃度の上昇に伴って La
回収率は向上し、0.5 M HCl を用いることで、SIR に吸着した La を完全に回収することができた。SDS を用いた SIR では pH が低いほど減少することから、樹脂に吸着した La が、水相の水素イオンと交換されることで、溶液に放出されたと考えられる。また、逆抽

100
80
60
40
20
0

回収率 / %

３．結果と考察

図1

00.5
HCl濃度 / M

1

SDS を含浸させた SIR からの HClを用いた La の逆抽出出を行った後の SIR によって、再度 La の抽出を試みたところ、純水により SIR を洗浄することで、1 回目と同様の La 抽出率を得ることができ、最低 1 回の再利用が可能であることがわかった。
４．成果報告1) 大石智也ら，第 25 回化学工学会学生発表会，オンライン開催，2023.3.
2) 大石智也，第 25 回工業高等専門学校生 化学研究発表会，大阪，2023.3.

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全反射近赤外分光法による高分子ブラシ層内の水の構造解析
源明誠 富山大学[目的]

固体高分子は高分子鎖が絡み合った状態で，特異な官能基を付与することで生体適合性や電気伝導性などの機能材料として，構造材やフィルムなどに使われている。近年開発された原子移動
ラジカル重合法による固体表面に高分子鎖を緻密に生長させた高分子ブラシは，次元規制された高分子鎖によって，防汚性や生体適合性などの機能を付与するとされる。この機能発現には水が関与しているとされるが，これまでにブラシ内部のみの評価はなされていない。本研究では，内部全反射近・中赤外吸収（ATR near/mid-IR）スペクトルから Poly(polyethylene glycol monomethoxy ether methacrylate)（P(PEGMA)）ブラシ内部のみの水構造を評価した。
[実験]

自作の高多重反射 ATR セルを使用し，種々濃度の P(PEGMA) 水溶液中の水，および ATR

結晶（シリコン）上に，高圧下における表面原子移動ラジカル重合法により調整した，種々膜厚（70,218, 1130 nm）の P(PEGMA) ブラシ中の水の ATR near/mid-IR スペクトルを得た。
[ 結 果 および 考 察 ]

図 1 に，OH 伸縮 振動結合音（syn+asyn）および秤動振動（ L），HOH 変角振動（），syn の結合音（syn + +L）含む，近赤外領域の純水の吸収スペクトルを示す。最高波数の成分は，L を含んでおり，水分子のダイナミクスに関する情報を与える。
種々の膜厚の P(PEGMA)ブラシ中の水の ATR-NIR スペ
クトルの評価から，膜内部のみのスペクトルを与えること 図 1. 純水の ATR-NIR スペクトルおよび成分分離のできるのは，乾燥時膜厚 1130 nm のブラシのみであった。一般にエバネッセント波の潜り込み深さ dp（分析深さ）は Harrick's 式で示され，本系においては 200 nm 程度と見積もられるが，それ以上の膜厚が必要であった。これは，Harrick's 式においては dp を表面の電場強度が 1/e になる深さと定義していることによるものである。
種々濃度（含水率 0－60 wt%）のP(PEGMA)水溶液および液体水に接触した P(PEGMA)ブラシ中の水の吸収強度の比較から，膨潤 P(PEGMA)ブラシの含水率を ～30 wt%と見積もられた。 図 2. P(PEGMA)水溶液および膨潤 P(PEGMA)ブラシ中の水の近赤外吸収
P(PEGMA)水溶液と P(PEGMA)ブラシ

スペクトルの成分分離結果

中の水の NIR 領域のスペクトル成分の分離結果を図 2 に示す。水分子の回転運動を反映する nL 成分の結合音であるsyn + +L バンドの吸収強度は，同含水率の P(PEGMA)水溶液の強度の半分程度であり，P(PEGMA)水溶液 ～10 wt%と同程度であった。これは，高分子ブラシの一端の固定化に起因する高分子
差の運動性低下に伴い，水和水の運動性も低下していることを示している。この高分子ブラシ中の水分子の運動性の低下は，ブラシ内における水の凍結挙動，あるいは膨潤ブラシの弾性特性に大きく影響を及ぼすと考えられる。
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3D プリンタを用いたモノリスの 3 次元構造制御
村瀬浩貴

共立女子大学

多孔材料は，各種の分離フィルタ，各種電池セパレータ，透湿防水布としての快適性衣料，海水淡水化膜や水浄化膜などの環境関連材料，血液透析膜や細胞培養基材などの医療材料など幅広い分野で利用されている。これまで，様々な多孔材料が実用化されてきたが，モノリス(Monolith)は３次元ネットワーク状の骨格構造を持ち，ネットワークの骨格サイズと，その空隙である連続空孔のサイズを独立に制御できる次世代多孔材料として注目されている。京都大学化学研究所の辻井敬亘教授と榊原圭太氏（元化学研究所助教、現産業技術総合研究所）は，界面化学的手法を駆使して，重合誘起スピ
ノーダル分解を経由するエポキシ系ポリマーモノリスで新規な多孔材料を創生してきた。一方，報告者はこれまで、Additive Manufacturing（AM, 3D Printing とも呼ばれる）の技術を応用して，新規な構造を有する複合繊維や繊維—樹脂複合型布帛の開発，セルロースナノファイバーの３次元造形に取り組んできた。本研究では AM の技術と，辻井教授らの界面制御技術・高性能モノリス合成技術を融合し，３次元構造を制御した新規ポリマーモノリスを創生することを目的とする。
辻井教授らの技術では，ポリビニルアルコール（PVA）の基材の上にエポキシ系モノリスを形成することで，孔の閉塞したスキン層の発生を防ぐことに特徴がある。PVA 製の鋳型を AM によって作製する
ことにより，任意の３次元形状のモノリス膜を作製することができる。本年度は、モノリスを成形する
際の鋳型を複雑化する検討を行った。今回、その構造モデルとして 3 次元ボロノイ構造を選択した。ボロノイ図（Voronoi Diagram）とは、ある空間に任意の位置に配置された複数の点（母点）に対して、それぞれの母点間の２等分線によって区切られた領域によって構成される平面である（ただし 2 次元ユークリッド平面の場合）。これを 3 次元ユークリッド空間に拡張したものが 3 次元ボロノイ図である。
任意の形状の 3 次元ボロノイ構造をモデル化するための 3D-CAD として、Rhinoceros (AppliCraft 社)とグラフィカルアルゴリズムエディターGrasshopper を用いた。Grasshopper を用いると、３次元空間に発現させる母点の数や、支柱の太さをパラメトリックに制御できる。Figure １は、母点の数を３水準変更した３次元ボロノイ構造の例と、AM で造形した３次元ボロノイ構造である。今後は、本構造の鋳型を PVA で作製する技術を開発する。

Figure 1. Models created with Rhinoceros with Grasshopper (left) and a 3D Voronoi structure
modelled with additive manufacturing (right).

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単電子トランジスタにおける巨大磁気抵抗効果の検討
真島豊

東京工業大学

本研究では、磁性ナノギャップ電極間に１つのナノ粒子を化学吸着したデバイス構造において、
磁場印加時にスピンに依存する単電子トンネル磁気抵抗効果を観察し、巨大磁気抵抗効果を実現す
ることを目的とした。
線幅 30 nm のコバルトと白金の交互積層ナノワイヤのアニール（加熱）処理のみで、10 kOe 以
上の高保磁力を有する L10 規則化強磁性単結晶ナノワイヤを Si/SiO2 基板上に直接作製する「ナノ構造誘起法」を開発した(1)。
電子線リソグラフィにより Si/SiO2 基
板上に、強磁性ナノワイヤ材料としての Co/Pt 交互積層ナノワイヤを直接形

図 1 ナノ構造誘起法により作製した L10 規則化 CoPt 単結晶ナノワイヤの SEM 像（左）と、 M-H カーブ （右）成し、アニール処理をした（図 1 左）。
ナノ構造誘起法では、アニール処理のみ
で 10 kOe を超える保磁力を有する強磁性ナノワイヤが形成されている（図１
右）。
2 次元微小角入射 X 線回折（GI-XRD）
パターンと、ナノビーム電子回折（NED）パターンにおいて（図 2 左・中央）、強磁性ナノワイヤが L10 型規則相を形成していることを確認した。ナノワ

図 2 強磁性ナノワイヤの 2 次元微小角入射 X 線回折（GI-XRD）パターン（左）。どんぐり型のナノワイヤの
断面 BF-TEM 像（中央左上）、赤丸で撮影したナノビー
ム電子回折（NED）パターン、超格子回折スポット（赤矢印）と、基本スポット（黄矢印）（中央）。高角度環状暗視野走査透過電子顕微鏡（HAADF-STEM）像（右）。

イヤ断面は、ナノスケールにおいて表面エネルギーが最小になるどんぐり型の形状になっていた（図２中央左上）。さらに、高角度環状暗視野走査透過電子顕微鏡（HAADF-STEM）像で断面を拡大し、ナノワイヤが双晶を含む単結晶になっていることを確認した（図 2 右）。
８ｎｍのギャップ長を有する規則化強磁性ナノギャップ電極をナノ構造誘起法により作製し、共同研究者の寺西教授が合成するナノ粒子を、自己組織化プロセスによりナノギャップ電極間に１つ化学吸着させた。磁性ソース電極／ナノ粒子／磁性ドレイン電極からなる単電子トランジスタにおいて、明瞭なクーロンダイアモンド特性を測定した。さらに、磁化の向きに起因したスピン依存単電子トンネル磁気抵抗効果を、電流の磁場掃引依存性により確認した。
1. R. Toyama, S. Kawachi, J. Yamaura, T. Fujita, Y. Murakami, H. Hosono, Y. Majima, Nanoscale Advances,
4, 5270-5280 (2022).

－116－2022-117－117－

2022-118
電子顕微鏡内での単一三次元量子ドット超格子の電子輸送特性と構造相転移挙動の同時観測
浅⾹透

名古屋⼯業⼤学

化学的なボトムアプローチで作られるナノサイズの半導体（量⼦ドット）は、省スペース・省電
⼒な電⼦回路の構成要素として期待されている。化学研究所の猿⼭（共同研究者）らにより独⾃に開発された Cu2-xS 量⼦ドット超格⼦ロッドは、迅速な⼀段階の液相法で得られる⾃⽴可能な三次元量⼦ドット集合体である。Cu2-xS 量⼦ドットは Cu+⽋陥量（x）によってホール密度やバンドギャッ
プを制御でき、かつ電圧印加や電⼦線照射により結晶構造が変化して異なる電⼦的特性を⽰すなど、
電⼦材料として特異な挙動を⽰し、ミクロな半導体素⼦としての可能性を有する。そこで、我々は観察試料に STM のプローブを⽤いて電圧印加が可能な機構をもつ透過型電⼦顕微鏡を（TEM）⽤いて Cu2-xS 量⼦ドット超格⼦ロッドへ電圧印加その場観察と電気的測定の同時計測を⾏い、構造と電気的特性に関する基礎物性を評価した。
Cu2-xS 量⼦ドット超格⼦ロッドは液相法により合成されたものを共同研究者の猿⼭⽒より譲り受け TEM 観察に使⽤した。超格⼦
ロッド 1 本を集束イオンビーム加⼯装置（FIB）によりピックアッ
プ、特殊形状 TEM グリッドにタングステンで接着し、TEM 観察試料とした（図 1）。電気測定およびその場 TEM 観察のために、⽚⽅の電極をグリッド、もう⽚⽅の電極を STM プローブとし、超格

図 1 TEM グリッドに設置した試料

⼦ロッドのみの電場応答を計測できるようにした（図 2）。
TEM 内で STM プローブを操作し、超格⼦ロッドの⼀端に接触させることで、電圧印加その場 TEM 観察を⾏い、同時に電流電圧特性の測定（IV 測定）を⾏うことに成功した。電圧印加時、TEM
像の分解能は⼤きく損なわれることはなく、通常の格⼦像の観察が可能であった。電圧は 0.8 V 程度まで印加することが可能であった。IV 曲線は⾮オーミックな特性を⽰し、整流効果と考えられる挙動を⽰した（図 3）。TEM グリッドとの界⾯と STM プローブは共

図 2 試料と電極の STM プローブにタングステンであり、試料は半導体である。本実験では⾦属−半導体接合界⾯が形成されており、ショットキー接合による整流効果が表れた可能性がある。また、電圧を上昇させ、電流が多く流れるようになった時、超格⼦ロッドの構造に変化が⾒られたが、この変化が純粋な電圧誘起あるいは電流誘起の現象なのか、電流増加時のジュール加熱によるものか、現時点では判断が難しい。今後、⾼分
解能 TEM 観察や組成分析による詳細な評価が必要である。

－118－

図 3 単⼀超格⼦ロッドの IV 曲線

2022-119
再生可能資源・木質バイオマスの先端化学材料への効率的変換法の開発
秦野修

奈良県⽴医科⼤学目的：
本研究は再生可能資源である木質バイオマスから、主成分であるセルロースやリグニン等
を、先端化学材料を含む有用化学物質への効率的変換/利用法の開発を目的とする。研究協力
者の化学研究所・中村研究室では、過酸化水素水と、有機酸触媒や金属錯体触媒を用いて、木材の効率的分解/合成/利用法の開発を行っている。この際、有機酸触媒等を木質ペレットに直接作用させ、軽量で高剛性な先端化学材料として注目されるセルロースナノファイバー（CNF）様の構造物が直接、生成されることを見出している。申請者は、スギ木幹部の薄い切片を作成して、形態学的側面から、これら触媒反応による組織構造の前後変化を可視化する系を構築した。この際、光学顕微鏡と SEM を併用して、リグニン、セルロース等の存在部位を可視化し（光学顕微鏡）、SEM を用いて電顕レベルの形態学的変化を追跡する系を構築した（CLEM 法: 光学・電子顕微鏡相関法）。本研究は、過酸化水素水と触媒等による木材分解過程を、主に組織形態学的変化の解析に重点を置き、木材から先端化学材料等の有用化学
物質への効率的分解/合成/利用法の開発・解析を行うことを目的とする。
実験方法、実験結果、考察：
本年度（2022 年）は、光学顕微鏡⽤の薄いスギ切⽚（9 μm 厚）を⽤いて、簡便な⽊材分解実験系を構築した。スギ⽊幹・⼼材部の⽊⼝⾯切⽚（約 4 mm x 5 mm x 0.009 mm）を作成して、35%、30 %、25 %、20 %、0 % H2O2 液中に浸して、静置化で 60 ℃保温を⾏な
い、切⽚の形がくずれる時間を調べたところ、30 % H2O2 液中では約 1.5 ⽇後、20 % H2O2
液中では約 2.5 ⽇後に⽬視で切⽚の形状が崩れ、ごく薄い切⽚を⽤いることにより、H2O2の添加のみで（触媒の添加なしで）効率的に仮道管細胞壁の分解が起こることが明らかになった。反応液の量は 0.04〜0.3 ml と変化させたが、ほぼ同様の結果であった。⼜、0 % H2O2
中では、切⽚の形状は４週間経過後も保たれていた。⼜、60 ℃以外の温度（50 ℃、65 ℃、
70 ℃、80 ℃）でも同様の実験を⾏ったところ、温度が⾼いほど、⼜、H2O2 濃度が⾼いほ
ど、早く切⽚の形状が崩れた。この実験系は、薄い切⽚を 60 ℃等の加温した H2O2 液中に静置するだけの簡便さで、ごく微量の⽊材量（約 4 x 5 x 0.009 mm = 0.18 mm3）と、ごく少量の過酸化⽔素⽔（0.04 ml 可能）を⽤いて、効率的にスギ⽊幹部の化学分解過程を追跡可能である。本実験系は微量の反応液で可能なため、96 ⽳プレート等を⽤いて、より効率的な化学分解を達成する触媒のスクリーニングにも応⽤可能と考えられる。
今後は、この反応過程における⽊質分解産物の同定を質量分析法等で⾏っていくと共に、分解過程の組織形態変化を Lignin, Cellulose, Hemicellulose 量等の変化に着⽬して⾏って
いきたい。

－119－

2022-120
Functional analysis of non-canonical strigolactones as plant hormones androot-derived signals
Yoshiya Seto

Meiji University【The aim of this study】Strigolactones (SLs) are plant hormones

HOthat regulate shoot branching, and also function as root-derived

O

carlactone（CL）chemical signals. SLs are biosynthesized from carotenoids via a key

P450

monooxygenase,

MORE

AXILLARYGROWTH1 (CYP711A). We previously identified methyl esterified
derivative of CLA, methylcarlactonoate (MeCLA) in Arabidopsis,and found that MeCLA can interact with the Arabidopsis SL receptor
protein, AtD14. On the other hand, CL and CLA were not able to

O

CLAMT

Arabidopsis, CL is further converted into carlactonoic acid (CLA) by
cytochromeO

carlactonoic acid
（CLA）

intermediate molecule called carlactone (CL). In a model plant,
a

O

A

B

Me

C

O

A
D

4-deoxyorobanchol(4DO)

canonical-SL＝ABCD 4-ring

O

O

O

D

O

methylcarlactonoate（MeCLA）

non-canonical SL＝lacks B or C ring

Fig. 1, The outline of the biosynthetic pathway forinteract with AtD14, suggesting that the methyl esterification step is canonical and non-canonical SLs.

critical to converting a biologically inactive precursor to a bioactive hormone molecule. Conventional SL
molecules have the tricyclic lactone ring part (ABC-ring) that is connected to another butanolide lactone part(D-ring) via an enol ether bridge. However, CL derivatives lack BC ring system and possess only the A and D
rings. After the discovery of CL derivatives, structurally similar molecules have been isolated from various
plant species. Currently, these new types of SL molecules are classified to be 'non-canonical' SLs, whereas theconventional SLs are called 'canonical' SL (Fig. 1). Although, these new types of SL molecules have been
identified, the functional difference between canonical and non-canonical SLs are not fully understood. In thiscollaborative project with Prof. Shinjiro Yamaguchi in ICR, Kyoto University, we planned to clarify the
biological role of non-canonical SL by focusing on carlactonoic acid methyltransferase (CLAMT), which is
the key enzyme to produce non-canonical SLs (Fig. 1).
【Results】To understand the functional difference between canonical and non-canonical SLs, we chose
tomato as a plant material in which both of these two types of SLs are biosynthesized from a common
intermediate, CLA. We found a CLAMT candidate gene in the tomato genome (SlCLAMT) and attempted toobtain the clamt knockout mutant using CRISPR-CAS9 method. We have successfully obtained several mutant
lines in all of which some nucleotides are inserted or deleted in the coding region of the SlCLAMT gene. We
grew these slclamt mutants and found that the growth of the axillary buds in slclamt mutant is activatedcompared with that in the WT plant. We compared the phenotype of the slclamt mutant with another SL
biosynthetic mutant, slccd8. As a result, the branching phenotype of slccd8 was much more severe comparedwith that of slclamt. These results strongly suggest that the CLAMT pathway products have an important rolein shoot branching inhibition in tomato.

－120－

2022-121
Preparation of multi-stimuli-responsive polymer via controlled radical
polymerization
Shinichi Yusa

University of Hyogo

Introduction: A lower critical solution temperature (LCST) type polymer can dissolve in water
below the LCST, however it cannot dissolve in water above the LCST. In this study, diblock
copolymers (E95Nn) composed of poly(di(ethylene glycol) ethyl ether acrylate) (PeDEGA, E) andpoly(N-isopropylacrylamide) (PNIPAM, N)
were prepared via organotellurium-mediatedradical polymerization (TERP). E95Nncomposed of PeDEGA (LCSTA) and
PNIPAM (LCSTB) shows a two-stage LCST(LCSTA < LCSTB). It is expected that E95Nn
can be applied for for drug delivery (DDS)(Fig 1). Hydrophobic drugs can be Fig. 1 Conceptual diagram of dual temperature-responsive
encapsulated in the PeDEGA core of polymer diblock copolymers in DDS.
micelles which are formed at LCSTA <temperature (T) < LCSTB, and have good retention in blood.
When drug-encapsulated micelles are introduced into blood,
the micelles accumulate in the tumor due to the EPR effect.
Furthermore, when the temperature of the affected area islocally heated above the LCSTB, the PNIPAM shells becomehydrophobic to aggregate at the heated area. Furthermore, it Scheme 1 Chemical structures of E95Nn.
is expected that endocytosis of the polymer micelles is
accelerated due to the hydrophobic interactions. After the
micelles are taken into the cells, cooling the affected area
below the LCSTA causes the micelles to dissociate inside thecells, achieving controlled release of the drug.
Results and discussion: The %T values of E95Nn PBS
solutions were measured as a function of the temperature (Fig.
2). All polymers were dissolved below 15 °C with unimer
state. Core-shell polymeric micelles with the PeDEGA blockcore and the PNIPAM shells were formed at 15–29 °C. Above
32 °C the hydrophobic PNIPAM shell chains aggregatedbetween the polymer micelles and the %T was further
decreased. Unimer state with hydrodynamic radius (Rh) of
4.08 nm can be observed at 10 °C with DLS. At 25 °C polymer
micelles with Rh of 38.6 nm were observed. SAXS and TEM
showed that the micelles formed at 25 °C.

Fig. 2 %T of E95N67 (◇), E95N298 (〇),and E95N339 (□) aqueous solutions as afunction of temperature. Inserts are TEM
observations for E95N67 at 25 and 50 °C.

Conclusions: E95Nn were prepared via TERP. E95Nn were unimer state below LCSTA, formed
spherical micelles at LCSTA ≤ T ≤ LCSTB, and aggregated micelles above LCSTB. Fluorescence
experiments showed that hydrophobic domains were formed above LCSTA in PBS.

－121－

2022-122
積層 CNT ターゲットへの高強度レーザー照射による高圧ガス生成に関する実験研究松井隆太郎 京都大学

研究背景と目的：集光強度が 1018-19 W/cm2 のフェムト秒高強度レーザーを物質に照射することで生成する高エネルギー密度プラズマは、小型の粒子線癌治療装置の開発をはじめとした医療・産業・学術への幅広い応用が期待されている。レーザーの標的には通常、炭素化合物等の固体薄膜が用いられているが、その場合に生成するプラズマはパルス幅と集光径で決まる時空間領域に局在する非定常状態になる。一方、我々は先行シミュレーション研究により、波長程度（サブm）の微細構造を付与した物質（ロッド）を標的とすることで、プラズマ中に準定常状態が導入可能であること、プラズマ温度が制御可能であることを見いだしている[1]。これに対して、nm オーダのミクロな構造物の集合体であり、ロッド径を極限まで下げた媒質と位置付けられる炭素ナノチューブ（CNT の質量密度は黒鉛の 20%）は、レーザー照射により、ミクロな構造に起因する指向性を持つ相対論電子が生成されることから、癌治療への利用可能性が指摘されてる[2]。本研究では、医療応用をはじめとするプラズマの新機能の創出を目指して、CNT に高強度レーザーを照射する実験を行い、レーザーとの相互作用特性と発生する高エネルギー電子の空間分布を調べた。
実験方法：我々は、本学エネルギー理工学研究所（松田一成教授）から提供された積層 CNT ターゲット（図 1(a)参照）を用いて、これに京大学化研の T6
レーザーを照射する実験を実施した。具体的には、厚さ 500 m のシリコン基板上に作製された高さ 300
m の積層 CNT に対して、パルス幅および集光径が図 1 (a)レーザー照射実験で使用した積層 CNT ター
ゲット（SEM 画像）。(b)レーザー照射配位。上面・側面の２方向に ESM を設置。

40 fs と 10 m（FWHM）で集光強度が 5×1018 W/cm2 の高強度レーザーを CNT の高さ方向に対して 22.5°で照射した。プラズマの電子温度を計測するため、CNT の側面（22.5°）と上面（90°）に、同一の性能を有する電子スペクトルメータを設置した（図 1(b)参照）。
結果と考察：CNT の側面方向で得られた電子温度は、使用したレーザー集光強度から見積もられる理論
値（242 keV）よりも高い値が得られた。また、正面方向と比較して、側面方向の電子温度は 1.5 倍程度大きくなった。同一のレーザー照射条件において、表面が均一の平坦構造であるシリコン基板を用いた場合、電子温度は側面・正面方向でほぼ等しかったことから、CNT への高強度レーザー照射で生成するプラズ
マの電子温度は、（正面方向からのレーザー照射にもかかわらず）異方性を持つことが明らかとなった。また、CNT の側面方向の電子エネルギースペクトルには、500 keV 付近の領域に特徴的な平坦構造が現出することを見いだした。今後、CNT 中での航跡場の励起など、この異方性の起源とともに、それを促進して方向性を持った高エネルギーの電子ビームとして取り出すなどの可能性を追求する。
成果報告：松井隆太郎，林 直仁，石原聖也，升野振一郎，井上峻介，橋田昌樹，時田茂樹，阪部周二，岸本泰明,レーザー学会学術講演会第 43 回年次大会．2023 年 1 月 20 日，名古屋。
参考文献：[1] R. Matsui, Y. Kishimoto et al.，International Conference on High Energy Density Sciences
2022，April 21st, 2022，Yokohama. [2] Dante Roa et al., Photonics 9, 403 (2022).
－122－2022-123
高強度レーザーと構造性媒質の相互作用による高エネルギー密度
プラズマの生成・保持に関する実験研究
岸本泰明

京都大学

【計画全体の目的】集光強度が I~1018-20 W/cm2 の高強度レーザーをサブm オーダの微細構造を有する
物質（構造性ターゲット）に照射することにより高エネルギー密度状態のプラズマが生成するとともに、その過程において現出するプラズマの自己組織化機能や構造形成機能を制御することにより、kT オーダの準定常
強磁場の生成やそれによる生成プラズマの慣性時間を超えた保持（閉じ込め）を実現できる可能性が提案
者等のシミュレーション研究により示されている[1]。本研究は、自然界にないナノメートルレベルの人工的な物質と光との相互作用を巧みに制御することにより新機能を創出するメタマテリアル概念に、レーザー照射によって生成されるプラズマの要素を取り入れた非線形領域のメタマテリアル科学と位置付けられる。これが実現すれば、中性子を出さない究極の核融合である陽子・ホウ素（P-B）反応など、これまでにない新たな応用が期待される。本研究では、この仮説を検証することを目的に、ナノ工学と材料工学を用いて構造性ター
ゲットを作製するとともに、これに京大化研 T6 レーザーを照射する実験を行うことにより本仮説を検証する。
【2022 年度の成果】2022 年度は、2021 年度の成果を基礎に、1)高強度磁場生成用の構造性ターゲット作
製、および、2)T6 レーザー照射・計測系の構築を進めるとともに、3)作製した構造性ターゲットに照射強度が最大 2×1019 W/cm2 レベルのレーザー照射実験を行う環境を構築した。以下に詳細を記述する。
1) サブm サイズの構造性ターゲットの作製:

電子線リソグラフィーとプラズマエッチングを含む半導体技術を併用することにより、レーザー
照射時に目的に沿った多様な機能を有するサブm オーダーの微細構造を有する構造性ターゲット作製を可能にする技術の向上・獲得を図った。図１は、照射レーザーを１00m オーダのリング構造に捕獲・電流路を形成することにより高強度の準定常磁場を生成するメタマテリアル様のターゲットの一例を示す。周辺には、レーザーの集光と強度調整用の多様なマーキングを配置している。リング中心には、レーザー照射時

図 1. 2022 年度に開発に成功した高強度磁場生成用の構造性ターゲットの例。

に特定な密度のプラズマを発生するロッド集合体を配置している。
2) T6 レーザー照射・計測系の構築： 多様な構造を有するターゲットに集光強度が 1017-20 W/cm2 レベルの高強度レーザーを複数の方向（上面・側面方向など）から照射可能な自由度の高い実験系を構築した。
図 2 は、生成された高エネルギー密度プラズマのエネルギー分布を２方向から同時計測するための電子エネルギースペクトルメータ（ESM）を設置した様子を示す。今後、密度計測および磁場計測系の構築を目指す。
3) レーザー照射実験の実施：1)および 2)で作製・構築したシステムを用いたレーザー照射実験を開始した。実験では、平面ターゲットと異なった空間充填率を有するロッド集合体の照射実験を実施、充填率の違いによる電子エネルギー分布の相違など、微細構造に起因する特性

図 2．2022 年度に設置した 2 台 ESM を有する構造性ターゲットとレーザーの相互作用実験の配位。左は図 1 で示したレーザーを閉じ込める円形リングを付与したロッド集合体を示す。

の違いなどを示す結果を取得し、関連学会等で報告を行った。
参考文献：[1]Y. Kishimoto, et al., 10th IFSA 2017, St Malo,France September 11-15 (2017)[2] 岸本泰明，松井隆太郎：「高強度レーザーと構造性媒質との相互作用による高エネルギー密度プラズマの生成と保持：背景理論と実験検証に向けた取り組み」レーザー学会第 43 回年次大会，2023 年 1 月 20 日

－123－

2022-124（国際）Determine the three-dimensional structure of 13C labeled α-synuclein(61-95)
in the Langmuir-Blodgett film and supported phospholipid bilayer by
MAIRS2Chengshan Wang

Middle Tennessee State University

A. Objectives:
1.

13

C labeled α-syn(61-95) containing residues 61-95 of α-synuclein will be synthesized andpurified.
2. Screen the conformation and orientation of specific amino acid residue of α-syn(61-95) in
Langmuir-Blodgett film.
3. Screen the conformation and orientation of specific amino acid residue of α-syn(61-95) insupported phospholipids bilayers.
B. Experimental methods:
Peptide of 13C labeled α-syn(61－95) 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 (π−A) isothermof α-syn(61－95) were conducted in a A Kibron µtrough. The Langmuir-Blodgett (LB) filmsof α-syn(61－95) were made by transferring the α-syn(61－95) 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 α-syn(61－95) were measured by a
JASCO

J-810

spectropolarimeter.

p-Polarized

Multiple-Angle

Incidence

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 α-syn(61－95) 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 α-syn(61－95) was synthesized and purified. Figure 1A shows the π−A isothermof the 13C labeled α-syn(61－95) and the isotherm is very similar to that of the unlabeled
α-syn(61－95). 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 α-syn(61－95)
is also similar to that of unlabeled peptide as shown in Figure 1B. For the LB films of the 13Clabeled α-syn(61－95), two negative peaks at 222 and 208 nm in addition to one positive peak at
192 nm are detected. Therefore, the 13C labeled α-syn(61－95) also transforms to α-helix at the－124－interface. On the other hand, pMAIRS was used to determine the tilted angle of the axis of
α-syn(61－95) 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 α-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
α-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 α-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 α-helix is equal to that of the 13C amide I
transition moment, the tilt angle of the axis of α-helix at 93G is also ~0º.
0.0009

(A)

10

1625
1655

4

Absorbance20

CD signal, mdeg

Surface pressure, mN/m

300.0006(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

Wavenumber, cm-1

1500

Figure 1. (A) Surface pressure-area isotherm of the 13C labeled α-syn(61－95) on purewater, (B) CD spectra of the LB films of the 13C labeled α-syn(61－95) on quartz
slides. (C) p-MAIRS results of the LB monolayer of the 13C labeled α-syn(61－95)
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 anovel method for membrane proteins even in monolayer structure with high resolution by pMAIRS,
which will be a supplement to X-ray crystallography and NMR.
E. Publication.
One paper about Figure 1 was published by Wang C., Zhou Y., Ewuola C., Akinleye T.,
Hasegawa T., Leblanc R. M. in Analytical Sciences, 2022, 38, 935-940.
－125－2022-125（国際）The 16th International Workshop for East Asian Young Rheologists
Tadashi Inoue

Osaka University【Purpose of project】The ICR budget was used to organize the 16th International Workshop on Young
Rheologists in East Asia (IWEAYR-16). The purpose of this workshop is to promote international
exchange among young faculty and graduate students in cooperation with researchers from various
countries in East Asia in several research fields, such as polymer science and materials science.
IWEAYR allows participants to present their research results and discuss and exchange research ideas
in a friendly atmosphere. The workshop will deepen our research activity and form the basis for futurecooperation. This year, IWEAYR-16 was held in Udon Thani, Thailand. Because registration took place
before November 2022, there were no participants from China, where travel was prohibited due to
Covid-19, but there were still more than 100 participants. Many undergraduate and graduate students
participated, and the mission of strengthening future collaboration was not compromised in the slightest
despite three years break. The budget was effectively utilized to support the participation of as many
Japanese researchers as possible.
【Place and schedule of workshop】IWEAYR - 16 was held from February 18 - 21, 2023, at Centra
Hotel & Convention Centre Udon Thani and Montatip Hall Expo & Convention Centre, Udon Thani,chaired by Doctor Adisak Takhulee of Udon Thani Rajabhat University, Thailand..
【 Purpose of the workshop 】 From the beginning, the purpose of this workshop is to promoteinternational exchange and collaboration among young faculties and graduate students who will be theleading researchers in the field of rheology and material science in the near future and, therefore, toprovide a place for research presentation and discussion, and to revitalize related fields. At the sametime, 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 was 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 (January2019),and Changchun (January 2020) (in a circulating order of Korea, Japan, China, and Thailand).
There have been some changes in the organization of the workshop due to various circumstances in the
hosting countries; every IWEAYR has served as a place for faculties and graduate students to engage ininternational exchange and collaboration.
【Participants】Doctor Takhulee, the organizer, was an alumnus of IWEAYR. He understands the
purpose of IWEAYR very well, and therefore the conference was conducted with meticulous attention
to detail. The number of participants in this IWEAYR-16 was 26(31) professors and 84 (91) students,
which was the average level in recent years, although China could not attend. (Numbers in () are thenumbers of participants IWEAYR-15). The breakdown by country was Japan 35 (10+25), Korea
71(12+59), China 0, and Thailand (4+9). The main participants were:
Kyung Hyun Ahn, Professor,
Seoul National University,
Korea,
Jaewook Nam, Professor,
Seoul National University,
Korea,
Kyu Hyun, Professor,
Pusan National University,
Korea,－126－

Youngdon Kwon, Professor,
Visit Vao-soongnern, Asso. Prof.

Sungkyunkwan University,
Korea,
Udon Thani Rajabhat University Thailand

Exkarach Deenang, Asso. Prof.
Hiroshi Watanabe, Professor,
Takashi Taniguchi, Asso. Prof.,
Hiroshi Suzuki Professor,
Ruri Hidema, Associate Prof.,

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

Opening Seremony

Thailand
Japan
Japan
Japan
Japan

Photo of Banquet【Overview of IWEAYR-16】Total number of submitted papers was 29(Oral) + 53(Poster). On the firstday, the session started with one invited talk. After that, long oral presentations (12) were given by
mostly Ph.D. students. After lunch, the short oral presentations (53) by master course students were
presented before the poster presentations. On the second day, long oral presentations (14) were given
by Ph.D. students. Then, a group excursion was organized. The four best presentation awards of Ph.D.
students were chosen by the participant's vote.
At this conference, there were many studies on battery slurry for manufacturing Li-ion batteries,
particularly by Korean groups whose major is chemical engineering. The studies on new materials suchas nano cellulose as well. In addition, there was basic research on the analysis of various rheologicalproperties and hierarchical structures of polymers. Some issues, such as theory, simulation, and flow
control of soft matter, were also presented.
The author has attended IWEAYR in Thailand four times. The host city, Udon, locates near the borderwith Laos. He wondered what kind of place, but the venue, Centra Hotel & Convention Centre Udon
Thani, was a very nice and modern hotel with a large shopping mall next to it. The workshop wassponsored by Thai universities and Thai companies, and the author felt the great development of theThai economy and, at the same time, the deterioration of Japan due to the weak yen. The immigration
procedures were also simplified at the time of the event, and the author felt that things were gradually
returning to the way they were before the COVID-19 pandemic.
【Summary】 All students enjoyed the workshop, and the author believes that this experience will help
maintain a network of young rheologists in East Asia. Also, Covid-19 feels us of the importance ofcontinuing such a workshop to keep the international relationship. In conclusion, IWEAYR-16
successfully achieved its purpose. Finally, the author should note that the next IWEAYR-17 will be heldin Pusan, Korea, in the wintertime.

－127－2022-126（国際）Tackling the Electronic Instability of Charge-Density Waves byElectron Energy-Loss Spectroscopy
Ming-Wen Chu National Taiwan University
This project (2022-126) aims at resolving the electron-phonon coupling in the chargedensity-wave (CDW) state of CuTe by electron energy-loss spectroscopy (EELS), in
collaboration with Prof. Hiroki Kurata at ICR. CuTe stands for a prototypical CDW, with
the quasi-one-dimensional crystal structure and iconic Fermi surface nesting bothcharacteristic of the Peierls-transition classics of CDWs. Due to the COVID-19 pandemic,
it has, however, been unlikely for my group to conduct the desired high-resolution EELS
study in Prof. Kurata’s laboratory. Nonetheless, we were still committed to the EELS
investigation of CuTe using in-house EELS with a momentum resolution of ~0.09 Å-1and energy resolution of ~0.54 eV, which are sufficient for tackling the plasmon
excitations in CuTe though insufficient for the desired electron-phonon coupling with atypical energy scale below 100 meV. As a result, we turned our interest to the subject ofplasmon dispersions in CDWs, whereby the impact of the static electronic order of CDWs
on the dynamical charge oscillation of plasmons remains a largely unsettled problem.
Here below, we show a plasmon dispersion map acquired in my laboratory in National
Taiwan University using the EELS with a compromised capability. This map serves as
the important first step toward our in-depth experiments to come in ICR in 2023 and has
manifested the quadratic dispersion as a function of momentum transfer (q) in agreementwith the free-electron gas behavior. The intriguing correlation with the CDW order of
CuTe is to be resolved shortly together with Profs. Kurata and Haruta in ICR.

Figure. The plasmon dispersion of CuTe along the CDW-order direction of X.

－128－

2022-127（国際）Micro- and Nano-structural Characterization by
Advanced Transmission Electron Microscopy of Novel Functional Materials
Torranin Chairuangsri

Chiang Mai University

Our research group from Thailand visited ICR onsite in collaboration with Prof. Hiroki KURATA, Assoc. Prof. Mitsutaka
HARUTA, Dr. Atsushi YAMAGUCHI and Mr. Tsutomu KIYOMURA, for characterizing nano-structure of novel functional
materials by advanced transmission electron microscopy. The results can be summarized as follows.
I. Novel SiO2/rGO/Polymer and FeOx/C composites from biomass as Anode in LIBs
Polyaniline-coated nano-silica@reduced graphene oxide (PANISiO2@rGO) composites were fabricated. STEM revealed that SiO2
nanoparticles were homogeneously loaded on graphene sheets and the
PANI fibrous network uniformly covers the SiO 2@rGO composites.
STEM also showed structural stability of the composites after cycling
without aggregation of the SiO2 nanoparticles. However, some SiO2
nanoparticles transformed to be Si nanoparticles after cycling. For
FeOx/C composites from biomass, HRTEM depicts the presence ofgraphitic domains scattered in amorphous structure. EELS fromcarbon revealed two peaks at 287 eV and 290-300 eV, suggesting an
amorphous carbon structure.

II. Annealed 28wt.%Cr-1wt.%(Mo/W) Cast Irons
Carbides in annealed 28 wt.% Cr-2.6 wt.% C high chromium cast irons
with the addition of Mo or W have been characterized by STEM and
EELS was also used to identify M7C3 and M23C6 carbides in theseirons. Fine structures in C K-edge spectra were found to be useful for
distinguishing between M7C3 and M23C6 carbides. The C K-edge of
M23C6 incorporates a shoulder-like feature at approximately 287 eV,
the second peak from M7C3 in the Mo1 and W1 irons has lower
intensity than that in the R iron, and the peak height ratio of the firstand second peaks from M23C6 in the Mo1 and W1 irons is lower thanthat in the R iron.

Fig. 1 (a) TEM image of the carbon matrix in FeOx/C composites, (b)The examples of graphitic domains within carbon region, (c) EELS
spectrum of the carbon matrix, and (d) Raman spectra from FeOx/Ccomposites as compared to those from raw materials.

Fig. 2 STEM-ADF image shows the microstructure of the R iron after annealing (a) and C K-edge spectra from (b) eutectic M7C3 and (c) coarse M23C6 in the irons.

Publications:
1. Rice husks-derived nano-SiO2 assembled on reduced graphene oxide distributed on conductive flexible polyaniline
frameworks towards high-performance lithium-ion batteries (RSC Advances, 12(23) (2022), 14621-14630).
2. Recycling water hyacinth stem waste for cost-effective production of carbon/FeO x nanocomposite anodes for sustainable
fast-charging lithium-ion batteries (submitted to Journal of Material Science: Materials in Electronics).
3. Electron microscopy of carbides in annealed 28wt.%Cr-1wt.%(Mo/W) cast irons (submitted to Materials Characterization).

－129－2022-128（国際）High-pressure synthesis of transition metal oxides with novel physicalproperties
Kunlang Ji 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, a unique high-pressure multianvil apparatus which reaches up
to 20 GPa and 2273 K is available to use. 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 finishing the 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 throughemails. The paper has been finally published on Angewandte Chemie International
Edition in 2022.
Experimental results: Co2InSbO6 recovered from high pressure has a new, ordered-R32
A2BCO6 variant of the corundum structure. Co2InSbO6 is also remarkable for showing an
unprecedented sequence of two cation redistributions, to (Co0.5In0.5)2CoSbO6 and then
Co2InSbO6 variants of the ordered-LiNbO3 A2BCO6 structure on heating. The cation
distributions change magnetic properties as the final ordered-LiNbO3 product has a sharp
ferrimagnetic transition at 65 K whereas the initial ordered-R32 material has a broader
feature indicative of short range spin ordering.
Discussion: The selective site exchange only between Co2+ and In3+ at different
temperatures results from the small size and charge 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, E. Solana-Madruga, M. A. Patino, Y. Shimakawa* and J. P. Attfield*,Angew. Chem. Int. Ed., 61, e202203062 (2022)－130－2022-129（国際）Synthesis and Characterization ofNovel Group 16 Element Compounds
Mao Minoura Rikkyo University
In general, germanium-chalcogen double bond compounds are known to behighly reactive and the double bond compounds dimerize easily. By utilizing bulky
protecting groups, germanium-chalcogen double bond compounds can be synthesized
and isolated; Tokitoh et al. reported the synthesis of germanium-chalcogen double bondcompounds with large aromatic Tbt groups. However, no stable germanium-chalcogendouble bond compounds have been reported for alkyl substituted compounds due to thedifficulty of 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 our experiences, compounds with bulky substituents,
such as Trp*, have low solubility and poor crystallinity. In fact, the synthetic studies of
Trp*-substituted germanium compounds initially yielded only crystals that were too small
to be analyzed structurally by X-ray diffraction. To improve the solubility andcrystallinity of Trp* compounds, alkyl chains were installed at the bridgehead position.
In this paper, we report the synthesis of Trp* groups having alkyl chains (R= Pr, Bu, Hex,
Oct), RTrp*, and applied them to the synthesis of dialkylgermylenes (RTrp*2Ge:) in the
expectation of improving those crystallinities by intermolecular interactions with thepacking forces in the solid states. The isolated RTrp*2Ge: showed better solubility andcrystallinity than the corresponding Trp*2Ge:.
Especially, HexTrp*2Ge: and HexTrp*2Ge=S
showed characteristic change in the packing
structure to form suitable single crystals for X-ray
analysis.
We thank Professors Norihiro Tokitoh,
Yoshiyuki Mizuhata, and Mariko Yukimoto for theirkind discussions.

－131－2022-130（国際）Analyzing chemical properties and origins of dissolved organic
matter in lakes and soils by FT-ICR-MS
Morimaru Kida

Kobe University

Objectives: Dissolved organic matter (DOM) represents one of the largest actively
cycled carbon pools on earth. The molecular composition of DOM plays a major rolein its long-term persistence in aquatic systems, yet the extreme complexity andheterogeneity of DOM have so far hindered its full characterization at the molecularlevel. The high resolution and mass accuracy of FT-ICR MS allow the assignment ofmolecular formulae to tens of thousands of compounds in DOM. We first aimed toestablish the very first platform to enable a high-quality FT-ICR-MS analysis of
DOM. Then, we aimed to elucidate the factors that influence the molecularcomposition of various DOM in lakes and soils.
Materials and methods: We first optimized the conditions for FT-ICR-MS
measurement of DOM using an international reference DOM sample and electrosprayionization (ESI). Because FT-ICR MS at ICR was unfortunately out of order during
the duration of this project, FT-ICR MS at RISH was used instead. After the optimal
condition was established, DOM samples collected from lakes and diverse soils wereanalyzed. Molecular formulae of detected masses were determined using an online
mass spectra processing pipeline, ICBM-OCEAN. Multivariate analysis was
conducted to identify environmental and edaphological factors that determine themolecular composition.
Results and discussion: A significant portion of the project duration was dedicatedto the optimization of the measurement conditions. This was further complicated by
the difference in machine conditions between ICR and RISH FT-ICR-MS. We could
eventually, however, start analyzing samples under the optimized conditions, and theanalysis is still ongoing.
Outcome reports: No reports yet published.

－132－2022-131
Preparation of high-efficiency spin-injection materials using optimization ofmagnetism and crystal structure
Masaaki Tanaka

Nagoya Institute of Technology

The spin-filtering effect, where the spin-polarized current is generated using electron tunnelingthrough a ferromagnetic insulator, is one of the candidates for the spin injection method. Independently, it is
known that magnetic insulator cobalt ferrite (CFO) films grown epitaxially on MgO (001) substrates havelarge perpendicular magnetic anisotropy (PMA) which is induced by the in-plane tensile strain. In this study,
the spin-filtering effect of insulative Fe-rich CFO (I-CFO) films with PMA grown on conductive Fe-rich CFO(C-CFO) films was investigated.
The multilayered films of C-CFO(20 nm)/I-CFO(3.0 nm)/MgO(1.0 nm)/Co(1.0nm)/{Tb(0.45nm)/Co(0.56 nm)}15/Co(2.0 nm) were prepared on MgO (001) substrates with I-CFO (20 nm) buffer layers
using the pulsed laser deposition (PLD) and electron beam deposition technique. The systematic change
between the I-CFO and C-CFO films was performed by the change of the source materials and gas conditions
during the PLD. The magnetization measurements clarified that the C-CFO/I-CFO layers have PMA. The
magnetic tunnel junctions (MTJs) with a junction diameter of several micrometers were fabricated using
photolithography and dry etching by an ion-milling method. This microfabrication was carried out at ICR,
Kyoto University. The 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. The tunnel magnetoresistance (TMR) ratioof －20 % was obtained at 100 K at the bias voltage of 100 mV. The estimated spin injection efficiency was－28%. It is found that the bias-voltage dependence of the TMR ratio can be interpreted by the FowlerNordheim tunneling mechanism, which means that the spin-polarized current is generated by the spin-filtering
effect of the ferromagnetic insulator I-CFO layers. The I-CFO spin-filtering layer is, therefore, applicable as aspin injection source for spintronics devices when perpendicularly spin-polarized electronic currents are
required.

成果報告
M. Tanaka, M. Furuta, T. Ichikawa, M. Morishita, Y.-M. Hung, S. Honda, T. Ono, and K. Mibu, “Generationof spin-polarized electronic currents using perpendicularly magnetized cobalt-ferrite spin-filtering barriers
grown on spinel-type-conductive layers”, Applied Physics Letters, 122, 042401 (2023).

－133－2022-132
Development of a highly efficient CsPbBr3 scintillator
Hikaru Saito Kyushu University
It has been reported that CsPbBr3 nanoparticles embedded in Cs4PbBr6 matrix(CsPbBr3/Cs4PbBr6 nanocomposite) exhibit high photoluminescence (PL) quantum yield [1]. The
size distribution and the density of CsPbBr3 nanoparticles in Cs4PbBr6 matrix have not been
analyzed by electron microscopy probably because this nanocomposite is very sensitive to electron
beams. Recently we have found sub-nanosecond cathodoluminescence (CL) decay from
CsPbBr3/Cs4PbBr6 nanocomposite by using Hanbury Brown-Twiss interferometry [2], which isapplicable to high performance scintillator for fast electron beams. To elucidate the CL mechanism,
we have attempted 4D-STEM and electron energy-loss spectroscopy (EELS) to analyze thenanostructure of CsPbBr3/Cs4PbBr6 nanocomposite.
Fig. 1 shows 4D-STEM obtained from CsPbBr3/Cs4PbBr6
nanocomposite at a probe current of 2.3 pA and an acceleration
voltage of 300 kV, indicating that cubic CsPbBr3 crystals witha size of about 10 nm were contained in the Cs4PbBr6 matrix.
4D-STEM can only detect CsPbBr3 nanoparticles satisfying
diffraction conditions, meaning that it is not appropriate forparticle density measurements. Therefore, we applied STEMEELS for a CsPbBr3/Cs4PbBr6 nanocomposite thin film. Fig. 2
shows the results obtained at a probe current of 1.6 pA and an Fig. 1 (a) ADF-STEM image ofenergy resolution of 50 meV and an acceleration voltage of 60 CsPbBr3/Cs4PbBr6 nanocomposite and (b)diffraction pattern from the rectangular

kV. EELS spectrum at each measurement point was area in (a). (c) Virtual DF image by using
intensity of the diffraction spot indicated bydecomposed into two component spectra corresponding to the rectangular area shown in (c).
CsPbBr3 (Fig. 2b) and Cs4PbBr6 (Fig. 2c), which clearly
indicates that high density CsPbBr3 nanoparticles with sizes ofabout 10-20 nm are embedded in the Cs4PbBr6 matrix.

This

information would be crucial to derive a model for the foundsub-nanosecond CL, leading to development of highperformance optical nanomaterials including fast scintillators.
[1] Ya-Meng Chen, et al., ACS Appl. Mater. Interfaces, 10,15905 (2018).

Fig. 2 (a) ADF-STEM image of a[2] Sotatsu Yanagimoto, et al., Phys. Rev. B, 103, 205418 CsPbBr3/Cs4PbBr6 nanocomposite thinfilm and (b) CsPbBr3 map derived by
EELS mapping. (c,d) EELS spectra
corresponding to Cs4PbBr6 and CsPbBr3
extracted from the areas indicated in (b).

(2021).

－134－

2022-133
核融合プラズマ対向材料中の水素・ヘリウム挙動の高精度測定宮本光貴 島根大学

タングステンは将来の核融合炉ダイバータ材料としての利用が予定されている．本研究では，タングステン中のヘリウムバブルが水素保持に及ぼす影響について，モノクロメー
タ搭載低加速原子分解能分析電子顕微鏡(STEM-EELS, 京都大学)を用いて直接捉えることを目的とした．
島根大学のイオン銃直結型透過型電子顕微鏡を用いて薄膜化したタングステン試料に比較的大きなヘリウムバブル(d ~ 10 nm)を導入するために，室温で 3 keV-He+を照射後，1473
K でアニールした．その後，室温で 3 keV-D2+を 1×1021 /m2 まで照射した試料を STEM-EELS
により，室温から 100 K 刻みの等時焼鈍を行い，各温度における重水素，およびヘリウムの存在位置を高い空間分解能で定量的に評価した．
図 にヘリウム予照射後，重水素照射したタングステンを昇温した際の各温度における(a)高角度散乱円環暗視野像(HAADF
像)，および(b)重水素，(c)ヘリウムの濃度分布像を示す．HAADF 像中の黒いコントラ
ストはヘリウム予照射に起因したヘリウ
ムバブルを示す．重水素マッピングからバ
ブル内に明瞭に高濃度の重水素が存在することが明らかとなり，重水素保持量の増加に寄与したと考えられた．バブル内の重水素濃度は温度の上昇に伴い低下し，473K
程度で放出されることが分かった．一方，バブル内のヘリウム濃度は温度の上昇に伴い上昇した. これはバブル外に多くのヘリウムが捕獲されており，高温下では，より安定な捕捉サイトとなるバブル内に蓄積していくことを示している．以上の結果より，重水素のほとんどはバブル内に，ヘリウムはバブル外にも捕捉され，イオン種によって捕捉挙動が異なることが示された．

図 ヘリウム予照射後，重水素照射したタン
グステンの昇温下における (a)高角度
散乱円環暗視野像と(b)重水素および(c)ヘリウムの濃度分布像．

なお，本研究は倉田博基教授，治田充貴准教授（京都大学化研），佐野航平，澤江伴弥（島根大学）らとの共同研究として実施されたものである．また，本成果については，2023
年 5 月に開催の国際会議 PFMC-19 にて報告予定である．
－135－

2022-134
Synthesis and Structural Characterization of
Lewis Base Adducts of Tetrylenes
Tsukasa Matsuo Kindai University
In this collaborative research, we examined the synthesis and structures ofLewis base adducts of tetrylenes incorporating the fused-ring bulky Rind groups(Rind = 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl).
The bulky Eind-based dibromodigermene, (Eind)BrGe=GeBr(Eind) (1), wasprepared by the reaction of (Eind)Li with GeCl2ꞏdioxane (Scheme 1). The
digermene 1 exists as the monomeric germylene, (Eind)BrGe:, in solution. The
following reaction with N-heterocyclic carbene (NHC = 1,3,4,5-tetramethylimidazol-2-yliden) produced the bis-NHC adduct of the formal germyliumylidene
cation, [(Eind)(NHC)2Ge:][Br] (2). The structure of 2 was confirmed by X-ray
crystallography (Figure 1).

Figure 1. Eind group and molecular structure of 2.

Scheme 1. Synthesis of 1 and 2.

－136－2022-135
Synthesis and structures of cationic aromatics
bearing chalconenopyrylium units
Noriyoshi Nagahora

Fukuoka University

Introduction
Thio- and selenopyrylium salts exhibit a unique electronic structure, which renders these compounds
interesting potential building blocks for sulfur-/selenium-containing aromatic molecules. Recently,
thiopyrylium-containing molecules have received substantial attention due to their fascinating structures,
optoelectronic and physicochemical properties. In this work, we present studies on the synthesis of linearly
fused thio- or selenopyrylium compounds via Lewis- or Brønsted-acid-promoted intramolecular cyclizationof thio- or selenoethers.

Results and Discussion
In order to optimize the reaction conditions, we initially investigated the Lewis/Brønsted-acid-induced
cyclization of diarylthioether 1a. When the Lewis acid Sc(OTf)3 was used, the cyclization of 1a proceeded athigh temperature to quantitatively afford thiopyrylium trifluoromethanesulfonate 2a. We also discovered that
TfOH is the most effective Brønsted acid for the promotion of the cyclization, which affords 2a in quantitative
yield at room temperature within 1 h. The reactions still proceeded when several substituted diarylthioethers
1b-d were treated with TfOH at room temperature for 2 h. Next, we focused formation of selenopyrylium salts
promoted by a Brønsted acid. Even the corresponding selenoethers reacted with TfOH affording
selenopyrylium trifluoromethanesulfonates 3a-c in acceptable yields. This versatile cyclization thus not only
extends the scope of the synthetic methods of pyrylium-fused cationic framework but also that of material
chemistry using thio- or selenopyrylium molecules.

Publications
1. (a) Nagahora, N.; Tanaka, R.; Tada, T.; Yasuda, A.; Yamada, Y.; Shioji, K.; Okuma, K. Org. Lett. 2020,22, 6192–6196. (b) Nagahora, N.; Kitahara, K.; Mizuhata, Y.; Tokitoh, N.; Shioji, K.; Okuma, K. J. Org.
Chem. 2020, 85, 7748–7756. (c) Hirano, K.; Yasuda, A.; Sasamori, T.; Shioji, K. Okuma, K.; Nagahora, N.
Heterocycles 2021, 102, 451–464.
－137－

2022-136
Theoretical design of low-dimensional silicon material embedded in a flat
two-dimensional sheet and exploration for operating principles
Masae Takahashi Tohoku University【Objectives】Two-dimensional (2D) Dirac materials represent a special class of quantum matter hosting
linearly dispersing Dirac cones. The Dirac cone categorized into type-I shows tilted anisotropic linear
dispersions in all k directions, together with a point-like Fermi surface. We report here designing a siliconbased type-I Dirac material with planar configuration, based on the first-principles calculations. The flat
structure obtained in this study is essential for the air stability of silicon -electron conjugated systems.
【Computational Details】We performed structural and electronic calculations in the density functional theory
framework, as implemented in CASTEP code (ver. 2018 and 2019). The geometries were fully optimized forboth the cell parameters and atomic coordinates under the constraints of group symmetry of D2h. The
calculation of phonon dispersion was performed using the linear response theory. The phonon dispersions
throughout the Brillouin zone confirmed that obtained structure is dynamically stable because of the absenceof any imaginary frequencies.
【Results and Discussion】The band
structure calculation has revealed thatthe obtained 2D material with planar
configurationisatype-I

Diracsemimetal with linear dispersion in thevicinity of the Fermi energy and isregarded as a qualitatively new classof 2D material that hosts anisotropic
Dirac fermions (Fig. 1). The Fermi

Fig. 1. Electronic band structure and the projected DOS.

velocity in the -X’ direction is estimated to be 0.5 ×106 and 0.7 ×106 m s−1, which is 2 and 1.5 times smaller
than that of graphene. The Fermi velocity in the direction perpendicular to the -X’ line is much smaller (0.3×106 m s−1). The most remarkable difference in the band structure from graphene is that the van Hove
singularity is located much closer to the Fermi energy than in graphene: the energy interval is 0.3 eV, whilethat in graphene is 2 eV. This is due to the smaller energy gap at the point than that in graphene. It wasrecently reported that the Fermi-level shift by 0.5 eV in graphene is achieved by chemical doping, suggestingthat the Fermi-level shift by 0.3 eV by chemical doping is quite possible. The obtained 2D material is a siliconbased air-stable Dirac material with an anisotropic Dirac cone inducing the anisotropic carrier mobility, which
has a high potential for application to various novel silicon-based electronic devices.
【Publications】[1] M. Takahashi, S. Chen, H. Matsui, N. Morimoto, Y. Ikemoto, Sci. Rep. 2022, 12, 20393.
[2] M. Takahashi, WIRMS2022, October 6-9, 2022, Hiroshima and Hybrid Format, Japan (Invited talk).

－138－2．国際会議、シンポジウム・研究会報告

24th International Colloquium on Magnetic Films and Surfaces (ICMFS2022)
実施報告書
主催：ICMFS2022 実行委員会

共催：京都大学化学研究所

国際共同利用・共同研究拠点、京都大学化学研究所

トロニクス学術連携研究教育センター、東北大学
ンター、大阪大学基礎工学研究科

スピントロニクス学術連携研究教育セ

スピントロニクス学術連携研究教育センター、慶応義塾大学グローバルリサーチインスティテュート、公益財団法人
法人

スピン

新世代研究所、一般財団法人

市村清新技術財団、公益財団

沖縄観光コンベンションビューロー、International

Union of Pure and Applied Physics、IEEE Magnetics Society
日時：2022 年 7 月 10 日（日）～7 月 15 日（金）場

所：沖縄科学技術大学院大学
2022 年 7 月 10 日（日）～7 月 15 日（金）の 6 日間にわたり、24th International Colloquiumon

Magnetic

Films

and

Surfaces(ICMFS2022)( 学 会 ホ ー ム ペ ー ジ

https://icmfs2022.jp/index.html)を開催した。International Colloquium on Magnetic
Films and Surfaces（ICMFS）は、磁性薄膜と表面に関する研究発表、知識の交換、情報の提供等を行う国際会議であり、1964 年から数年おきに世界各地で開催されている歴史ある会議である。参加者は世界 20 カ国以上から 150～300 人程度である。本会議は 2021 年 7 月
11 日～2021 年 7 月 16 日に沖縄で開催する予定であったが、新型コロナウイルス感染症拡大防止の観点から開催を 2022 年に延期した。
第 24 回目となる今回は、京都大学化学研究所
化学研究所

国際共同利用・共同研究拠点、京都大学

スピントロニクス学術連携研究教育センター、東北大学

学術連携研究教育センター、大阪大学基礎工学研究科

スピントロニクス

スピントロニクス学術連携研究教育センター、慶応義塾大学グローバルリサーチインスティテュート、公益財団法人
新技術財団、公益財団法人

新世代研究所、一般財団法人

市村清

沖縄観光コンベンションビュー

ロー、International Union of Pure and Applied Physics、IEEE Magnetics Society の支援を受けた。
コロナ渦でのハイブリッド会議となったが、総勢 289 名の参加者のうち 215 名が現地参加であった。また海外からの参加者 116 名のうち現地参加者は 66 名に上った。この参加者数からも、研究者が対面の会議や議論を熱望している現状がうかがわれる。学生の参加も118 名（国内 76 名、海外 42 名）と学生参加費を 25000 円と格安とした効果があった。これも京都大学化学研究所国際共同利用・共同研究拠点をはじめとする各所の援助によるものである。若手育成は本会議の大きな目的の一つであり、十分な成果があったといえる。
本会議は従来 International Conference on Magnetism(ICM)のサテライト会議として開催されてきた。今回も上海開催が予定されていた ICM のサテライト会議となるはずであっ－139－

たが、コロナ渦により ICM 上海が中止され単独開催となった。
従来 ICM で行われていた IUPAP
Magnetism Award と IUPAP Young Scientist Prize の表彰式を ICMFS で行い、受賞者による
Plenary 講演と招待講演が行われた。
最後に、本コロキウムを開催するにあたりご支援をいただいた京都大学化学研究所国際共同利用・共同研究拠点に厚く御礼を申し上げる。
文責：小野

－140－

輝男

化学研究所国際共共拠点・分子材料化学セミナー

実施報告書

1. 日程

2022 年 8 月 5 日
2. 会議名化学研究所国際共共拠点・分子材料化学セミナー
3. 主催機関
京都大学化学研究所
4. その他

共催・協賛機関など（掲載が必要な場合のみ）

5. 世話人（化学研究所を代表する報告者、役職名も変更可＜例：プログラム委員長＞）

梶 弘典 (京都大学化学研究所)
6. 参加者数
20 名
7. 開催場所
京都大学宇治キャンパス 共同研究棟大セミナー室
8. 報告文新型コロナウイルスに関する国内外の往来が今年度から可能となったため、今回、テネシー大学のBin Hu 教授と名古屋大学の阿波賀邦夫教授をお招きし、京都大学化学研究所で講演を行って頂く機会を得た。Bin Hu 教授からは、Spin-orbital Coupling Effects in Organic Molecules and 2D-superlattice
Perovskites と題した講演をお願いし、最近特に注目を集めている、熱活性化遅延蛍光(TADF)、また、
二次元超格子ペロブスカイトに関し、スピン軌道相互作用という観点からご講演をいただいた。阿
波賀邦夫教授からは、Interdisciplinary Research on Solid-State Science and Electrochemistry of MolecularMaterials と題した講演をして頂いた。分子クラスター電池や金属有機構造体(MOF)電池に始まり、大型の研究費の取り方に至るまで、分野外の研究者にも極めてわかりやすい講演が行われ、会は成功裏に終了した。

－141－

Program－142－

第 6 回 MAIRS ワークショップ
主催：（公社）日本分光学会・赤外ラマン研究部会

共催：京都大学化学研究所共同利用・共同研究拠点

協

賛：日本化学会，応用物理学会，日本分析化学会，分子科学会

日 時：2022 年 11 月 18 日（金） 13:00～17:00
場 所：京都大学化学研究所・共同研究棟 大セミナー室，および Zoom 配信によるハイブリ
ッド形式
2016 年からシリーズ化して開催している，

ノ溝配列における赤外吸収の増強（島田

赤外分科会企画の部会イベントである“MAIRS ワークショップ”の第 6 回を，昨透・弘前大）
5.

金属酸化物上の脂肪族分子の pMAIRS

年に引き続いて対面とオンラインのハイブ測定を用いた吸着挙動追跡（細見拓郎・

リッド方式で実施した．一件当たりの講演に東大）

ゆとりを持たせるため，今年は講演件数を少なめに設定したが，例年以上に話題の分野に広がりを持たせることができた．参加者は，
対面に 19 名，オンラインで 41 名で合計 60名であった．学生の参加者が 18 名と，若手の参加者も多かった．
今年も日本化学会，日本分析化学会，分子科学会，応用物理学会の 4 学協会の協賛を得て実施し，これら協賛学会からの参加者は分

基調講演の尾崎先生は，尾崎研で開拓さ光学会員と同額の参加費とした．また，コロれた遠紫外（FUV）分光法による表面分析に

ナ禍での出費の厳しさも勘案して低価格についてご講演いただいた．紫外領域を極端紫設定し，とくに学生は例年通り無料とした．

外・深紫外と FUV に分けて初心者にもわかハイブリッド開催をスムーズに実現する

りやすくて丁寧に説明していただき，吸収がため，専門業者にマイクなどの設定を任せ，強すぎるがゆえに利用が難しかった FUV に最終的に 60,247 円の黒字で終了した．

挑戦し，σ結合の化学という位置付けて進め

6 回目の今回は“第 6 回 MAIRS ワークシてこられたことや，装置開発の経緯を詳しく

ョップ｜薄膜概念の拡張”として開催した．

ご説明いただいた．その上で，ATR 法を組み対面式の会場は京大化研で，プログラムは次合わせて実現した ATR-FUV 分光法が，結果のとおりである．

的に界面から数十 nm という領域を解析でき1.

基調講演：ATR－遠紫外分光法で表面をることの実証なども示された．今後，この領診る（尾崎幸洋・関西学院大）域で MAIRS の実施が待たれる．

2.

3.
4.

In situ MAIRS-蒸着複合装置を用いた有

東北大の丸山先生は，真空蒸着法を利用

機-無機ハイブリッド材料の薄膜反応過した複合膜の成膜過程を追うため，MAIRS2程の観察（丸山伸伍・東北大）

を導入する理由をわかりやすくご説明されフッ素系撥油剤の評価（山崎秀樹・日東た．また，MAIRS で配向を議論するというよ分析センター）

りは，MAIRS 固有の機能である「無配向状態

pMAIRS 法で解析するシリコン表面ナのスペクトル Aiso が得られる」ことを前面－143－

に打ち出し，成膜の仮定での成分の増減を柳田研で行われているナノワイヤ上での呼Aiso とケモメトリックスを組み合わせて実気分子の吸着と反応に関する詳細な検討結現されていた．また，その結果から薄膜成長

果が大迫力で報告された．ZnO ナノワイヤは，過程のアレーニウスプロットも初めて実現

基板に垂直に伸びたナノサイズの太さを持し，MAIRS によって物理化学としての深み

つ針がたくさん生えた基板で，このワイヤにが増すことを述べられて，非常に印象的だっ

吸着する呼気分子は，基板に直接吸着する場

た．

合に比べて配向が 90 度ずれる．MD 計算や

日東分析センターの山崎さんは，PTFE を実験と組み合わせた予想を pMAIRS で実証

薄くした網目状の化合物である日東電工のする実験に成功しており，とくにメチル基のTemish という製品に関する構造－物性相関

非対称伸縮振動の分裂をうまく利用した解の研究を紹介された．すべてお一人で実験・

析は，分光学会での議論にふさわしく，

解析されたデータが多数紹介された．たとえMAIRS をフル活用しているという意味でも，ば，静的接触角測定で違いが出ないものでも，素晴らしい取り組みだった．

滑落角にすると大きな違いが出る例など，印

このように，今年の講演会は，MAIRS が象的な写真やデータを多数見ることができユーザーの手によってこれまで以上に自由た．また，MAIRS で現れるフォノンバンドかに羽ばたき，想像以上の広がりを示し始めて

らモルフォロジーの変化を議論するポインいることを実感できる充実の内容となった．

トも紹介され，MAIRS の新たな使い方とし会のスムーズな運営を可能にしてくれた，て聴衆に強い印象を残した．

国際共共拠点にこの場をお借りして，厚く御弘前大の島田先生は，表面増強赤外分光

礼を申し上げる．

（SEIRAS）の増強機構についての研究であった．過去に提唱されたホットスポット説とプラズモンの誘電率変化説の二つの機構は，いずれも完全ではなく，それぞれが説明できないポイントを持つことを説明され，研究の動機が明確であった．ここで新たに提案された機構は，不連続な微粒子上でしか SEIRASが起こらないことに注目したもので，微粒子のサイズと間隔を系統的に制御した実験を丁寧に行った．その結果，サイズと間隔の比をパラメータにすると，ばらばらに見えていた実験値がすべてひとつの曲線に載ることがわかり，理論的にも説明がつくことが判明した．これを非金属のシリコンでも検討し，プラズモンでなくてもこのような誘電率の効果が，SEIRAS の根幹に関わっていることを示し，強いインパクトを与えた．質疑でも，この点を高く評価するコメントがあり，この説が今後大いに重要視されることを印象付
けた．
最後のトリは東大の細見先生によって，－144－

長谷川健（分子環境解析化学研究領域）

3．成果発表論文
紙数の都合により、目次に記載した論文の一部についてのみ、別刷りを次頁以降に掲載する。

Reprinted from Nature, 607, 86–90 (2022)

ArticleNitrogen reduction by the Fe sites ofsynthetic [Mo3S4Fe] cubes
https://doi.org/10.1038/s41586-022-04848-1
Received: 29 April 2021
Accepted: 9 May 2022
Published online: 6 July 2022
Check for updates

Yasuhiro Ohki1 ✉, Kenichiro Munakata2, Yuto Matsuoka1, Ryota Hara2, Mami Kachi2,
Keisuke Uchida2, Mizuki Tada2, Roger E. Cramer3, W. M. C. Sameera4,5, Tsutomu Takayama6,
Yoichi Sakai6, Shogo Kuriyama7, Yoshiaki Nishibayashi7 & Kazuki Tanifuji1

Nitrogen (N2) fixation by nature, which is a crucial process for the supply of
bio-available forms of nitrogen, is performed by nitrogenase. This enzyme uses aunique transition-metal–sulfur–carbon cluster as its active-site co-factor([(R-homocitrate)MoFe7S9C], FeMoco)1,2, and the sulfur-surrounded iron (Fe) atoms
have been postulated to capture and reduce N2 (refs. 3–6). Although there are a few
examples of synthetic counterparts of the FeMoco, metal–sulfur cluster, which haveshown binding of N2 (refs. 7–9), the reduction of N2 by any synthetic metal–sulfur
cluster or by the extracted form of FeMoco10 has remained elusive, despite nearly
50 years of research. Here we show that the Fe atoms in our synthetic [Mo3S4Fe]
cubes11,12 can capture a N2 molecule and catalyse N2 silylation to form N(SiMe3)3 under
treatment with excess sodium and trimethylsilyl chloride. These results exemplify thecatalytic silylation of N2 by a synthetic metal–sulfur cluster and demonstrate theN2-reduction capability of Fe atoms in a sulfur-rich environment, which is reminiscentof the ability of FeMoco to bind and activate N2.

Nitrogen (N2) is an essential element to maintain every known form oflife on Earth. Although the element is inexhaustible in the atmosphereas N2, only diazotrophs or lightning in thunderstorms can transform
this stable molecule into bio-available forms (for example, ammonia(NH3) and nitrogen oxides) in the natural world. Other organisms consequently rely on the products of the fixation processes and limited
pre-existing sources to afford the necessary nitrogen. In this sense, N2
fixation is one of the most crucial bottlenecks in Earth’s ecosystem.
Key players of N2 fixation are nitrogenase enzymes that reduce N2 to
NH3. The most studied of these, molybdenum (Mo)-nitrogenase, has aunique metal–sulfur–carbon co-factor described as [(R-homocitrate)
MoFe7S9C] (FeMoco; Fig. 1)1,2 and performs the catalytic reduction
at ambient temperature and pressure. As FeMoco is found only innitrogenase, its chemical and physical properties have attracted significant interest regarding its desirable N2-reduction activity. How
FeMoco reduces N2 has long been studied by biochemical analyses ofthe enzyme3,13 and by structural and functional modelling of FeMocowith small-molecule complexes14,15 and metal–sulfur (M–S) clusters16,17.
Although the detailed N2-reduction mechanism of FeMoco remains
elusive, a growing number of studies suggest that FeMoco eliminates
one of the µ2-bridging sulfur (S) atoms and captures substrates atthe produced vacant coordination sites on the iron (Fe) atoms4–6.
Analogously, a common approach to generating small-molecule N2
complexes has been removal of a metal-bound ligand under reducing
conditions. However, applying this method to the available synthetic
counterparts of FeMoco, namely, M–S clusters, has been challenging. As
these clusters contain coordinative S atoms in their inorganic cores, avacant metal site often attracts core S atoms of M–S clusters rather thanN2, which leads to aggregation17. Limiting the number of vacant metal
atoms in the core is thus a plausible approach and led to the isolation of
N2-bound clusters in several previous and recent examples, including
ours7–9. Nevertheless, catalytic reduction of N2 by these clusters remains
unknown despite its relevance to the natural system.
Our framework to overcome these hurdles implements a triangular[Mo3S4] fragment bearing robust Mo–CpR bonds (CpR = C5Me5 (Cp*),
C5Me4SiMe3 (CpL) and C5Me4SiEt3 (CpXL), where Si is silicon, Me is methyl
and Et is ethyl)11,12 as a platform to structurally encumber and protect
a fourth metal incorporated into the vertex (Fig. 1). A titanium (Ti)derivative [Cp*3Mo3S4Ti] captures and activates N2 in the presence ofpotassium graphite (KC8), indicating that the [Mo3S4Ti] cube is robust
under reducing conditions and avoids undesirable aggregation8. In contrast, catalytic reduction of the bound N2 was not observed, probably
owing to the strong Ti–N bond that inhibits product release. We thenhypothesized that a softer Fe atom as found in the biological systems
might function more successfully to carry out N2 reduction instead of
the harder Ti atom. The results below demonstrate the capture andcatalytic silylation of N2 by the vertex Fe atoms of [Mo3S4Fe] cubes.
Although it is likely that there are mechanistic differences between thesilylation of N2 and NH3 production by nitrogenase, our results demonstrate that an Fe centre built into a M–S core and in a S-rich coordination
environment can activate inert N2 sufficiently for chemical conversion.
The treatment of our reported [Mo3S4Fe] clusters, [CpR3Mo3S4FeCl](CpR = Cp* (1a), CpR = CpL (1b) and CpR = CpXL (1c))11,12 with strong
reductants (KC8 for 1a and sodium naphthalenide Na(C10H8) for
1b and 1c) under N2 in tetrahydrofuran (THF) led to the formation of thecorresponding N2 clusters (Fig. 2a). The N2 coordination mode varies

Institute for Chemical Research, Kyoto University, Uji, Japan. 2Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Nagoya,Japan. 3Department of Chemistry, University of Hawaii, Honolulu, HI, USA. 4Instituted of Low Temperature Science, Hokkaido University, Sapporo, Japan. 5Department of Chemistry, Universityof Colombo, Colombo, Sri Lanka. 6Department of Chemistry, Daido University, Nagoya, Japan. 7Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo, Japan.
✉e-mail: ohki@scl.kyoto-u.ac.jp
186 | Nature | Vol 607 | 7 July 2022

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N

N

FeMoco[(R-homocitrate)MoFe7S9C]
Proposed N2-binding stateThis work

Fig. 1 | A proposed N2-binding state for FeMoco and a N2-bound Mo–Fe–S
cluster in this work. Orange, iron; teal, molybdenum; yellow, sulfur; grey,
carbon; blue, nitrogen.

depending on the bulkiness of the CpR ligands, so that a [Mo3S4Fe]
dimer bridged by N2, [{Cp*3Mo3S4Fe}2(µ-N2)]2– (2a), and monomers
each bearing a terminal N2 ligand, [CpR3Mo3S4Fe(N2)]– (CpR = CpL (2b)and CpR = CpXL (2c)), were obtained. The N2 binding modes of 2a–2cwere assigned primarily from the 15N NMR spectra of 15N2-labelled clusters (Supplementary Figs. 1–3). Cluster 2a exhibited a single signal
at a chemical shift δ = –40.9 ppm as expected from the equivalent N
atoms of the bridging 15N2. Conversely, 2b and 2c gave two signals at
δ = 22.0 ppm and δ = –5.3 ppm for 2b and δ = 22.6 ppm and δ = –5.7 ppm
for 2c, corresponding to the inequivalent proximal and distal N atoms
in these molecules. Terminal N2 binding in 2b and 2c was further confirmed by infrared-active N–N stretches observed at 1,896 cm–1 and
1,902 cm–1, respectively, both of which exhibited a bathochromic shift
upon 15N2 labelling (Supplementary Figs. 7 and 8). Despite our efforts,
no meaningful N–N stretch for 2a was detectable via resonance-Ramanor infrared measurements (Supplementary Fig. 6), perhaps owing
to slightly broken symmetry of the N2 binding mode. X-ray crystallographic analyses revealed the molecular structures of 2a and 2c(Fig. 2b,c, Supplementary Figs. 11 and 12, and Supplementary Table 5).
The structure of 2a is an N2-bridged [Mo3S4Fe] dimer with an inversion
centre at the middle of the two N atoms, whereas 2c is a monomericcluster bearing a terminally bound N2. The N–N distances (1.151(4) Åfor 2a and 1.136(5) Å for 2c) are in between those of free N2 (1.098(1) Å)and N2H2 (1.252 Å), suggesting a weakened N–N bond. Likewise, theN–N stretching frequencies of 2b and 2c are close to the lower end of
those reported for N2 complexes of FeII or FeI (ref. 18), and the activationlevels are even comparable to an Fe0–N2 complex supported by S- andcarbon (C)-based ligands19.
Successful activation of N2 at the Fe atoms of 2a–2c prompted us
to pursue the catalytic reduction of N2 using the [Mo3S4Fe] cubes.
Reduction to NH3 was observed but was not catalytic, giving at most
1.6 ± 0.1 equiv. NH3 (per 2c) under typical conditions14,15,20 (Supplementary Table 4). Protonation of S atoms possibly occurs in this reaction,
which weakens the Fe–S bonds and releases a vertex Fe atom from
[Mo3S4Fe], in a relevant manner to degradation of the cubes under electrochemical oxidation11,12. Nonetheless, more importantly, we foundthat the chloride (Cl) clusters 1a–1c and N2 clusters 2b and 2c all catalytically reduce N2 to N(SiMe3)3 in the presence of excess sodium (Na) and trimethylsilyl chloride (ClSiMe3). A minimum of 122.9 ± 3.0 equiv. (per 1c)and up to 248.0 ± 15.6 equiv. (per 1b) of N(SiMe3)3 were generated after

100 h under a N2 (1 atm) atmosphere at room temperature (Table 1
and Supplementary Tables 1 and 2). Although the cause of the differences in the activity of these complexes has not been conclusively
identified at this point, we assume that the steric, not electronic, effectsof the CpR ligands play a major role (vide infra) because the CpR substituents did not notably affect the redox behaviours of 1a–1c (half-wave
potential E1/2 ([Mo3S4Fe]5+/4+) = –0.17 V (1a), –0.19 V (1b) and –0.24 V (1c)versus Ag/Ag+)12 or the redox features of 2b and 2c observed in cyclic
voltammetry (Supplementary Fig. 14).
The N(SiMe3)3 yields, on a per-active-metal basis produced by 1band 2c, are about three-times higher than those of other Fe catalysts
reported so far (Supplementary Table 3)21–25, and are comparable tothe highest yields by Mo (ref. 26) and Co (refs. 27,28) catalysts. Similar to
known systems, the catalytic reactions in THF concurrently formed
Me3SiSiMe3, Me3SiOC4H9 and Me3SiOC4H8SiMe3 as by-products (Supplementary Figs. 15–17). These by-products should originate fromreactions of the trimethylsilyl radical ·SiMe3 with itself or the THF solvent28, as treatment of ClSiMe3 with alkaline metals has been accepted
to generate ·SiMe3 (ref. 26). Although the THF solvent is much moreabundant than the N2 reactant, the selectivity for N(SiMe3)3 was highin the case of 1b and reached 37.2% (Table 1, entry 2). It is striking thatany of the corresponding [Mo3S4] platforms, [CpR3Mo3S4] (CpR = Cp*(4a), CpR = CpL (4b) and CpR = CpXL (4c)), several relevant FeS clusters
or FeCl2 (ref. 20) did not provide N(SiMe3)3 at significant levels under
the same conditions (Table 1 and Supplementary Table 3). After a catalytic run using 1a, a mass spectrum of the reaction mixture revealed[Mo3S4Fe] cubes binding ring-opening products of THF (Supplementary
Fig. 19), indicating sufficient stability of the cubic core during catalysis.
Moreover, a carbon monoxide (CO)-trapping experiment revealed
the formation of a low yield (11%) of [Cp XL3Mo3S4Fe(CO)] (5) from acatalytic reaction mixture with 1c, Na and ClSiMe3 (200 equiv. each)under N2 (Supplementary Figs. 24–27), implying the generation of[Mo3S4Fe] species with labile ligands (for example, THF or N2) on Fe.
These results suggest that the Fe centre of each [Mo3S4Fe] cube is theactual N2-reduction site.
Considering previous proposals for analogous reactions26,28, we
propose a mechanism for N2 silylation by our [Mo3S4Fe] cubes (Supplementary Fig. 18). In this pathway, we suppose that the Cl atom

Table 1 | Catalytic reduction of N2 into N(SiMe3)3 promoted by[Mo3S4Fe] clusters

Entry

Precatalyst

N(SiMe3)3 yield (equiv. per
catalyst)a1

1a127.0 ± 34.6

2

1b248.0 ± 15.6

31c122.9 ± 3.0

42b142.5 ± 16.0

52c

227.1 ± 40.8

63

258.3 ± 6.1

7

Cp*3Mo3S4 (4a)6.5 ± 1.5

8

CpL3Mo3S4 (4b)9.6 ± 2.7

9

CpXL3Mo3S4 (4c)12.9 ± 8.7

Na and ClSiMe3 (2,000 equiv. of each) were added to the catalyst in THF at room temperatureand stirred for 100 h under 1 atm N2. Reactions by 2a were not examined owing to the low
isolated yield and the lower performance of the Cp* (C5Me5) system. Yields represent the
average of three runs. aYields were obtained from three independent experiments (n = 3) andare shown as mean ± s.d.

Nature | Vol 607 | 7 July 2022 | 87－146－

Article
a

THF

Cp*
N2 (1 atm)
2 KC8
THF
(CpR = Cp*)

Mo

CpR
S

CpR

Mo

Cp*
S

S Mo

N Fe

N

S
S

Cl

SiMe3

S

K

2a
Fe

Mo

N Fe

Fe
Mo

Cp*

THF THF

S

K

Mo

S

K

Cp*

S

Mo S
Mo

Fe N

S

CpR
Mo

S

Mo S

b

Cp*

S

Mo

Cp*
S

THF

K

SiEt3

S

1a (CpR = Cp*)
1b (CpR = CpL)
1c (CpR = CpXL)
N2 (1 atm)
2 Na(C10H8)
THF
then + 15-crown-5(CpR = CpL or CpXL)

Cp*

CpL

CpXL

c
Si

CpR

CpR
S

Mo

Mo S
Mo

O O
O
O
Na O

S
Fe N

N

N N
Na

Fe
S

THF

S

CpR

Mo
S

Si

2b (CpR = CpL)
2c (CpR = CpXL)dCpR = CpXLClSiPh3Si
CpXL(1) N2 (1 atm)
2 KC8
(2) ClSiPh3
THF(CpR = CpXL)

CpXL
S

Mo

Mo S
Mo

CpXL

Si

Fe

S

S

SiPh3
Fe N

N N
Mo

N

S

S

Si
3

Fig. 2 | Synthesis and chemical modification of N2-bound [Mo3S 4Fe]
clusters. a, Synthetic schemes for the N2-bound [Mo3S 4Fe] clusters 2a–2cand subsequent silylation of the bound N2 to give 3. b–d, The structure of

2a (b), 2c (c) and 3 (d). The equivalence of 2a (1/2 equiv.) is omitted forreadability. Carbon and oxygen atoms are drawn as capped sticks for clarity.

on Fe is removed by ·SiMe3 to generate a vacant Fe site that binds N2.
In the resultant Fe–N2 species, the more exposed distal N atom probably undergoes the first silylation to generate the Fe–NNSiMe3 species. Further silylation and reduction would dissociate a hydrazido
anion [Me3SiN–N(SiMe3)2]–, as theoretically proposed for Mo- andCo-catalysed reactions26,28. Dissociation of the hydrazido anion canregenerate a vacant Fe site for the next catalytic cycle. It is noted that wecannot exclude the possibility that the catalysis is mediated by unidentified species generated in the solution. However, the isolation of theN2-bound clusters establishes the substrate binding by the [Mo3S4Fe]
clusters. Below, we additionally describe stoichiometric experimentsthat indicate the feasibility of the initial silylation of N2.
The initial silylation of the N2 ligand is arguably the most vital stepin N2 reduction. To validate it, the in situ-generated 2c (from 1c and2.3 equiv. KC8) was treated with 1.1 equiv. ClSiPh3 (where Ph is phenyl)
to furnish a monosilylated N2 species ([CpXL3Mo3S4Fe(N2SiPh3)], 3) in
20% yield (Fig. 2a,d and Supplementary Figs. 4, 9 and 13). The samecluster 3 was alternatively generated from 2c and ClSiPh3 in C6D6 (Supplementary Fig. 5). The X-ray structure of 3 shows an elongated N–N
distance (1.193(7) Å) from that found in the N2-bound 2c (1.136(5) Å),in accordance with a weakened N–N bond (stretching frequency
ν N–N = 1,706 cm –1). These values are close to those previously

reported for Fe complexes bearing [N2SiR3] ligands (Supplementary
Table 6)22,29,30. Although the phenyl substituents on the Si atom of 3
differ from the methyl groups employed in the catalytic process, the isolation of 3 supports the possible generation of an Fe–NNSiMe3 analogueof 2c in the catalytic cycle. This assumption was further reinforced when
3 was used as the precursor for the successful catalytic silylation of N2,yielding 258.3 ± 6.1 equiv. of N(SiMe3)3 (Table 1, entry 6).
The irreversible chemical modification of the bound N2 molecule
highlights a reactivity difference between our system and a N2-bridged[MoFe3S4] dimer reported recently9. Treatment of [{Cp*MoFe3S4(IPr)2}2(µ-N2)] (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene)
with [CpL2Ti] has been reported to give an equilibrium mixture of
the [MoFe3S4]2(µ-N2) dimer and a heterometallic N2-bridged complex [{Cp*MoFe3S4(IPr)2}(µ-N2)(CpL2Ti)], but no further chemical
conversions or catalytic reduction of the bound N2 was reported.
The difference in reactivity between this N2 bridging system and theterminally bound N2 system reported herein points to the importance of a terminal Fe–N2 moiety for the successful reduction of N2.
In addition, the isolation of a stable intermediate analogue by our[Mo3S4Fe] platform indicates its potential utility as a synthetic toolkit
to investigate catalytic as well as stoichiometric activation of othersmall molecules.

88 | Nature | Vol 607 | 7 July 2022

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a

b
)H

C5Me5 (Cp*)

c
)H

)H

C5Me4SiMe3 (CpL)

C5Me4SiEt3 (CpXL)

Fig. 3 | Structural models of N2-bound [Mo3S4Fe] clusters. A space-fillingmodel is applied to two CpR ligands, whereas the other CpR is omitted to show the[Mo3S4Fe]–N2 moiety. a, C5Me5 (Cp*). b, C5Me4SiMe3 (CpL). c, C5Me4SiEt3 (CpXL).

Panels a and c were prepared from the crystal structures of 2a and 2c; panel b
was prepared via software using the Cl-bound cluster 1b.

Structural models of the N2-bound clusters reveal that the CpR ligands
surround the N2 ligand and the [Mo3S4Fe] cores (Fig. 3). The –SiMe3 and–SiEt3 groups of the CpR ligands are forced into the space around the
Fe sites of the [Mo3S4Fe] cubes (Fig. 3b,c) to minimize steric repulsion
between the CpR ligands. Thus, the –SiR3 groups efficiently offer stericprotection of the [Fe–N2] moiety and prevent dimerization of cubes
through either an Fe–N2–Fe bridge or an inter-cube Fe–S interaction.
In contrast, the less bulky Cp* ligands lead to a more exposed Fe site
(Fig. 3a) and allow the approach of the Fe site of another [Mo3S4Fe] cube
to give an Fe–N2–Fe dimer. The bulkiness of the CpR ligands should
affect the catalytic activities as well, as we suggest that the first N–Si
bond formation occurs at the distal N atom. In an Fe–N2–Fe dimer, both
N atoms are protected until one of the Fe–N interactions breaks togenerate monomers. In the catalytic reactions using Fe–Cl cubes, chloride abstraction (initiation) is expected to be slower with the bulkier
CpR ligands.
To better understand the properties of 2a–2c and 3, zero-field 57
Fe Mössbauer spectra were measured at 78 K using powdered crystals(Supplementary Fig. 10). The spectra were fitted as single quadrupole
doublets with the following values of the isomer shift (δ) and the quadrupole splitting (|∆EQ|): δ = 0.479(4) mm s−1 (2a), δ = 0.410(2) mm s−1(2b), δ = 0.401(3) mm s−1 (2c) and δ = 0.263(3) mm s−1 (3), respectively; |∆EQ| = 1.258(8) mm s−1 (2a), |∆EQ| = 1.422(5) mm s−1 (2b),|∆EQ| = 1.466(5) mm s−1 (2c) and |∆EQ| = 0.906(5) mm s−1 (3), respectively.
The δ values of 2a–2c are lower than those of the precursors 1a–1c featuring FeII centres (δ = 0.555(2)–0.563(3) mm s−1), even though 2a–2c aresupposedly more reduced. A reduced Fe centre typically shows a higherδ than an oxidized Fe in similar coordination environments, owing toshielding of electrons in s orbitals by the increased 3d electron densities. This has also been verified for [Fe4S4] and [Fe3S4] clusters bearing
thiolate ligands31. The opposite trend observed here could be ascribedto π back-donation from Fe to the N2 ligand. As suggested from theoretical calculations, such increased covalency of the Fe–ligand bondleads to high electron density at the Fe nucleus and, consequently, alow δ value32. Thus, although determination of the Fe oxidation state
is not straightforward, we tentatively assign the Fe centres in 2a–2c
as close to FeII but only slightly reduced. Kohn–Sham frontier orbitals of optimized 2a and 2c reveal major contributions of Mo atoms in
the occupied orbitals to store reducing equivalents (SupplementaryFigs. 21–23). The density-functional-theory-calculated δ values of 2a, 2c
and 3 based on the crystal and optimized structures are qualitatively inagreement with the experimental data (Supplementary Tables 7–10),
supporting the utility of orbital analysis.
The covalent nature of Fe–N interaction can also rationalize the δvalue of 3. As illustrated by the N–N bond distance and N–N stretchingfrequency of the cluster, silylation of the N2 ligand has led to stronger
back-donation from Fe and a shorter Fe–N distance (1.687(5) Å) thanthose of 2a and 2c. This is consistent with a highly covalent Fe–N interaction and does not contradict the decrease of the δ value in 3 comparedwith 2a–2c, implying a major contribution of a resonance structure of
Fe=N=N–SiPh3. A notably bent N–N–Si angle of 3 (133.4(5)°), a linear

Fe–N–N alignment (171.6(6)°) and computed Mayer bond orders (Fe–N,
1.49 (3) versus 0.89 (2a) and 1.12 (2c); N–N, 1.68 (3) versus 2.00 (2a) and2.31 (2c); Supplementary Tables 11–13) are in good agreement witha diazenido assignment. The effect of the Fe–N interaction on the δvariation of a series of clusters can be illustrated by a plot of their Fe–N
bond distances versus δ values. The plot using data points of 2a, 2c and3 exhibits a pseudo-linear relationship as shown in Supplementary
Fig. 20. Interestingly, similar relationships were also seen in [(SiPi-Pr3)
Fe(N2)]0/– and [(SiPi-Pr3)Fe(N2SiMe3)] (SiPi-Pr3 = Si(o-C6H4Pi-Pr2)3]−)30, and[LSnFe(N2)]0/– and [LSnFe(N2SiMe3)] (L = [N(o-(NCH2Pi-Pr2)(C6H4)3]3–)33,
and regression lines from each series have nearly the same slope.
Overall, the above results represent the first catalytic silylation of N2
by a synthetic M–S cluster and suggest some key features for successful N2 reduction. Sufficient stability of the M–S core under reducing
conditions can make an Fe centre sufficiently electron-rich to activate
N2. These results imply that suppression of intermolecular aggregation of M–S cores is a key to stabilizing a terminal N2-bound species
and maintaining the reactivity at the distal N atom of the bound N2
molecule. In this sense, the steric protection given by the CpR ligands
loosely mirrors the role of a protein matrix isolating metal centres tocontrol reactivity and avoid undesirable decomposition. Although N2
reduction to NH3 or to N(SiMe3)3 should have substantial mechanistic
differences, our results provide compelling clues that the N2 moleculecan become susceptible to reduction by Fe centres in S-rich environments, as is the case with FeMoco.

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N2 to N(SiMe3)3 via an Fe-hydrazido resting state. J. Am. Chem. Soc. 140, 10691–10694(2018).
25. Liang, Q. et al. [2Fe–2S] cluster supported by redox-active o-phenylenediamide ligands
and its application toward dinitrogen reduction. Inorg. Chem. 60, 13811–13820 (2021).
26. Tanaka, H. et al. Molybdenum-catalyzed transformation of molecular dinitrogen intosilylamine: experimental and DFT study on the remarkable role of ferrocenyldiphosphine
ligands. J. Am. Chem. Soc. 133, 3498–3506 (2011).
27. Li, M., Gupta, S. K., Dechert, S., Demeshko, S. & Meyer, F. Merging pincer motifs andpotential metal-metal cooperativity in cobalt dinitrogen chemistry: efficient catalytic
silylation of N2 to N(SiMe3)3. Angew. Chem. Int. Ed. 60, 14480–14487 (2021).
28. Siedschlag, R. B. et al. Catalytic silylation of dinitrogen with a dicobalt complex. J. Am.
Chem. Soc. 137, 4638–4641 (2015).
29. Piascik, A. D. et al. Cationic silyldiazenido complexes of the Fe(diphosphine)2(N2)platform: structural and electronic models for an elusive first intermediate in N2 fixation.
Chem. Commun. 53, 7657–7660 (2017).
30. Lee, Y., Mankad, N. P. & Peters, J. C. Triggering N2 uptake via redox-induced expulsion of
coordinated NH3 and N2 silylation at trigonal bipyramidal iron. Nat. Chem. 2, 558–565(2010).
31. Rao, P. V. & Holm, R. H. Synthetic analogues of the active sites of iron−sulfur proteins.
Chem. Rev. 104, 527–560 (2004).
32. Neese, F. Prediction and interpretation of the 57Fe isomer shift in Mössbauer spectra bydensity functional theory. Inorg. Chim. Acta 337, 181–192 (2002).
33. Dorantes, M. J., Moore, J. T., Bill, E., Mienert, B. & Lu, C. C. Bimetallic iron–tin catalyst for N2
to NH3 and a silyldiazenido model intermediate. Chem. Commun. 56, 11030–11033(2020).
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims inpublished maps and institutional affiliations.
© The Author(s), under exclusive licence to Springer Nature Limited 2022

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ICR, Kyoto University (for Y.O. and W.M.C.S.), and The Kyoto University Research Fund for Young
Scientist (Start-Up) (for K.T.).

Data availability
X-ray data are available free of charge from the Cambridge Crystallographic Data Centre under reference numbers CCDC 2079174–2079176
and 2141451. All other experimental, spectroscopic, crystallographic andcomputational data are included in the Supplementary Information.

Author contributions Y.O. designed the study. K.M., Y.M., R.H., M.K., K.U. and K.T. conducted
the experiments. M.T. participated in the discussion. Y.O. and K.T. interpreted the data. R.E.C.
analysed the single-crystal XRD data. W.M.C.S. collected and analysed the computational
data. T.T. and Y.S. collected and analysed the Mössbauer spectra. S.K. and Y.N. conducted
experiments for ammonia synthesis. Y.O. and K.T. wrote the manuscript with input from all
authors.

Acknowledgements We thank T. Ohta (Sanyo-Onoda City University) for attempted
resonance-Raman measurements of 2a and 15N-labelled 2a. We acknowledge supercomputing
resources at the Research Center for Computational Science at Okazaki and the Institute for
Chemical Research at Kyoto University (Japan). This work was financially supported by
Grant-in-Aids for Scientific Research (19H02733, 20K21207, 21H00021 for Y.O., 20H05671 and
20K21203 for Y.N., 20K15295 for S.K. and 21K20557 for K.T.) from the Japanese Ministry of
Education, Culture, Sports, Science and Technology (MEXT), CREST grant (JPMJCR21B1 for Y.O.
and JPMJCR1541 for Y.N.) from JST, the Takeda Science Foundation, the Tatematsu Foundation,and the Yazaki Memorial Foundation (for Y.O.), International Collaborative Research Program ofCompeting interests The authors declare no competing interests.
Additional information
Supplementary information The online version contains supplementary material available athttps://doi.org/10.1038/s41586-022-04848-1.
Correspondence and requests for materials should be addressed to Yasuhiro Ohki.
Peer review information Nature thanks Daniël Broere, Thomas Rauchfuss and the other,anonymous, reviewer(s) for their contribution to the peer review of this work.
Reprints and permissions information is available at http://www.nature.com/reprints.

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Reprinted from Nat. Nanotechnol., 17, 823–828 (2022)

Letters
https://doi.org/10.1038/s41565-022-01159-4

Field-free superconducting diode effectin noncentrosymmetric superconductor/
ferromagnet multilayers
Hideki Narita 1 ✉, Jun Ishizuka 2, Ryo Kawarazaki1, Daisuke Kan1,3, Yoichi Shiota 1,3,
Takahiro Moriyama 1,3, Yuichi Shimakawa 1,3, Alexey V. Ognev4, Alexander S. Samardak4,
Youichi Yanase5,6 and Teruo Ono 1,3,4,7 ✉The diode effect is fundamental to electronic devices and is
widely used in rectifiers and a.c.–d.c. converters. At low temperatures, however, conventional semiconductor diodes possess a high resistivity, which yields energy loss and heating
during operation. The superconducting diode effect (SDE)1–8,
which relies on broken inversion symmetry in a superconductor, may mitigate this obstacle: in one direction, azero-resistance supercurrent can flow through the diode, but
for the opposite direction of current flow, the device enters
the normal state with ohmic resistance. The application of amagnetic field can induce SDE in Nb/V/Ta superlattices witha polar structure1,2, in superconducting devices with asymmetric patterning of pinning centres9 or in superconductor/ferromagnet hybrid devices with induced vortices10,11. The need foran external magnetic field limits their practical application.
Recently, a field-free SDE was observed in a NbSe2/Nb3Br8/
NbSe2 junction; it originates from asymmetric Josephson tunnelling that is induced by the Nb3Br8 barrier and the associated NbSe2/Nb3Br8 interfaces12. Here, we present another
implementation of zero-field SDE using noncentrosymmetric[Nb/V/Co/V/Ta]20 multilayers. The magnetic layers provide
the necessary symmetry breaking, and we can tune the SDE byadjusting the structural parameters, such as the constituent
elements, film thickness, stacking order and number of repetitions. We control the polarity of the SDE through the magnetization direction of the ferromagnetic layers. Artificiallystacked structures13–18, such as the one used in this work, areof particular interest as they are compatible with microfabrication techniques and can be integrated with devices such as
Josephson junctions19–22. Energy-loss-free SDEs as presented
in this work may therefore enable novel non-volatile memories and logic circuits with ultralow power consumption.
We fabricated noncentrosymmetric ferromagnet/superconductor multilayers [Nb (4.5 nm)/V (4.5 nm)/Co (1.7 nm)/V (4.5 nm)/Ta(4.5 nm)]20 by replacing the V layers in Nb/V/Ta superlattices1,2,23,24
with symmetric V/Co/V units to control the Rashba superconductor25 by magnetization. The crystalline structure of the multilayers
was characterized by low-angle and high-angle X-ray diffraction
profiles (Methods and Supplementary Fig. 1). Figure 1a shows aschematic of the measurement configuration, wherein the magnetic
field, electrical current and polar axis are perpendicular to eachother. Figure 1b shows a photomicrograph of the device with thepolar axis along the z direction. Electric current and magnetic field
were applied along the y and x directions, respectively.
Figure 1c shows the temperature dependence of the resistivityof the device at an electrical current density of 0.455 kA cm–2 undervarious magnetic fields ranging from 0 to 0.5 T.
The superconducting transition temperature, Tc (the temperature at which the resistivity drops to half of that above the transition), of the device was determined to be 2.6 K in the absence of amagnetic field. The Tc of the present device is lower than that of thepreviously studied [Nb (1 nm)/V (1 nm)/Ta (1 nm)]40 device1. Thisis possibly due to the pair-breaking effect of the Co layers16 and/or the difference in the repetition number (Supplementary Fig. 2).
Furthermore, vortices were observed to start breaking the superconducting phase with increasing magnetic field, and the superconducting phase completely disappeared above 0.5 T at the lowest
measurement temperature of 1.9 K. The superconducting coherence
length ξ(0) at 0 K was estimated to be 24 nm (Supplementary Fig. 3).
The magnetization curves of the multilayers at different temperaturesin Fig. 1d show the characteristic ferromagnetic responses with acoercive field of 0.065 T in the multilayers above and below the Tc.
Figure 1e presents the magnetic field dependences of the resistivity at several electrical current densities evaluated at 1.9 K. We
observed switching between normal and superconducting states,
similar to that observed in previous studies13,14. This is caused by theinterplay between superconductivity and ferromagnetism. Previous
reports have suggested that the switching between the normal andsuperconducting states is due to the internal exchange field at thesuperconductor–ferromagnet interface13,14. In our experiments,
the switching between the normal and superconducting states
was observed in the current density range of 0.455–20.45 kA cm–2.
Because of the suppression of superconductivity by the external
magnetic fields, the electrical resistivity increases monotonicallywith the magnetic fields at a low current density of 0.455 kA cm–2.
As the current density increases, the hysteresis of magnetoresistance becomes more pronounced, and the conventional magnetoresistance of Co is observed above 22.72 kA cm–2, where theInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, Japan. 2Institute for Theoretical Physics, ETH Zurich, Zurich, Switzerland. 3Center for
Spintronics Research Network, Institute for Chemical Research, Kyoto University, Uji, Japan. 4Laboratory of Spin-Orbitronics, Institute of High Technologies
and Advanced Materials, Far Eastern Federal University, Vladivostok, Russia. 5Department of Physics, Graduate School of Science, Kyoto University, Kyoto,
Japan. 6Institute for Molecular Science, Okazaki, Japan. 7Center for Spintronics Research Network, Graduate School of Engineering Science, Osaka University,
Toyonaka, Japan. ✉e-mail: narita.hideki.3x@kyoto-u.ac.jp; ono@scl.kyoto-u.ac.jp

1

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Polar axis

Co
V
Nb
Ta
V
Co
V

nt

y

x

rre

Cu

y

Magnetiz

ation

Nb

Magnetic

50 µm

field

c

d

8
6
4

M (emu cm–3)

0T
0.1 T
0.2 T
0.3 T
0.4 T
0.5 T

2
0

1

2

3

4

ZFC

0

1.8 K
1.9 K
2.5 K
2.6 K
5.0 K

–20
–40

0.455 kA cm–2

ρ (µΩ cm)

12

–60
–1.0

5

–0.5

0

12

4

4

0

0

0

12

12

4

18.18 kA cm–2
ρ (µΩ cm)

13.6 kA cm–2
8

20.45 kA cm–2

8

8

4

4

–0.2

0

0.2

1.0

12

9.1 kA cm–2

8

–0.4

0.5

B (T)

0.455 kA cm–2
1.9 K
B⊥J

8

0

0.15

20

T (K)

e

x

40

10
ρ (µΩ cm)

–0.15

60

12

0

.
z

0.4

0

12.12

22.72 kA cm–2

12.08
12.04

–0.4

–0.2

B (T)

0
B (T)

0.2

0.4

12.00

–0.4

–0.2

0

0.2

0.4

B (T)

Fig. 1 | Device structure, transport, magnetic properties and SDe. a, Schematic of the SDE and measurement configuration. The magnetic field is applied
perpendicular to both the polar axis and the electrical current. b, Photomicrograph of the device. The wires of the [Nb/V/Co/V/Ta]20 multilayers were
electrically connected to the Au (100 nm)/Ti (5.0 nm) metal electrodes. V, voltage. The red scale bar corresponds to 50 µm. c, Temperature (T) dependenceof the device resistivity (ρ) at an electrical current density (0.455 kA cm–2) in the multilayers under a magnetic field in the range of 0 to 0.5 T. d, Magnetization
loops at several temperatures for the multilayers above and below Tc. e, Magnetic field dependence of the resistivity in the multilayers for several electricalcurrent densities at 1.9 K. The direction of the magnetic field was perpendicular to the polar axis and the electrical current.

superconductivity is completely destroyed. The observation of theconventional magnetoresistance of Co also indicates that the device
fabrication process does not alter the ferromagnetic properties ofthe multilayers.
Figure 2a,b shows the resistivity as a function of the current
density, J, under various magnetic fields for positive and negative
currents at 1.9 K. We observed the SDE in our noncentrosymmetric superconductor/ferromagnet multilayers; the critical current
density Jc (the current density at which the resistivity increases
to half of that above the transition) depends on the polarity of
the current. Note that Jc is determined by the transition from thesuperconducting state to the normal conductive state. Therefore,
there is no influence from the Joule heating. The variation in
Jc with the magnetic field at 1.9 K is shown in Fig. 2c. In these824

Jc measurements, the magnetic field was initially set to +0.5 T,
which is sufficiently large to saturate the magnetization, determined from the results in Fig. 1c. Subsequently, Jc was measured
by sweeping the magnetic field in the order of +0.5, 0, −0.5, 0,+0.5 T. Jc also exhibits hysteresis, reflecting the magnetic hysteresis of the Co layer. Jc shows a symmetric behaviour with respect
to zero field (dashed line) for the sweep of the magnetic field in
the order of −0.5, 0, +0.5, 0 T. The pronounced peak around thecoercive field can be attributed to enhanced vortex pinning on the
network of proliferating domain walls26.
Figure 2d shows the magnetic field dependences of the
non-reciprocal components of the critical current densities,
ΔJc = |+Jc| − |−Jc|, at different temperatures (+Jc and −Jc are thecritical current densities corresponding to positive and negative

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12

+J

b 12

B (T)
+0.15
+0.0080–0.008
–0.04

–J

8

ρ (µΩ cm)ρ (µΩ cm)

a

4

8

0

10

20

30

B (T)
–0.15
–0.0080+0.008+0.04

4Upward sweep

Downward sweep
0

–J

+J

40

50

60

0

70

0

10

20

30

40

50

60

70

∣J ∣ (kA cm–2)–2∣J ∣ (kA cm )c+0.5 T → –0.5 T → +0.5 T∣Jc∣ (kA cm–2)

80

1.9 K

+Jc

–Jc

0.05

0.10

60

Downward sweep
Upward sweep

40
20
0
–0.15

–0.10

–0.05

0

0.15

B (T)

d

6

ΔJc (kA cm–2)

4

1.9 K

2.0 K

2.1 K

2.2 K

2.3 K

2.4 K

2
0
–2
–4
–6
6

ΔJc (kA cm–2)

4
2
0
–2
–4
–6

–0.12 –0.06

0

0.06

0.12

–0.12 –0.06

B (T)

0

0.06

0.12

B (T)

–0.12 –0.06

0

0.06

0.12

B (T)

Fig. 2 | Magnetic field and temperature dependences of SDe. a, Current density (J) dependence of the resistivity under various magnetic fields for positive
and negative currents at 1.9 K. The magnetic field was swept from +0.5 T to −0.5 T (downward sweep). b, Dependence of the resistivity on J under various
magnetic fields for positive and negative currents at 1.9 K. The magnetic field was swept from −0.5 T to +0.5 T (upward sweep). c, Jc as a function of themagnetic field at 1.9 K. First, the magnetic hysteresis of Jc was measured from +0.5 to −0.5 T (downward sweep) for positive (red) and negative (black)currents. Subsequently, the sweep direction was reversed, and the magnetic field was swept from −0.5 to +0.5 T (upward sweep) for positive (blue) andnegative (green) currents. The arrows indicate the sweep directions. d, Non-reciprocal component of the critical current density, ΔJc, as a function of themagnetic field at various temperatures. The magnetic hysteresis of ΔJc was measured from +0.5 to −0.5 T (downward sweep, black). Subsequently, thesweep direction was reversed, and the magnetic field was swept from −0.5 to +0.5 T (upward sweep, red). The arrows indicate the sweep direction.

currents, respectively). Here, the magnetic field was initially set to+0.5 T. Then, ΔJc was measured by sweeping the magnetic field in
the order of +0.5, 0, −0.5, 0, +0.5 T. In the downward sweep fromthe magnetic field of +0.5 T at 1.9 K (black dots), a negative peakof ΔJc appears at approximately +0.008 T, and ΔJc approaches zeroat 0 T. As the magnetic field decreases further, large negative andpositive peaks of ΔJc appear at approximately −0.008 and −0.04 T,
respectively. The ΔJc value then gradually decreases to zero ataround −0.5 T. After saturating the magnetization at −0.5 T, ΔJc
was measured again by sweeping the magnetic field in the orderof −0.5, 0, +0.5 T. Moreover, the magnetic field dependence of ΔJc
in the upward sweep shows a trend (red dots) opposite to that ofthe downward sweep (black dots). The microscopic origin of theobserved peaks and dip structures in the magnetic field dependenceof ΔJc is not clear. However, it is possibly related to the evolution ofcomplex magnetic domains. We also checked the reproducibilities

of Jc and ΔJc in two additional devices (Supplementary Fig. 4), andwe observed that there was no clear hysteresis of ΔJc in the configurations of B ∥ x and B ∥ z (Supplementary Fig. 5). This hysteresis
behaviour of ΔJc for B ∥ y is in clear contrast with the SDE observedin Nb/V/Ta superlattices1, wherein no hysteresis is observed. Notethat the symmetric [Nb/V/Co/V/Nb]20 multilayers without a polarstructure do not exhibit the clear non-reciprocal components of thecritical current densities even though they exhibit hysteresis in themagnetization curves (Supplementary Fig. 6). Therefore, the polarstructure is essential to realize the magnetization-mediated SDE.
The polarity control of SDE in a zero field is essential to develop
non-volatile devices based on SDEs. We demonstrate it using theminor hysteresis loops of the magnetization. Figure 3a shows themagnetic field dependences of Jc for positive and negative currents
in minor hysteresis loops. For this, the magnetic field was swept in
the order of +0.5, 0, −0.15 T (downward sweep) and then −0.15, 0,

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80∣Jc∣ (kA cm–2)c+0.5 T → –0.15 T → +0.15 T+Jc –Jc

1.9 K

60–0.5 T → +0.15 T → –0.15 T

80
Downward sweep
Upward sweep

40
20∣Jc∣ (kA cm–2)

a

60

20
0

d

6
4

ΔJc (kA cm–2)

ΔJc (kA cm–2)

Downward sweep
Upward sweep

40

0

b

+Jc –Jc

1.9 K

2
0
–2
–4
–6
–0.15 –0.10 –0.05

0

0.05

0.10

6
4
2
0
–2
–4
–6
–0.15 –0.10 –0.05

0.15

B (T)

0

0.05

0.10

0.15

B (T)

e

–M, +M, 0 T, 1.9 K

80

J (kA cm–2)

40
0
–40
–80

f

ρ (µΩ cm)

12

8

4

0

0

2

4

6

8

10

12

14

Time (min)Fig. 3 | Field-free SDe controlled by magnetization. a, Magnetic field dependences of Jc for positive and negative currents in minor hysteresis loops at 1.9 K.
Magnetic field was swept in the order of +0.5, 0, −0.15 T (downward sweep) and then −0.15, 0, +0.15 T (upward sweep). b, Magnetic field dependence of
ΔJc in the minor hysteresis loops obtained by Fig. 3a. c, Magnetic field dependences of Jc for positive and negative currents in minor hysteresis loops at 1.9 K.
Magnetic field was swept in the order of −0.5, 0, +0.15 T (upward sweep), and then +0.15, 0, −0.15 T (downward sweep). d, Magnetic field dependenceof ΔJc in the minor hysteresis loops obtained by Fig. 3c. e, Repeated application of current densities J = 72.7 kA cm–2 and J = −72.7 kA cm–2 at 1.9 K withouta magnetic field. f, Non-volatile SDE at 1.9 K. Red and black dots represent the results for negative magnetization (−M) and positive magnetization (+M),
respectively. The device shows a superconducting state or normal conducting state depending on the polarity of the current. Note that the polarity of theSDE depends on the direction of magnetization. The −M or +M state is achieved after sweeping the magnetic field in the order of +0.5, 0, −0.15, 0 T or
−0.5, 0, +0.15, 0 T, respectively.

+0.15 T (upward sweep). The limiting field of the minor loops is
0.15 T, as shown by the dashed line in Fig. 1d. Owing to the asymmetrical magnetic field sweeping, Jc shows asymmetry with respect
to the zero field (dashed line). Consequently, we observe the positive ΔJc in the zero field after sweeping the magnetic field in theorder of +0.5, 0, −0.15, 0 T, as shown in Fig. 3b. Moreover, Jc also
shows asymmetry with respect to zero field after sweeping the magnetic field in the order of −0.5, 0, +0.15, 0 T, resulting in a negative
ΔJc under the zero-field condition, as shown in Fig. 3c,d. Therefore,
we could control the polarity of the SDE by magnetization.
Here, we demonstrate the non-volatile SDE. With repeated application of current densities in Fig. 3e, the red and black dots in Fig. 3f
represent the resistivities measured with J = 72.7 kA cm–2 at 1.9 K for
negative (−M) and positive (+M) magnetizations, respectively. The−M (+M) is the state after sweeping the magnetic field in the orderof +0.5, 0, −0.15, 0 T ( − 0.5, 0, +0.15, 0 T). The device exhibits a826

superconducting state or a normal conducting state depending on
the polarity of the current, and the polarity of the SDE depends onthe direction of magnetization.
Finally, we discuss theoretical viewpoints in detail. We performeda first-principles band structure calculation in the non-magnetic
electronic state for a Nb/V/Co/V/Ta supercell, where two atomic
layers of body-centred cubic Nb, V, Co, V and Ta were repeatedly
stacked, as shown in Fig. 4a,b. The Rashba splitting of bands at the
Fermi energy EF was observed as ER = 1–10 meV, which is close to
the value of a Nb/V/Ta superlattice. Although the Rashba splittingof Co bands was minor (~1 meV), the density of states due to the
Co bands near EF was predominantly larger than that due to the Nb,
V and Ta bands, as shown in Fig. 4b. To gain more insight, we also
performed a spin-polarized band structure calculation with themagnetization direction [010] and obtained a ferromagnetic groundstate, where the total energy was lower than that of the non-magnetic

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2.0

Paramagnetic

10
Nb

Partial density of states (eV–1)

1.5

Energy (eV)

1.0
0.5
0
–0.5
–1.0

V1

8

Co
V2
Ta

6

4

2

–1.5
–2.0

Г

X

M

0

Г Z

–4

–2

0

2

4

2

4

Energy (eV)cdFerromagnetic

2.0

Ferromagnetic

10

Partial density of states (eV–1)

1.5

Energy (eV)

1.0
0.5
0
–0.5
–1.0

8

6

4

2

–1.5
–2.0

Г

X

M

0

Г Z

–4

–2

0
Energy (eV)Fig. 4 | Band structure of a bulk Nb/V/co/V/Ta superlattice. a, Band structure obtained from first-principles calculation for paramagnetic state. b, Partial
density of states for paramagnetic state. c, Band structure for ferromagnetic state. d, Partial density of states for ferromagnetic state. The V layer between
Nb and Co is labeled with V1 and that between Co and Ta is labeled with V2.

state, as shown in Fig. 4c,d. The magnitude of the magnetic moment|M| at Co atoms was calculated as |M| = 1.93μB where μB is the Bohrmagneton. The V atoms adjacent to Co atoms had a considerable
magnetization |M| = 0.5μB–1μB, while others had only |M| = 0.01μB–
0.05μB. Thus, the atoms that are not adjacent to Co atoms can stabilize the superconductivity against the Pauli depairing effect due
to the ferromagnetic spin polarization. We indeed noticed that thepartial densities of states are almost unchanged for Nb, V and Ta
atoms, and all atoms contribute at EF in the ferromagnetic state, as
shown in Fig. 4d. In other words, the superconducting transition
temperature of this system may be determined from the total density of states consisting of three types of atoms.
Pairing states that exhibit the diode effect would correspondto helical superconductivity, which has been investigated in noncentrosymmetric superconductors such as CePt3Si (refs. 27,28), thesurface/interface of SrTiO3/LaAlO3 (ref. 29) and heavy-fermion
superlattices30. The asymmetric band dispersion is essential forthe helical superconductivity, and it appears in the noncentrosymmetric ferromagnet. Our spin-polarized band structure calculation indeed shows asymmetric behaviours (Supplementary Fig. 7).
The SDE has been analysed by the Ginzburg–Landau theory andmicroscopic Hamiltonian3,6–8. Higher-order gradient terms in the
Ginzburg–Landau expansion exhibit the non-reciprocity of critical current, and the microscopic calculation predicts an anomalous‘sign-reversal effect’ in the helical superconducting state6. Thus,

it will be intriguing to clarify the asymmetric and sign-reversing
behaviour observed in Fig. 2d in future works.
The experiments revealed that noncentrosymmetric superconductor/ferromagnet multilayers exhibited magnetization-mediatednon-reciprocal critical currents, that is, a magnetization-mediatedSDE. The field-free SDE demonstrated here enables rectification
without an external magnetic field. However, significant issues
still need to be overcome for practical application. The rectification still requires precise control of the applied current and temperature, which are major limitations for practical device operation.
Therefore, it is essential to explore materials with a larger ΔJc andhigher Tc to realize a wide temperature range of operation. The proposed method of symmetry breaking using artificial stacked structures is versatile and controllable. Furthermore, the electronic band
structure can be controlled by modulating the thickness and periodof each constituent layer, which offers a promising route for exploring new materials for practical application. Our findings pave theway for obtaining rewritable superconducting diode logic circuits
using the non-volatility of magnetic materials.

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data and code availability are available at https://doi.org/10.1038/
s41565-022-01159-4.
Received: 20 November 2021; Accepted: 23 May 2022;
Published online: 30 June 2022

References

1. Ando, F. et al. Observation of superconducting diode effect. Nature 584,
373–376 (2020).
2. Miyasaka, Y. et al. Observation of nonreciprocal superconducting criticalfield. Appl. Phys. Express 14, 073003 (2021).
3. Wakatsuki, R. et al. Nonreciprocal charge transport in noncentrosymmetricsuperconductors. Sci. Adv. 3, e1602390 (2017).
4. Yasuda, K. et al. Nonreciprocal charge transport at topological insulator/
superconductor interface. Nat. Commun. 10, 2734 (2019).
5. Itahashi, Y. M. et al. Nonreciprocal transport in gate-induced polar
superconductor SrTiO3. Sci. Adv. 6, eaay9120 (2020).
6. Daido, A., Ikeda, Y. & Yanase, Y. Intrinsic superconducting diode effect.
Phys. Rev. Lett. 128, 037001 (2022).
7. Yuan, N. F. Q. & Fu, L. Supercurrent diode effect and finite
momentum superconductors. Proc. Natl Acad. Sci. USA 119,e2119548119 (2022).
8. He, J. J., Tanaka, Y. & Nagaosa, N. A phenomenological theory ofsuperconductor diodes. New J. Phys. 24, 053014 (2022).
9. Lyu, Y.-Y. et al. Superconducting diode effect via conformal-mapped
nanoholes. Nat. Commun. 12, 2703 (2021).
10. Aladyshkin, A. Yu., Fritzsche, J. & Moshchalkov, V. V. Planar superconductor/
ferromagnet hybrids: anisotropy of resistivity induced by magnetic templates.
Appl. Phys. Lett. 94, 222503 (2009).
11. Aladyshkin, A. Yu. et al. Reverse-domain superconductivity insuperconductor-ferromagnet hybrids: effect of a vortex-free channel on thesymmetry of I-V characteristics. Appl. Phys. Lett. 97, 052501 (2010).
12. Wu, H. et al. The field-free Josephson diode in a van der Waals
heterostructure. Nature 604, 653–656 (2022).
13. Zhu, Y., Pal, A., Blamire, M. G. & Barber, Z. H. Superconducting exchange
coupling between ferromagnets. Nat. Mater. 16, 195–199 (2017).
14. Li, B. et al. Superconducting spin switch with infinite magnetoresistanceinduced by an internal exchange field. Phys. Rev. Lett. 110, 097001 (2013).

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15. Baek, B., Rippard, W. H., Benz, S. P., Russek, S. E. & Dresselhaus, P. D.
Hybrid superconducting-magnetic memory device using competing orderparameters. Nat. Commun. 5, 3888 (2014).
16. Obi, Y., Ikebe, M., Wakou, H. & Fujimori, H. Superconducting transition
temperature and dimensional crossover in Nb/Co and V/Co multilayers.
J. Phys. Soc. Jpn 68, 2750–2754 (1991).
17. Monton, C., de la Cruz, F. & Guimpel, J. Magnetic behavior ofsuperconductor/ferromagnet superlattices. Phys. Rev. B 75, 064508 (2007).
18. Banerjee, N. et al. Controlling the superconducting transition by spin-orbit
coupling. Phys. Rev. B 97, 184521 (2018).
19. Misaki, K. & Nagaosa, N. Theory of the nonreciprocal Josephson effect.
Phys. Rev. B 103, 245302 (2021).
20. Baumgartner, C. et al. A Josephson junction supercurrent diode.
Nat. Nanotechnol. 17, 39–44 (2022).
21. Davydova, M., Prembabu, S. & Fu, L. Universal Josephson diode effect.
Sci. Adv. 8, eabo0309 (2022).
22. Bauriedl, L. et al. Supercurrent diode effect and magnetochiral anisotropy in
few-layer NbSe2. Preprint at arXiv https://doi.org/10.48550/arXiv.2110.15752(2022).
23. Ando, F. et al. Fabrication of noncentrosymmetric Nb/V/Ta superlattice andits superconductivity. J. Magn. Soc. Jpn 43, 17–20 (2019).
24. Ando, F. et al. Investigation of the upper critical field in artificially engineered
Nb/V/Ta superlattices. Jpn. J. Appl. Phys. 60, 060902 (2021).
25. Wakatsuki, R. & Nagaosa, N. Nonreciprocal current in noncentrosymmetric
Rashba superconductors. Phys. Rev. Lett. 121, 026601 (2018).
26. Curran, P. J. et al. Continuously tunable critical current insuperconductor-ferromagnet multilayers. Appl. Phys. Lett. 110, 262601 (2017).
27. Baur, E. et al. Heavy fermion superconductivity and magnetic order innoncentrosymmetric CePt3Si. Phys. Rev. Lett. 92, 027003 (2004).
28. Kaur, R. P., Agterberg, D. F. & Sigrist, M. Helical vortex phase in thenoncentrosymmetric CePt3Si. Phys. Rev. Lett. 94, 137002 (2005).
29. Reyren, N. et al. Superconducting interfaces between insulating oxides.
Science 317, 1196–1199 (2007).
30. Naritsuka, M. et al. Extremely strong-coupling superconductivity in artificial
two-dimensional Kondo lattices. Phys. Rev. B 96, 174512 (2017).
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims inpublished maps and institutional affiliations.
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Letters

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Methods

Device fabrication. The [Nb/V/Co/V/Ta]20 multilayers were grown on MgO(100)substrates by direct current (d.c.) magnetron sputtering in a high-vacuum systemwith a base pressure of approximately 5 × 10−6 Pa. Before the film growth, theMgO(100) substrate was heated at 600 °C for 30 min in a sputtering chamber toremove impurities. Subsequently, the MgO substrate was heated to 300 °C during
the deposition. All the films were deposited under an Ar pressure of approximately
0.1 Pa. The Nb, V, Co, V and Ta layers were repeatedly sputtered on the MgOsubstrate in the same sequence for 20 cycles. The deposition rates were maintained
constant at 0.36, 0.22, 0.45 and 0.18 Å s–1 for Nb, V, Ta and Co, respectively. The
total deposition time was approximately 5 h. After deposition, the films were cooled
from 300 to 30 °C. X-ray diffraction was performed using a conventional four-circle
diffractometer (PANalytical, X’pert MRD) with Cu Kα1 radiation (wavelength,
λ = 0.154 nm). Supplementary Fig. 1a,b shows the low-angle and high-angle X-ray
diffraction profiles of the multilayers, respectively. In this study, the thickness of theferromagnetic layer was adjusted to realize ferromagnetic properties, and it was set
to be sufficiently small to avoid the Bloch domain wall effect.
The deposited films were then patterned into a wire (dimensions,
50 μm × 1,000 μm × 0.44 μm) using conventional photolithography and Ar-ion
milling. Finally, Au (100 nm)/Ti (5.0 nm) metal electrodes were electricallyconnected to the wire. The surface layer was removed through weak Ar-ion milling
before the electrode deposition to create ohmic contacts.
Transport and magnetization measurements. During the transport measurements,
the temperature and magnetic field were controlled using a commercial refrigerator(Quantum Design, Physical Property Measurement System) with d.c. applied using
a current source (Yokogawa 7651). The voltage was measured using a four-terminal
configuration with a nanovoltmeter (Keithley 2182A).
The magnetization of the sample was studied under a magnetic field parallelto the film surface, using a superconducting quantum interference device
magnetometer (Quantum Design MPMS3). Before starting the measurements,
the magnetic field was reduced from 1.0 to 0 T using an oscillating field sequence
to remove any trapped flux in the superconducting magnet. Subsequently, themagnetic hysteresis loops of the zero-field-cooled (ZFC) magnetization were
measured in the ‘d.c. and no overshoot’ mode using film samples with dimensionsof 7 mm × 2 mm. ZFC means that the sample was cooled from 10 K without themagnetic field before magnetization measurements. The magnetization of the
MgO substrate was subtracted to determine the intrinsic magnetic properties of themultilayers with the field parallel to the surface.
Details of band structure calculation. We conducted first-principles calculations
for non-magnetic and ferromagnetic states on a bulk Nb/V/Co/V/Ta superlattice.
We adopted the full-potential linearized augmented plane wave plus local orbitals
method within the generalized gradient approximation in the WIEN2k package31,32.
A supercell was constructed with ten atoms consisting of two layers of Nb, V, Co,
V and Ta atoms. We used the muffin-tin radius RMT of 2.50 a.u.; the maximum
reciprocal lattice vector Kmax as RMTKmax = 8.0; and 21 × 21 × 4 k-point sampling forself-consistent calculation. Supplementary Fig. 7 shows the band structures and thepartial densities of states in non-magnetic and ferromagnetic states. If we neglect
the Co bands, the band structure is similar to that in the Nb/V/Ta superlattice.

The partial densities of the states of Co show an exchange splitting, while they arealmost unchanged for Nb, V and Ta. Thus, Nb, V and Ta layers form spin-splitting
bands with weak magnetization. Therefore, it is verified that Nb/V/Co/V/Ta is anoncentrosymmetric superconductor that exhibits a SDE without a magnetic field.

Data availability

The data that support the findings of this study are available from thecorresponding authors upon reasonable request.

References

31. Blaha, P. et al. WIEN2k: an Augmented Plane Wave Plus Local Orbitals
Program for Calculating Crystal Properties (Techn. Universität, 2018).
32. Blaha, P. et al. WIEN2k: an APW+lo program for calculating the properties
of solids. J. Chem. Phys. 152, 074101 (2020).

Acknowledgements

This work was partly supported by Japan Society for the Promotion of Science
KAKENHI (grant nos 15H05702, 15H05884, 15H05745, 18H04225, 18H01178,
18H05227, 19H05823, 20H05665, 21K13883 and 21K18145); the Cooperative Research
Project Program of the Research Institute of Electrical Communication, Tohoku
University; and the Collaborative Research Program of the Institute for Chemical
Research, Kyoto University. This study was also supported by the Futaba Foundation’s
Futaba Research Grant Program, and Iketani Science and Technology Foundation.
A.V.O., A.S.S. and T.O. acknowledge the Russian Ministry of Science and Higher
Education for state support of scientific research conducted under the supervision ofleading scientists in Russian institutions of higher education, scientific foundations andstate research centres (project no. 075-15-2021-607).

Author contributions

H.N. and T.O. conceived the project. H.N. deposited the multilayers and fabricatedthe devices. H.N. performed the measurements and data analysis. H.N. and T.O. wrote
the manuscript with the assistance of the other authors. J.I. and Y.Y. calculated theband structure and assisted with the analysis of the experimental results. All authors
contributed jointly to the interpretation of the results.

competing interests

The authors declare no competing interests.

Additional information

Supplementary information The online version contains supplementary material
available at https://doi.org/10.1038/s41565-022-01159-4.
Correspondence and requests for materials should be addressed to Hideki Narita or
Teruo Ono.
Peer review information Nature Nanotechnology thanks the anonymous reviewers fortheir contribution to the peer review of this work.
Reprints and permissions information is available at www.nature.com/reprints.

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4．参考資料

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
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京都大学化学研究所長
共同研究ステーション長

辻井敬亘
寺西利治

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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。
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経費上限／件 （千円）
国際共同研究国内共同研究分野選択型萌芽的研究

1,000

800

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2,000

1,500

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1,000

800

課題提案型発展的研究

2,000

1,500

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1,000

800

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800

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1. ※を付した事項は当研究所で記入します。
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3. 申請者（研究代表者）と共同研究者の役割分担を明記して下さい。事前に共同研究者の承諾を得ていただくことが必要です。
4. 申請書は 3 頁以内にまとめて下さい。
3-3．提出期限および提出先応募に当たっては、前記の申請書にご記入の上、令和４年１月２１（金）までに、下記宛に電子メール添付書類（Word 書類）としてお送り下さい。
問い合わせ先京都大学化学研究所 共同研究推進室
E-mail: icr-hub@scl.kyoto-u.ac.jp，電話: (0774)38-3121-3－161－

4．課題選考と採択通知
応募課題の採否は、当研究所の共同研究委員会で審査し、運営評議会の承認を経て決定されます。審査に際しては、共同研究の申請内容だけでなく、予算枠や、共通設備・機器・資料の使用時間等も考慮いたします。採否の結果（内定）については、令和４年３月に当研究所の所長から研究代表者に通知いたします。
5．研究の実施および研究成果報告
5-1．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、予算の範囲内で、研究経費（備品費および消耗品費）と旅費が支給されます。また、研究協力者（学生も含めることが可能です*）にも予算の範囲内で旅費が支給されます。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絡下さい。なお、当研究所には、共同研究者のための宿泊施設はありません。
＊研究協力者について、学生の場合は原則として大学院生といたします。なお、傷害保険等に加入していることが必要です。
5-2．研究成果報告採択された研究課題については、研究成果報告書を次に記す作成要領に従って記載・提出していただきます。その報告書は、まとめて当研究所の国際共同利用・共同研究報告書集として公開させていただく予定です。また、その内容を研究成果報告会でご報告いただくことがあります。なお、報告会についての詳細は、採択課題の研究代表者に後日お知らせいたします。
5-3．研究成果報告書の作成要領
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頁、連携・融合促進型研究については２頁の報告書を（様式５）を用いて作成下さい。Ａ４版の用紙には１頁あたり１，２００字程度が記載できます。図表などカラーを用いても構いませんが、報告書集刊行の際はモノクロ印刷になることもありますので、その点をお含み置き下さい。
１頁の１行目の中央に研究課題名、３行目に右詰めで研究代表者の氏名と所属、５行目から本文を記載して下さい。なお、当研究所で対応した共同研究者は報告書の共著者とはせず、必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、報告書は英文でご作成ください。
5-4．報告書の内容
形式は自由ですが、例えば、実験的研究では、目的、実験方法、実験結果、考察、成果報告（論文、学会発表等）をお書き下さい。なお、連携・融合促進型研究で研究集会を開催した場合には、研究集会のプログラ
ム、参加者名簿（所属機関・部局・職名を明記）、および、作成された場合は要旨集またはプロシーディング
スを添付して下さい。
5-5．報告書の提出
提出締切日は、令和５年２月末日とします。電子ファイル（Word ファイルと PDF ファイル）を、下記宛にお送り下さい。なお、ファイル名は「課題番号＋代表者名（姓）」として下さい（例：2022-1 田中.doc、
2022-1 田中.pdf）。
問い合わせ先京都大学化学研究所 共同研究推進室
E-mail: icr-hub@scl.kyoto-u.ac.jp，電話: (0774)38-3121
5-6．研究成果の公開
学術論文などによる研究成果の公開に際しては、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。英文での謝辞例を次に示します。
謝辞例: This work was supported by the International Collaborative Research Program of Institute for
Chemical Research, Kyoto University (grant # XXXX).
日本語での謝辞は、この英文表記に準ずるものとして下さい。

-4－162－

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Carboboration and Carbosilylation by Merging Iron and Visible-Light Photocatalysis

島川 祐一

中村 正治

National Taiwan University, Center for Condensed Matter
Sciences

DEPARTMENT OF CHEMISTRY, VISVA-BHARATIUNIVERSITY, SANTINIKETAN-731235, INDIA

University of Colombo, Department of Chemistry2022-6 Wei-Tin Chen

2022-7 ALAKANANDA HAJRA

2022-8 W. M. C. Sameera

Development of 1,4-Addition Reactions via Iron Catalysis

Peptide Bolaamphiphile Anchored Nickel-based Metallohydrogel as Electrocatalyst for Hydrogen Production

分野選択型

分野選択型

島川 祐一

水畑 吉行
時任 宣博

水畑 吉行

中村 正治

中村 正治

Chinese Academy of Science (CAS), Institute of High Energy
Physics (IHEP), Chinese Spallation Neutron Source (CSNS)

Institute for Inorganic Chemistry, University of Bonn

Tohoku University, Department of Chemistry

Department of Chemistry, Indian Institute of Engineering
Science and Technology, Shibpur

Department of Chemistry, Indian Institute of Technology
Indore2022-12 KOEDTRUAD Anucha

2022-13 Rainer Streubel

2022-14 Takeaki Iwamoto

2022-15 LAKSMIKANTA ADAK

2022-16 Apurba K. Das

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発展的 国際島川 祐一

2

Institut Charles Gerhardt Montpellier (ICGM, CNRS), D4:
Chemistry of Materials, Nanostructures, Materials for Energy

分野選択型

Development of Unsymmetrical π-Electron Systems of Heavier Main Group Elements and Elucidation of Their Property

非対称型高周期典型元素π電子系の開拓と物性解明

Small molecule activation using anionic crypto-FLPs

新規なアニオン性FLPを用いた小分子活性化

High-pressure synthesis and ionic conducting study of novel Na-antiperovskites containing hydride and cluster anions as solid electrolytes inbatteries

ハイドライドおよび陰イオンクラスターを含んだ新規Na―アンチペロブスカイト型固体電解質材料の高圧合成とイオン伝導の研究

Preparation and Characterization of Novel Magnetic Quadruple Perovskites by High Pressure

高圧合成技術を用いた新規磁気四重極ペロブスカイトの作製とその特性評価

High pressure synthesis of novel hexagonal perovskite oxides containing unusually high-valence Fe ions and investigation of their magnetic
properties

異常高原子価Fe イオンを含む新規六方晶ペロブスカイト酸化物の高圧合成および磁気特性の研究

Development and device evaluation of new D-π-A emitters based on rigidified triarylborone acceptors

2022-11 Midori Estefani AMANO PATINO

剛直なフッ素化三配位ホウ素骨格をアクセプターとする新規発光材料の開発とデバイス評価

Computational mechanistic study on the Co-catalyzed nitrogenase model reactions.

コバルトを反応点とするニトロゲナーゼのモデル反応の理論解析

島川 祐一

発展的 国際

萌芽的 国際Verification of radiochemical reaction mechanism for FLASH radiotherapy with electron beams

電子線を用いた超高線量率放射線がん治療（FLASH）の作用機序の解明の試み

2022-10 Zhenhong Tan

22

発展的 国際

発展的 国際萌芽的

Enhanced production of fast ions by TNSA with Pre-pulse Laser

プリパルス付与による高変換TNSA イオン加速機構実証

Institute of High Energy Physics (IHEP) of the Chinese
Academy of Sciences, China Spallation Neutron Source(CSNS)

分野選択型

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2

2

1

発展的

Development of new nano-structure target for ISOL

ナノ構造を持つ ISOL 用標的の開発

梶 弘典

大木 靖弘

分野選択型

分野選択型

分野選択型

1

萌芽的

Julius-Maximilians-Universität Würzburg, Institut für
Anorganische Chemie

2022-9 Todd B. Marder

Design and Tailoring Advanced Functional Materials: Symmetry Operation and High Pressure Synthesis

小河原 亮

国立研究開発法人量子科学技術研究開発機構

分野選択型

1

Crystal Structure Analysis of GraE from Root-Nodule-Forming Bacterium

根粒菌由来GraE タンパク質の結晶構造解析

2022-5 小平 聡

若杉 昌徳

分野選択型

発展的

Synthesis and optical characterization of helical gold nanowires with branches

分岐構造を有するらせん状金ナノワイヤーの合成および光学特性評価

課題名（和文・英文）

光産業創成大学院大学・光産業創成研究科

国際2022-4 花山 良平

若杉 昌徳

1

萌芽的

実施
状況

理化学研究所・仁科加速器科学研究センター

分野選択型

1

選択
分野

2022-3 大西 哲哉

藤井 知実

分野選択型

型

関西大学・化学生命工学部

倉田 博基

化研内
研究協力者

2022-2 老川 典夫

研究代表者所属

地方独立行政法人大阪産業技術研究所

研究代表者

2022-1 中川 充

課題番号化学研究所 国際共共拠点 R4年度採択課題 (応募195件, 採択 136件, 採択率 69.7 %, 国際共同研究割合46.3％)

－164－

阿久津 達也

阿久津 達也

遠藤 寿

馬見塚 拓

馬見塚 拓

谷藤 一樹

関西学院大学・理学部

横浜国立大学・大学院工学研究院

山陽小野田市立山口東京理科大学・工学部応用化学科

岡山大学・大学院自然科学学域

筑波大学・数理物質系化学域

Monash University, Biomedicine Discovery InstituteNational Yang Ming Chiao Tung University, Department of
Biological Science and Technology/Institute of
Bioinformatics & Systems Biology

CEA/Genoscope, UMR8030

LS2N, CNRS UMR6004

Nagoya Institute of Technology, Department of Computer
Science

東邦大学・理学部生物分子科学科

東邦大学・理学部情報科学科

大阪大学・微生物病研究所

京都大学・大学院農学研究科応用生物科学専攻

帯広畜産大学・グローバルアグロメディシン研究センター

Department of Molecular Biology and Biochemistry,
Department of Chemistry, University of California, Irvine

2022-19 小田 晋

2022-20 山口 佳隆

2022-21 橋本 徹

2022-22 光藤 耕一

2022-23 笹森 貴裕

2022-24 Jiangning Song2022-25 Jinn-Moon Yang

2022-26 Morgan Gaïa2022-27 Samuel Chaffron

2022-28 Masayuki Karasuyama

2022-29 岸本 利彦

2022-30 ホセ ナチェル

2022-31 渡辺 登喜子

2022-32 吉田 天士

2022-33 茅野 光範

2022-34 Markus W. Ribbe

緒方 博之

緒方 博之

阿久津 達也

田村 武幸

緒方 博之

若宮 淳志

若宮 淳志

中村 正治

中村 正治

梶 弘典

大木 靖弘

鈴鹿医療科学大学・保健衛生学部医療栄養学科

2022-18 若林 成知

大木 靖弘

徳島大学・大学院社会産業理工学研究部

2022-17 小笠原 正道

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萌芽的

萌芽的

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萌芽的

萌芽的

Fe ラベリングを用いた窒素還元酵素Fe タンパクの触媒的・生化学的動態解析
Investigations into Catalytic and Biochemical Behaviors of Nitrogenase Fe protein using

57

Effective molecular network analysis and application to medical and agricultural research

効果的な分子ネットワーク解析方法の発展と医学・農学への応用

Microbial ecology in the dark sea

無光層における微生物生態

Development of a comprehensive detection method for coronaviruses originated in wildlife

野生動物の保有するコロナウイルスの包括的検出法の開発研究

Control and Analysis of Complex Networks via Probabilistic Minimum Dominating Sets

確率的最小支配集合による複雑ネットワークの制御と解析

57

Fe labeling

Revealing evolution mechanism of adaptation to high temperature based on omics data and flux balance analysis.

オミクスデータと流束均衡解析に基づく高温適応進化の機序解明

A Study on Statistical Machine Learning for Efficient Graph Structured Data Analysis

統計的機械学習による効率的なグラフ構造データ解析法の開発

Revealing marine microbial-viral interactions through community interactome analyses

群集インタラクトーム解析による海洋微生物・ウイルス間相互作用の解明

Evolution of giant viruses and relationships with the origin of Life

巨大ウイルスの進化と生命の起源との関係

Integrating omics data and module-based network with deep learning to develop cancer type predictive models

深層学習を用いたオミクスデータとモジュールに基づくネットワークデータの統合解析による腫瘍細胞分類

Developing machine learning approaches for prediction of protein stability changes upon missense mutations

タンパク質のミスセンス突然変異による安定性の変化予測のための機械学習方式の開発

Creation of Effective Oxidation Scavenger for Efficient Perovskite-based Solar Cells

高性能ペロブスカイト太陽電池作成に有効な高活性酸化スカベンジャーの開発

Development of heteroacenes with excellent photophysical and electrochemical properties

優れた光物性・電気化学的特性を併せ持つ新奇ヘテロアセン分子の開発

Synthesis of Alkyl Ethers Using Two Different Alcohols Catalyzed by Organosilane Compound

有機ケイ素化合物を触媒としたアルコールの脱水型エーテル合成

Synthesis and its catalysis of dinuclear complexes utilizing a pincer-type N,N,P ligand

3 座ピンサー型N,N,P 配位子を利用した複核錯体の合成とその触媒作用

Highly Efficient Solution-Processed Organic Light-Emitting Diodes Employing Multiple Resonance-Induced Thermally Activated Delayed
Fluorescence Emitter

MR-TADF 発光材料を用いた高効率塗布型有機EL 素子の開発

Synthesis of Self-Assembled Organoboran Compounds, Elucidation of Self-Assembly Process, and Creation of New Functions

自己集合性含ホウ素化合物の合成、集合過程解明ならびに機能開拓

Synthesis of Fe-containing phosphorus ligands and their application in the preparation of metal-cluster molecules

鉄含有リン系配位子の合成と金属クラスター錯体の合成への利用

－165－

若宮 淳志

松宮 由実

村田 靖次郎橋川 祥史

Department of Applied Chemistry, Graduate School ofEngineering, Osaka University

Nagoya University, Department of Molecular andMacromolecular Chemistry

Rudjer Boskovic Institute, Division of organic chemistry andbiochemistry, Laboratory for physical organic chemistry

Inner Mongolia University (IMU), College of Chemistry andChemical Engineering

山口東京理科大学・工学部応用化学科

大阪府立大学・大学院理学系研究科

大阪工業大学・工学部応用化学科

北海道大学・大学院理学研究科

2022-36 Akinori Saeki

2022-37 Atsushi Takano

2022-38 MARGETIC, Davor2022-39 CHAOLUMEN

2022-40 太田 雄大

2022-41 亀尾 肇

2022-42 平井 智康

2022-43 永木 愛一郎

村田 靖次郎

佐藤 健

松宮 由実

宗林 由樹

東北大学・未来科学技術共同研究センター

東京理科大学・理学部第一部化学科

久留米工業高等専門学校・一般科目（理科系）

大阪工業大学・工学部応用化学科

東北大学・学際科学フロンティア研究所（FRIS）

Dipartimento di Ingegneria Chimica, dei Materiali e della
Produzione Industriale, Università degli Studi di Napoli“Federico II”

Changchun Institute of Applied Chemistry, Chinese Academyof Sciences (CAS)

Academia Sinica, Research Center for Environmental
Changes

2022-45 髙橋 裕

2022-46 土戸 良高

2022-47 黒飛 敬

2022-48 村田 理尚

2022-49 上野 裕

2022-50 Giovanni Ianniruberto

2022-51 Shilong Wu

2022-52 HO, Tung-Yuan

村田 靖次郎村田 靖次郎

茅原 栄一

登阪 雅聡

静岡大学・グリーン科学技術研究所（および理学部）

2022-44 小林 健二

茅原 栄一

山子 茂

竹中 幹人

大木 靖弘

大木 靖弘

黄瀬 雄司

School of Physical & Mathematical Sciences, Division ofChemistry & Biological Chemistry, Nanyang Technological
University2022-35 Atsushi GOTO

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萌芽的

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発展的

萌芽的

萌芽的

萌芽的

発展的 国際

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萌芽的 国際

発展的 国際

発展的 国際Trace metal elemental and isotopic composition in the North Pacific Ocean: sources and internal cycling (3)北太平洋における微量金属の元素・同位体組成：起源と内部循環 (3)Nonlinear Extensional Rheology of Entangled Poly(n-alkyl methacrylate) Melts with Fixed Number of Entanglements and Kuhn Segments per Chain

一定の絡み合い数とKuhn セグメント数を持つポリ(n-アルキルメタクリレート)メルトの非線形伸長レオロジー

Non-linear viscoelasticity of unentangled polymers

非からみあい高分子の非線形粘弾性

Isolation of ultra-unstable chemical species toward unprecedented element strategy

未踏超不安定構造の単離および物性解明による新概念材料設計指針の創出

Development of Organometallic n-Type Materials with High Electrical Conductivity

高導電性n 型有機金属材料の開発

Synthesis and Applications of Novel Azaazulene Trimer toward Electronic materials

有機電子材料を指向したアザアズレン３量体の合成と応用

Synthesis of Highly Strained Macrocyclic π-Conjugated Molecules via a Multinuclear Au(I)-Pt(II) complex

金(I)及び白金(II)多核錯体を経由した高歪み環状共役化合物の合成

Elucidation of the lubrication properties of hyperbranched polymers and their optimization

超分岐構造高分子の滑剤作用の解明と最適化

Host-Guest Complexation of Cyclohexa-2,7-anthrylene Ethynylene Derivatives with [n]CPP

環状ヘキサ-2,7-アントリレンエチニレン誘導体と環状パラフェニレンとのホスト-ゲスト化学に基づく複合化

Synthesis of functional vinyltellurides using flow reactors

フロー合成法を用いた官能性ビニルテルリド合成法

Evaluation an Effect of Structure in Chiral Silica on Molecular Recognition

キラルシリカの構造と分子認識との相関解明

Dinitrogen Fixation based on nickel→Z-type (σ-Electron Acceptor) Ligand Interaction

ニッケル→Z 型 (σ電子受容性) 配位子相互作用を鍵要素とする窒素固定

Developing bioinspired molecular catalysts for materials science and medicinal chemistry.

金属酵素化学モデルの創製と材料・医化学への応用

Synthesis of Novel Nanotube Molecules with Different Hole Directions by Introducing a Double Heptalene Structure

ダブルヘプタレン構造の導入による異なる開口方向をもつ新規ナノチューブ分子の合成

Exploration of Cycloaddition Properties of Guanidine Functionalized Isatins

グアニジン修飾イサチンの付加環化反応に関する研究

Precise synthesis and viscoelastic properties of ring polymers with high purity and high molecular weight.

高純度、高分子量環状高分子の精密合成と粘弾性

Exploration of perovskite solar cell composition: correlating device performance and fundamental property

ペロブスカイト太陽電池の組成探索：素子性能と基礎物性の相関

Precise synthesis and controlling higher order structure of tadpole-like Janus cellulose nanocrystal

おたまじゃくし状ヤヌス型セルロースナノクリスタルの精密合成と高次構制御

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佐藤 健

Graduate School of Organic Materials Science, Yamagata
University

Osaka University, Graduate School of Science, Department of
松宮 由実
Macromolecular Science

大阪大学・大学院基礎工学研究科物質創成専攻

近畿大学・理工学部

京都教育大学・教育学部理学科

関西学院大学・工学部

岡山理科大学・理学部化学科

北海道大学・触媒科学研究所

2022-54 Sathish K. Sukumaran

2022-55 Osamu Urakawa

2022-56 五月女 光

2022-57 中口 譲

2022-58 向井 浩

2022-59 藤原 明比古

2022-60 大坂 昇

2022-61 飯田 健二

分野選択型

小野 輝男

Korea Advanced Institute of Science and Technology,
Department of Physics

University of Ulsan, Department of Physics

Far Eastern Federal University, Institute of High Technologies
and Advanced Materials, Department of General and小野 輝男
Experimental Physics

Laboratory for Physical Chemistry, ETH Zürich

Helmholtz-Zentrum Dresden-Rossendorf, Germany

産業技術総合研究所・デバイス技術研究部門

東京大学・理学系研究科物理学専攻

2022-64 Kab-Jin Kim

2022-65 Sanghoon Kim

2022-66 Alexey Ognev

2022-67 Takuya F. Segawa

2022-68 Gopalakrishnan Balasubramanian2022-69 諸田 美砂子

2022-70 石橋 未央

小野 輝男

小野 輝男

水落 憲和

水落 憲和

分野選択型

小野 輝男

京都大学・生命科学研究科

2022-63 河内 孝之

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山口 信次郎群馬大学・大学院理工学府

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長谷川 健

寺西 利治

竹中 幹人

竹中 幹人

宗林 由樹

宗林 由樹

梶 弘典

竹中 幹人

Stony Brook University, Department of Material Science andChemical Engineering2022-53 Tadanori Koga

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Research and development of magnon quantum logic gate devices using synthetic antiferromagnets

人工反強磁性体のマグノンを用いた量子情報演算素子の基盤技術開発

Demonstration of topological phase control in chalcogenide superlattices

カルコゲナイド系超格子のトポロジカル相制御の実証

Research toward stable NV centers at shallow region and spin dynamics in diamond

表面近傍NV 中心の安定化とスピンダイナミクスの研究

Research on the efficiency enhancement of the NV centers creation in nanodiamond

ナノダイヤモンド中のNV 中心作製効率化研究

Investigation on high efficient spin-orbit torque effect in multilayers with combine anisotropy and DMI

磁気異方性とジャロシンスキー守谷相互作用によるこう効率スピン軌道トルクの開拓

Observation of orbital Hall effect in transition metal dichalcogenides.

Characteristics of quantum magnon in magnetic insulators

磁性絶縁体での量子マグノン研究

Identification of active gibberellins in the basal land plant Marchantia polymorpha

基部陸上植物苔類ゼニゴケにおける活性型ジベレリンの単離と同定

Physicochemical characterization of novel hybrid partially fluorinated phospholipid bilayers

新規ハイブリッド型部分フッ素化リン脂質二分子膜の構造・物性の解析

Construction of Theoretical Guidelines for Designing Plasmonic Nanoalloys

プラズモニック合金ナノ粒子を設計するための理論的指針の構築

Conformation analysis on polymer in food-grade oil

食品油脂中の高分子鎖のコンフォメーション解析

Nano-scale structure characterization of organosulfur polymer

硫黄ポリマー材料におけるナノ構造不均一評価

Exploration of liquid membrane transportation of metal ions with a polymer membrane containing ionic liquid by use of electric field response of ions

イオンの電場応答を利用したイオン液体含有高分子膜による金属イオンの液膜輸送の開発

Effect of microplastics on distribution of trace heavy metals in sea water

海水中の微量重金属の分布に及ぼすマイクロプラスチックの影響（２）Analyzing Structural Fluctuation in Thermally Activated Delayed Fluorescence Materials with Ultralow-Frequency Raman Spectroscopy

超低波数ラマン分光による熱活性化遅延蛍光材料の構造揺らぎ解析

Control of Mechanical Properties in Polymer Blend Materials by Hydrogen Bonding Interaction

水素結合相互作用によるポリマーブレンド材料の力学特性の制御

High Frequency Response of Polymeric Liquids: Rheology and Dielectric Relaxation

高分子液体の高周波応答: レオロジーおよび誘電緩和

Resolving the structure-dynamics-property relationship in polymer nanocomposites under uniaxial stretching-II

高分子ナノコンポジットの補強メカニズムの解明-II

－167－

公立小松大学・生産システム科学部生産システム科学科

大阪公立大学・大学院理学系研究科生物科学専攻

三重大学・大学院医学系研究科消化器内科学

Peking University, School of Life Sciences

College of Resources and Environment, Southwest University2022-84 粕谷 素洋

2022-85 中瀨 生彦

2022-86 江口 暁子

2022-87 QU, Li-Jia

2022-88 Xianzhu Dai

2022-79 Yusuke Azuma

大阪公立大学・大学院理学研究科物質分子系専攻

Małopolska Center of Biotechnology, Jagiellonian University2022-78 Ebinazar B. Namdas

2022-83 三枝 栄子

The University of Queensland, School of Mathematics andPhysics, Centre for Organic Photonics & Electronics

2022-77 Anne S. Ulrich

理化学研究所・開拓研究本部

梶 弘典

Karlsruhe Institute of Technology (KIT), Institute of Organic
Chemistry (IOC) and Institute of Biological Interfaces (IBG2), Chair of Biochemistry at IOC

2022-82 木村 謙介

二木 史朗

Institute for Advanced Chemistry of Catalonia

2022-76 Sílvia PUJALS

東京理科大学・薬学部

二木 史朗

Cardiff University, School of Chemistry, Professor

2022-75 Thomas Wirth2022-81 西川 元也

宗林 由樹

Xiamen University, Department of Marine Chemistry andGeochemistry2022-74 Pinghe Cai

大阪大学・大学院工学研究科

上杉 志成

Tsinghua University, Department of Chemistry2022-73 Yan-Mei Li

2022-80 菊地 和也

水落 憲和

産業技術総合研究所・先進パワーエレクトロニクス研究セン
ター

2022-72 牧野 俊晴

栗原 達夫

青山 卓史

二木 史朗

二木 史朗

長谷川 健

長谷川 健

梶 弘典

上杉 志成

上杉 志成

二木 史朗

中村 正治

水落 憲和

金沢大学・ナノマテリアル研究所

2022-71 徳田 規夫

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特定 発展的Construction of heterologous protein secretion system at low temperatures by using cold-adapted microorganisms

低温適応微生物を用いた低温異種タンパク質分泌生産系の構築

Role of PIP5K Genes in Pollen Tube Development

花粉管形成におけるPIP5K 遺伝子の役割

Investigation of cellular uptake mechanism using extracellular vesicles

細胞外小胞の標的細胞への移行メカニズムの解明

Design of intracellular delivery systems for extracellular vesicles

エクソソームの細胞内への送達設計

Molecular characterization of fluoropolymer at frictional interface

フッ素系樹脂の摩擦界面における分子挙動の解明

Fabrication of luminescent thin films using amphiphilic lanthanide complexes

両親媒性希土類錯体を利用した薄膜発光体の作製

Construction of two-dimensional donor-acceptor systems by the collaboration of organic synthesis, single-molecule measurement, andcomputational chemistry.

有機合成・単分子測定・計算化学の協同による2 次元ドナー・アクセプター分子系の構築

Remote Control of Cells by Synthetic Small Molecules

合成小分子化合物による細胞の遠隔操作

Real-Time Visualization of Cellular Phase-Separating Proteins

細胞内相分離タンパク質のリアルタイム可視化

Intracellular delivery of biofunctional proteins using artificial protein nanocages

人工タンパク質ナノケージを用いた細胞内への機能性タンパク質の送達

In-depth analysis of efficiency roll-off in highly efficient TADF-based organic electroluminescence devices

熱活性化遅延蛍光を基盤とする高効率有機EL デバイスにおける効率低下の詳細解析

Structural and functional analysis of curvature-inducing peptides and application

曲率誘導ペプチドの構造活性相関と応用

Novel strategy for intracellular delivery of nanomedicines

ナノ医薬の新規細胞内効率的送達法

Advanced Oxygen – mediated Flow Chemistry

Evaluation of CaCO 3 dissolution rates in deep-sea sediments by a novel tracer method

Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune Therapy

がん免疫療法のための自己集合性アジュバント含有ワクチン

Research of quantum technology and diamond synthesis for higher sensitivity of NV quantum sensor

量子センサの高感度化に向けたリンドープダイヤモンド合成と量子科学技術研究

Research of surface state for diamond quantum information device

ダイヤモンド量子情報素子のための表面状態研究

－168－

山口 信次郎

増口 潔

佐藤 健

柘植 知彦

梶 弘典

竹中 幹人

辻井 敬亘

寺西 利治

寺西 利治

若杉 昌徳

若宮 淳志

Chinese Academy of Sciences, CAS Center for Excellencein Molecular Plant Sciences, Institute of Plant Physiology andEcology

University of California San Diego, Division of Biological
Sciences, Department of Cell and Developmental Biology

Department of Mathematical and Physical Sciences, Japan
Women’s University

National Center of Biotechnology (CNB-CSIC), Plant
Molecular Genetics Dept.

Fudan University, School of Pharmacy

Tsinghua University, Department of Chemistry

Stony Brook University, Department of Material Science andChemical Engineering

Yokohama National University, Faculty of Environment andInformation Sciences

Michigan State University, Chemical Engineering andMaterials Science

RMIT University, School of Engineering

Université de Strasbourg, Institut de Physique et Chimie desMatériaux (IPCMS)

Hiroshima University, Physics

Novel Materials and interfaces for photovoltaic solar cells,
Helmholtz-Zentrum Berlin, Germany

山口大学•大学院創成科学研究科

奈良先端科学技術大学院大学・先端科学技術研究科

北海道大学・工学研究院応用化学部門

東京大学・大学院薬学系研究科

2022-90 Zuhua He

2022-91 Yunde Zhao

2022-92 Ryoko Shimada

2022-93 RUBIO, Vicente2022-94 Lu Zhou

2022-95 Lian Duan2022-96 Maya Endoh2022-97 Ken Nakano

2022-98 Robert C. Ferrier, Jr.

2022-99 Yasuhiro Tachibana

2022-100 Jean-Pierre Bucher

2022-101 Kensuke Homma

2022-102 Antonio Abate2022-103 肥塚 崇男

2022-104 安喜 史織

2022-105 長浜 太郎

2022-106 金井 求

梶 弘典

小野 輝男

青山 卓史

柘植 知彦

辻井 敬亘

上杉 志成

栗原 達夫

University of Naples Federico II, Department of Chemical
Sciences2022-89 Maria Michela Corsaro

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発展的 国際Structural optimization of amyloid photooxygenation catalysts for the treatment of Alzheimer's disease

アルツハイマー病治療に向けたアミロイド光酸素化触媒の構造最適化

Electronic and spintronic properties of multilayer system including NiCo 2O4 and Fe 3O4

Fe 3O4/NiCo 2O4 多層膜の電子およびスピン物性の解明

Regulatory Role of Phytohormone Cytokinin on Leaf Epidermal Cell Differentiation

葉表皮細胞の分化制御における植物ホルモン・サイトカイニンの役割

Biochemical characterization of aldehyde dehydrogenases involved in the biosynthesis of plant volatile benzenoids

植物揮発性ベンゼノイド生合成におけるアルデヒド脱水素酵素の機能解析

Tin-perovskite thin film crystallization on new hole-transporting materials

新規正孔輸送層上でのSn ペロブスカイト半導体薄膜の結晶化

Search for four-wave-mixing in the vacuum - Unveiling dark components in the Universe -宇宙暗黒成分解明へ向けた真空内四光波混合の探索

Interdisciplinary Approach to Nanostructured Materials for Applications

応用に向けたナノ構造材料への学際的アプローチ

Development and characterization of metal oxide nanocrystalline films for solar water splitting

太陽光水分解のための金属酸化物ナノ結晶膜の作製と物性評価

Synthesis of Polyether Nanocomposite Solid Polymer Electrolytes for Lithium Ion Batteries

リチウムイオン電池用ポリエーテル系ナノコンポジット固体電解質の合成

Verification and Development of Dynamic Stiction Theory

動的固着理論の検証と展開

Fabrication of nanotopographical polymer surfaces for bactericidal properties-IV

高分子ナノ表面構造による殺菌効果-IV

Developments of highly efficient and high color purity organic electroluminescent devices based on thermally activated delayed fluorescent materials
exhibiting ultrafast reverse intersystem crossing process

迅速な逆項間交差を示す熱活性化遅延蛍光材料を用いた高効率・高色純度有機EL 素子の作製

Site-Selective Protein Acetylation and Phosphorylation by Small Molecules

小分子化合物による位置選択的タンパク質アセチル化とリン酸化

Chromatin, epigenetic and proteolytic regulation of RNA processing in plant morphogenesis

植物形態形成におけるRNA プロセシングを制御する遺伝子発現制御ネットワーク

Phase separation in mixture of nematic liquid crystal and solvent

ネマチック液晶/溶媒混合系における相分離

Analysis of novel transporters for strigolactones or their biosynthetic intermediates

新規ストリゴラクトン輸送体タンパク質の解析

Molecular mechanisms for the inactivation of a growth hormone in rice

イネの成長ホルモンの不活性化機構の解析

Structural and functional analysis of the surface polysaccharides of outer membrane vesicles released by bacteria

細菌が放出する外膜小胞の表層多糖の構造機能解析

－169－

明治大学・農学部

兵庫県立大学・大学院工学研究科

京都大学・大学院エネルギー科学研究科

京都大学・大学院エネルギー科学研究科

Middle Tennessee State University, Chemistry2022-120 瀬戸 義哉

2022-121 遊佐 真一

2022-122 松井 隆太郎

2022-123 岸本 泰明

2022-124 Chengshan Wang

共立女子大学・家政学部被服学科

2022-115 村瀬 浩貴

奈良県立医科大学・医学部

富山大学・学術研究部工学系

2022-114 源明 誠

2022-119 秦野 修

大阪公立大学工業高等専門学校・環境物質化学コース

2022-113 倉橋 健介

名古屋工業大学・大学院工学研究科

高エネルギー加速器研究機構・物質構造科学研究所

2022-112 齊藤 高志

2022-118 浅香 透

物質・材料研究機構・国際ナノアーキテクトニクス研究拠点

2022-111 土屋 敬志

東京都立大学・大学院理学研究科化学専攻

弘前大学・大学院理工学研究科

2022-110 増野 敦信

2022-117 山添 誠司

立命館大学・生命科学部生物工学科

2022-109 豊竹 洋佑

東京工業大学・フロンティア材料研究所

近畿大学・農学部応用生命化学科

2022-108 倉田 淳志

2022-116 真島 豊

早稲田大学・先進理工学部

2022-107 浦谷 浩輝

長谷川 健

若杉 昌徳

若杉 昌徳

山子 茂

山口 信次郎

中村 正治

猿山 雅亮

寺西 利治

寺西 利治

連携・融合促
進型

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大野 工司

辻井 敬亘

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島川 祐一

菅 大介

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栗原 達夫

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Determine the three-dimensional structure of 13C labeled α-synuclein(61-95) in the Langmuir-Blodgett film and supported phospholipid bilayer by
MAIRS2

Study of the generation and sustainment of high energy density plasmas due to the interaction between high power laser and structured medium

高強度レーザーと構造性媒質の相互作用による高エネルギー密度プラズマの生成・保持に関する実験研究

Study and experiment of the high-pressure gas generation by the high-power laserirradiation to the stacked CNT target

積層CNT ターゲットへの高強度レーザー照射による高圧ガス生成に関する実験研究

Preparation of multi-stimuli-responsive polymer via controlled radical polymerization

制御ラジカル重合による多重刺激応答性高分子の合成

Functional analysis of non-canonical strigolactones as plant hormones and root-derived signals「非典型的」ストリゴラクトン類の植物ホルモンおよび根圏シグナルとしての機能解析

Development of efficient conversion method of woody biomass, renewable biological resources, to advanced chemical materials

再生可能資源・木質バイオマスの先端化学材料への効率的変換法の開発

Simultaneous observation of electron transport property and phase transition of a single 3D quantum dot superlattice in an electron microscope

電子顕微鏡内での単一三次元量子ドット超格子の電子輸送特性と構造相転移挙動の同時観測

Development of bi-functional catalysts by modification of supported metal surface with metal oxide clusters

担持金属表面に金属酸化物クラスターを修飾した二元機能触媒の創製

Giant magnetic resistance on Single-Electron Transistor

単電子トランジスタにおける巨大磁気抵抗効果の検討

Manipulation of Three Dimensional Structure of Polymer Monoliths by 3D Printer

3D プリンタを用いたモノリスの3 次元構造制御

Structural Analysis of Water in Polymer Brush Layer Using Attenuated Total Reflection Near-infrared Spectroscopy

全反射近赤外分光法による高分子ブラシ層内の水の構造解析

Metal separation by solvent impregnated resin using surfactant

界面活性剤を利用した溶媒含浸樹脂による金属分離

Syntheses of novel fluoride-ion conductors using high pressures

高圧合成による新規フッ化物イオン伝導体の探索

Novel functional properties of metal oxides explored by electrochemical proton insertion

電気化学的プロトン脱挿入を利用した金属酸化物の新奇物性探索

Thermal conduction of pseudo-ordered oxide glasses

擬秩序ガラスの熱伝導

Analysis of membrane lipid-dependent fermentation stress response in acetic acid bacteria

酢酸菌における膜脂質依存的な発酵ストレス応答の解析

Analysis of the physiological functions of extracellular vesicles produced by intestinal bacteria and their application

腸内細菌が生産する細胞外膜小胞の生理機能解析と応用

Establishment of the thermally activated delayed fluorescence kinetics incorporating the dynamical effects

動的効果を考慮した熱活性化型遅延蛍光速度論の確立

－170－

九州大学・先導物質化学研究所

島根大学・総合理工学部

2022-131 田中 雅章

2022-132 斉藤 光

2022-133 宮本 光貴

東北大学・大学院農学研究科

名古屋工業大学・大学院工学研究科

2022-130 Morimaru Kida

2022-136 高橋 まさえ

GSAS, Kobe University2022-129 Mao Minoura

福岡大学・理学部

水畑 吉行

Rikkyo University, College of Science, Department ofChemistry2022-128 Kunlang Ji

2022-135 長洞 記嘉

島川 祐一

Centre for Science at Extreme Conditions and School ofChemistry, University of Edinburgh

2022-127 Torranin CHAIRUANGSRI

近畿大学・理工学部

倉田 博基

Chiang Mai University, Industrial Chemistry2022-126 Ming-Wen Chu

2022-134 松尾 司

倉田 博基

National Taiwan University, Center for Condensed Matter
Sciences

水畑 吉行

水畑 吉行

水畑 吉行

倉田 博基

倉田 博基

小野 輝男

中村 正治

松宮 由実

Osaka University, Department of Macromolecular Science

2022-125 Tadashi Inoue

国際施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

国際施設・機器利用型

国際Theoretical design of low-dimensional silicon material embedded in a flat two-dimensional sheet and exploration for operating principles

平面二次元シートに埋め込まれた低次元ケイ素材料の理論設計と動作原理の探求

Synthesis and structures of cationic aromatics bearing chalconenopyrylium units

カルコゲノピリリウム骨格をもつカチオン性芳香族化合物の合成と構造解析

Synthesis and Structural Characterization of Lewis Base Adducts of Tetrylenes

テトリレン・ルイス塩基付加体の合成と分子構造の解明

High accuracy measurement of hydrogen and helium behavior in plasma facing materials for nuclear fusion devices

核融合プラズマ対向材料中の水素・ヘリウム挙動の高精度測定

Development of a highly efficient CsPbBr3 scintillator

高効率CsPbBr3 シンチレータの開発

Preparation of high-efficiency spin-injection materials using optimization of magnetism and crystal structure

磁性及び結晶構造の最適化による高効率のスピン注入材料の作製

Analyzing chemical properties and origins of dissolved organic matter in lakes and soils by FT-ICR-MS

FT-ICR-MS を用いた湖沼及び土壌環境中溶存有機物の化学特性および起源解析

Synthesis and Characterization of Novel Group 16 Element Compounds

新規有機16 族元素化合物の合成と性質解明

High-pressure synthesis of transition metal oxides with novel physical properties

Micro- and Nano-structural Characterization by Advanced Transmission Electron Microscopy of Novel Functional Materials

国際施設・機器利用型
施設・機器利用型

Tackling the Electronic Instability of Charge-Density Waves by Electron Energy-Loss Spectroscopy

The 16th International Workshop for East Asian Young Rheologists

東アジア圏の若手レオロジストのための第16 回ワークショップ

国際

国際施設・機器利用型

連携・融合促進型

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 年度 成果報告書

4

京都大学化学研究所 令和 4 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