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

3

京都大学化学研究所 令和 3 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 3 年度

成果報告書

まえがき京都大学化学研究所は、平成２２年度から「化学関連分野の深化・連携を基軸とす
る先端・学際研究拠点」（平成２８年度から第二期）として国内外の共同利用・共同研究を推し進め、それを新たな糧としてより多様でグローバルな化学研究の展開と若手研究者の育成・輩出を図って参りました。特に本拠点では、化学関連コミュニティの研究者の皆様からの要請を踏まえながら、化学研究所の研究分野の広がりと深さに加えて、これまでの様々な連携実績を活かし、国内外の研究機関の相互協力を担保す
るハブ環境も提供しています。先端・学際的分野深耕にあたっては、関連コミュニテ
ィの研究者の皆様と化学研究所の教員が推進する分野選択型、課題提案型、施設・機器利用型、連携・融合促進型等の多彩な共同研究と、拠点として主催・共催する各種
国際会議、シンポジウム、研究会等を通じて、多様性と先進性を担保し、さらに、国際的視点に基づいて次代の化学関連分野を担う若手研究者の育成にも注力しています。また、拠点運営では、所外、学外の関連分野有識者と化学研究所の教員を委員とする共同研究委員会および運営評議会を核として、共同研究課題の公募・採択などを戦略的に遂行しております。
このようなグローバルな拠点活動が評価され、化学研究所は、平成３０年１１月１３日文部科学大臣から国際共同利用・共同研究拠点に認定され、「化学関連分野の深化・連携を基軸とする先端・学際グローバル研究拠点」として活動を強化しています。
国際拠点活動の四年目（最終年度）にあたる令和３年度には、化学研究所教員が一丸となって、１９９件の応募の中から採択された１３３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、採択数の４４％に当たる
５９件（若手国際枠７件を含む）の国際共同研究を遂行しました。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。令和４年度からは第二期の国際共同利用・共同研究拠点活動が始まります。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３年度の本拠点における研究成果をとりまとめたものです。本
報告書をご一読頂き、今後の本拠点の目指すべき方向や活動の推進方法などに関する忌憚のないご意見・ご提案などをお聞かせ下されば幸甚に存じます。
化学研究所所長 辻井 敬亘令和3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
アスペクト比の制御された金ナノらせんの合成および光学特性評価
2021-1
大阪産業技術研究所
中川 充
蓄積リングのための位置感度型アクティブ標的の開発
2021-2
理化学研究所 山口 由高
2021-3
Crystal Structure Analysis of GraE from Root-Nodule-Forming Bacterium
Kansai University Tadao Oikawa
プリパルス付与による高変換TNSAイオン加速機構実証2021-4
大阪大学レーザー科学研究所
砂原 淳
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
2021-5
試
量子科学技術研究開発機構
小平 聡
ナノ構造を持つ ISOL 用標的の開発
2021-6
理化学研究所 大西 哲哉
2021-7※ Electronic Structure of Biomimetic [Mo 3S4Fe] Clusters and its Relation to thecatalytic N2-Reduction: A Computational Study
Hokkaido University W. M. C. Sameera
元素科学分野2021-8※ Development and device evaluation of new D-π-A emitters based on
fluorinated triarylborone acceptors
Julius-Maximilians-Universität Würzburg Todd B. Marder2021-9※ Gas sensing properties research of metal oxides
Chinese Academy of Sciences Haichuan Guo2021-10※ Design and Tailoring Advanced Functional Materials:
Symmetry Operation and High Pressure Synthesis
National Taiwan University Wei-tin Chen
2020-11※ Investigating iron nitrides prepared by new high-pressure synthesis with
Mössbauer spectroscopy
University of Edinburgh Simon D. Kloß2021-12※ Small molecule activation using anionic crypto-FLPs
University of Bonn Rainer Streubel
2021-13※ Development of Unsymmetrical π-Electron Systems of Heavier Main Group
Elements and Elucidation of Their Property
Tohoku University Takeaki Iwamoto
2021-14※ C−H Borylation and Silylation under visible-light enabled Fe-catalysis
Visva-Bharati University Alakananda Hajra
2021-15※ Development of Iron-based Electrocatalysts for Electrocatalytic Conversionof Biomass into Value Added Chemicals
Indian Institute of Technology Indore Apurba K. Das
2020-16※ Iron-Catalyzed Asymmetric Carbozincation and Ring-Opening Reactions ofOxabicyclic Alkenes
Indian Institute of Engineering Science and Technology Laksmikanta Adak
2021-17Synthesis of ferrocenyl-phosphines and their application in the preparation of
Fe clusters
Tokushima University Masamichi Ogasawara※ 国際共同利用・共同研究

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2021-18極低温強磁場対応THz-STMの開発

東海大学 立崎 武弘
微弱な分子振動モードと結合させた極薄膜半導体における励起子発光の変調
2021-19大阪府立大学 桐谷 乃輔
高強度テラヘルツパルスを駆使したマルチフェロイック物質における2021-20
マグノン・フォノン励起
東京工業大学 佐藤 琢哉
高圧合成法を利用したエネルギー材料の開発
2021-21横浜国立大学 藪内 直明
Study on the physical mechanism on novel-ternary nanoparticle formation
2021-22
Meio University Yasutomi Tatetsu
Development of collaborative reaction fields based on dinuclearization of2021-23mononuclear complexes
Yokohama National University Yoshitaka Yamaguchi
磁性微粒子を用いたウルシオール塗膜の機能発現
2021-24
橘 洋一
京都市産業技術研究所
2021-25
Creation of Effective Oxidation Scavenger for Efficient Perovskite-based
Solar Cells
University of Tsukuba Takahiro Sasamori
2021-26
Development of heteroacenes with excellent photophysical andelectrochemical properties
Okayama University Koichi Mitsudo
バイオ情報学分野
2021-27※ 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
2021-28※ Developing Data-driven Deep Learning Approaches for Accurate
Identification of Protease Specific Substrate Targets and Cleavage Sites
Monash University Jiangning Song2021-29※ Unveiling the genomic contents of ecologically important marine giant viruses
CNRS Tom O. Delmont
2021-30※ Revealing associations between giant viruses and eukaryotes in the global
ocean through community networks inference and mining
CNRS Samuel Chaffron
2021-31※ A Study on Statistical Machine Learning for Efficient Graph Structured Data
Analysis
Nagoya Institute of Technology Masayuki Karasuyama2021-32
Control and Analysis of Complex Networks via Probabilistic Minimum
Dominating Sets
Toho University Jose C. Nacher
Comprehensive analysis of viral succession during the transition of multiple
2021-33
types of algal blooms
Fukui Prefectural University Keizo Nagasaki
2021-34
Development of the method for the detection of coronavirus diversity
Osaka University Tokiko Watanabe
効果的な分子ネットワーク解析方法の開発と医学・農学への応用
2021-35
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
2021-36※ Synthesis of inorganic molecules for elucidation of biosynthetic pathways ofiron-sulfur clusters
University of California, Irvine Markus W. Ribbe2021-37※ Development of new blue TADF emitters with horizontal molecularorientations
University of St Andrews Eli Zysman-Colman
2021-38※ Exploration of Cycloaddition Properties of Guanidine Functionalized
Isobenzofurans
Rudjer Boskovic Institute Davor Margetic
2021-39※ Development of hole transport materials for tin-perovskite and device
characterization
Osaka University Akinori Saeki
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
2021-40
鈴鹿医療科学大学 若林 成知
ジベンゾフェナジンを電子アクセプターとするスルースペース電荷移動型
2021-41
熱活性化遅延蛍光材料の創製
大阪大学 武田 洋平
2021-42
Chiral Silica with preferred-handed helical structure via chiral transfer
Osaka Institute of Technology Tomoyasu Hirai
高効率光電変換を志向した非対称型有機半導体分子の開発
2021-43
大阪大学 鈴木 充朗
ソルバトクロミズムを示さないπ共役双性イオンの合成と物性
2021-44
大阪大学 清水 章弘
Host-Guest Complexation of Cyclohexa-2,7-anthrylene Ethynylene
2021-45
Derivatives with [n]CPP
Shizuoka University Kenji Kobayashi
超分岐構造高分子の滑剤作用の解明と最適化
2021-46東北大学
髙橋 裕
現象解析分野2021-47※ Trace metal elemental and isotopic composition in the North Pacific Ocean:sources and internal cycling (2)Academia Sinica Tung-Yuan Ho
2021-48※ Resolving the structure-dynamics-property relationship in polymer
nanocomposites under uniaxial stretching
Stony Brook University Tadanori Koga
2021-49※ Development of simulation scheme for wall-slip of polymers
Università degli Studi di Napoli “Federico II” Giovanni Ianniruberto
2021-50※ High Frequency Response of Polymeric Liquids: Rheology and Dielectric
Relaxation
Yamagata University Sathish K. Sukumaran
2021-51※ Molecular understanding on the structures and dynamics of end-modified polymers
Suranaree University of Technology Visit Vao-soongnern
光エネルギー変換に対する振電効果：固体NMRと時間分解EPRの連携による解明
2021-52
神戸大学 小堀 康博
2021-53
Effect of microplastics on distribution of trace heavy metals in seawater
Kindai University Yuzuru Nakaguchi
イオン液体含有高分子膜を用いた金属イオンの液膜輸送に関する研究
2021-54
京都教育大学
向井 浩※ 国際共同利用・共同研究

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2021-55
2021-55

硫黄系高分子薄膜材料における硫黄元素が構成するナノ構造の空間不均一性評価
硫黄系高分子薄膜材料における硫黄元素が構成するナノ構造の空間不均一性評価
関西学院大学 藤原 明比古
2021-56
Structure analysis of polymer materials having sulfur atoms in関西学院大学
a wet state by 藤原 明比古
Structuresmall-angle
analysis of polymer
2021-56
resonant
scatteringmaterials
methodshaving sulfur atoms in a wet state byresonant small-angle scattering methods
Nagoya Institute of Technology Katsuhiro Yamamoto
Nagoya Institute of Technology Katsuhiro Yamamoto
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
2021-57
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
2021-57
北海道大学 飯田 健二
北海道大学 飯田 健二
部分フッ素化両親媒性分子の膜物性・構造に対するRf鎖長依存性の解析
2021-58
部分フッ素化両親媒性分子の膜物性・構造に対するRf鎖長依存性の解析
2021-58
群馬大学 園山 正史
群馬大学
園山 正史
2021-59
A spectroscopic analysis on bio-degradation processes of polymer thinfilm
A spectroscopic analysis on bio-degradation processes of polymer thin film
2021-59
surfaces
surfaces
Kyoto Institute of Technology Takashi Aoki
of Technology
Takashi Aoki
2021-60
Identification of an active gibberellin compoundKyoto
in theInstitutebasal land
plant
Identification ofan active gibberellin compound in the basal land plant
2021-60
Marchantia
polymorpha
Marchantia polymorpha
Kyoto University Takayuki Kohchi
Takayuki Kohchi
2021-61
Glass Transition and Molecular Dynamics of Guest LowKyoto
Mass University
Molecules in
Glass
Transition
and Molecular
2021-61theClathrateof Polymer
CrystalsDynamics of Guest Low Mass Molecules in
the Clathrate of Polymer Crystals
Osaka University Osamu Urakawa
Osaka University Osamu Urakawa
課題提案型共同研究
課題提案型共同研究
2021-62※ Nonlinear Rheological Behavior of Telechelic Ionomer with Distribution of
Nonlinear
RheologicalBehavior of Telechelic Ionomer with Distribution of2021-62※ Ionic
Stickers
at the Ends
Ionic Stickers at the Ends
Chinese Academy of Sciences Zhijie Zhang
Academyof Sciences
2021-63※ Role of PX-PH-type phospholipase Ds in plant Chinese
intracellular
membrane
traffic Zhijie Zhang
2021-63※ Role of PX-PH-type phospholipase Ds in plant intracellular membrane traffic
MRC Laboratory of Molecular Biology Yohei Ohashi
of Molecular Biology Yohei Ohashi
pollenLaboratory
development
2021-64※ Role of phosphoinositide signaling in MRC
2021-64※ Role of phosphoinositide signaling in pollen development Peking University Sheng Zhong
PekingTherapy
University Sheng Zhong
2021-65※ Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune
2021-65※ Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune
Therapy
Tsinghua University Yan-Mei Li
Tsinghua University Yan-Mei Li
2021-66※ Site-selective protein acetylation by a small molecule2021-66※ Site-selective protein acetylation by a small molecule
Fudan University Lu Zhou
Fudan University Lu Zhou
2021-67※ Orbitronics with new material systems
2021-67※ Orbitronics with new material systems
University of Ulsan Sanghoon Kim
University of Ulsan Sanghoon Kim
2021-68※ Study of characteristics of spin wave in magnetic insulator
2021-68※ Study of characteristics of spin wave in magnetic insulator
KAIST Kab-Jin Kim
KAIST Kab-Jin Kim
2021-69※ Application of ferrimagnets for spintronics devices
2021-69※ Application of ferrimagnets for spintronics
devices Federal University Alexander Samardak
Far Eastern
Eastern
Federal University
Alexander Samardak
2021-70※ Highly efficient red thermally activatedFar
delayedfluorescenceemitters with
2021-70※ stericallyHighly efficient
reddonorthermally
activated delayed fluorescence emitters withhinderedskeletonsterically hindered donor skeleton
Kyung Hee University Jang Hyuk Kwon
Kyung
Hee University Jang Hyuk Kwon
2021-71※ Developments of highly efficient and high color purity
organic
2021-71※ electroluminescent
Developments of highly
efficienthigh coloractivatedpurity organic
devicesbased andon thermallydelayed fluorescentelectroluminescent
basedon thermally
activated
ultrafast
reverseintersystemcrossingdelayed fluorescentmaterials
exhibitingdevices
materials exhibiting ultrafast reverse intersystem crossing Tsinghua University Lian Duan
Tsinghua
University Lian Duanof outer
2021-72※ Structural and functional analysis of the surface polysaccharides
Structural andfunctional
analysisof the surface polysaccharides of outer
2021-72※ membrane
vesiclesreleasedby bacteria
membrane vesicles released by bacteria
University of Naples Federico II Maria Michela Corsaro
University
NaplesII Mariaby
Michela Corsaro
2021-73※ Construction of heterologous protein
secretionofsystem
at Federico
low temperatures
Constructionof heterologous
protein secretion system at low temperatures by
2021-73※ using
cold-adapted
microorganisms
using cold-adapted microorganisms
Southwest University Xianzhu Dai
Southwest University Xianzhu Dai※ 国際共同利用・共同研究※ 国際共同利用・共同研究
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2021-74※ Optimizing sampling devices and procedures to quantify sources of metals andmicroplastics in Metro Manila, Philippines’ water resources
Polytechnic University of the Philippines Abigail P. Cid-Andres2021-75※ Fabrication of Nanotopographical Polymer Surfaces for Bactericidal
Properties-III
Stony Brook University Maya Endoh2021-76※ Synthesis of Polyether Nanocomposite Solid Polymer Electrolytes for Lithium
Ion BatteriesMichigan State University Robert C. Ferrier, Jr.
2021-77※ Verification and development of dynamic stiction theory
Yokohama National University Ken Nakano
2021-78※ Development of semiconductor quantum dot solid films and their charge
carrier dynamics
RMIT University Yasuhiro Tachibana
2021-79※ Interdisciplinary Approach to Nanostructured Materials for Applications
Université de Strasbourg Jean-Pierre Bucher
2021-80※ Novel strategy for intracellular delivery of nanomedicines
Institute for Bioengineering of Catalonia Sílvia Pujals
2021-81※ Structural and functional analysis of curvature-inducing peptides andapplication
Karlsruhe Institute of Technology Anne S. Ulrich2021-82※ Research toward stable NV centers at shallow region and spin dynamics indiamond
Leibniz institute for surface engineering Gopalakrishnan Balasubramanian2021-83※ Research of quantum controls in multi-qubit diamond quantum processors andquantum sensors
Australian National University Marcus W. Doherty
2021-84※ Molecular mechanisms for the inactivation of a growth hormone in rice
Chinese Academy of Sciences Zuhua He
2021-85※ Analysis of novel transporters for strigolactones or their biosynthetic
intermediates
University of California San Diego Yunde Zhao
2021-86※ 1,3-Dipolar Cycloaddition Reactions of Cycloparaphenylenes with
Azomethine Ylide
Nanyang Technological University Shingo Ito
2021-87※ Dendritic Amphiphilic Block Copolymers as Additive for
Polyvinylidenedifluoride Based Membranes
University of Montpellier Mona Semsarilar
2021-88※ Search for four-wave-mixing in the vacuum- Unveiling dark components in the Universe –Graduate School of Advanced Science and Engineering Kensuke Homma
2021-89※ Development of Perovskite and Perovskite-like Emitters and Their
Applications
National Tsing Hua University Hao-Wu Lin
モデルポリアルキルスチレン類を用いた分子構造と粘弾性パラメータの相関解析
2021-90名古屋大学 高野 敦志
2021-91
Study on the Regulatory Network of Plant Epidermal Cell Differentiation
Hiroshima University Rumi Tominaga
免疫賦活化するナノ集合体
2021-92
大阪大学
山崎 晶※ 国際共同利用・共同研究

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2021-93

自己集合性分子による心筋細胞移植の効率化

2021-94

共役系ポリマーの開発と非フラーレン型太陽電池の高効率化

信州大学

2021-95
2021-962021-972021-982021-992021-100
2021-1012021-1022021-103
2020-1042021-1052021-1062021-1072021-1082021-1092021-1102021-111
2021-1122021-113

柴 祐司

93

広島大学
尾坂 格 94
Demonstration of topological phase control in chalcogenide superlattice
AIST Misako Morota 95
Study of spin dynamics in garnet nanocrystal thin films prepared by coprecipitation method
Gifu University Keisuke Yamada 96
Study on electronic and magnetic behavior of perpendicularly magnetizedcobalt ferrite films
Nagoya Institute of Technology Masaaki Tanaka 97
Electronic and spintronic properties of multilayer system including
NiCo2O4 and Fe3O4
Hokkaido University Taro Nagahama 98
ナノ秒オーダーの逆項間交差を示す熱活性化遅延蛍光材料の開発
大阪大学 相澤 直矢 99
時間分解分光計測による熱活性化遅延蛍光における逆項間交差の機構解明
豊田工業大学
山方 啓 100
Functional characterization of extracellular vesicles produced by intestinalbacteria and development of their applications
Kansai University Shino Yamasaki 101
Analysis of membrane lipid-dependent fermentation stress response
in acetic acid bacteria
Ritsumeikan University Yosuke Toyotake 102
擬秩序ガラスの熱伝導弘前大学 増野 敦信 103
異常高原子価イオンを含む機能性酸化物合成とその構造物性研究
高エネルギー加速器研究機構 齊藤 高志 104
界面活性剤を抽出剤として利用した固相抽出によるEu分離法の開発
大阪府立大学工業高等専門学校 倉橋 健介 105
Fine synthesis of polymer brush on nano-platelet for functional photonic LC
Osaka University Yoshiaki Uchida 106
高分子ブラシ層内の水の構造および凍結挙動の解析
富山大学
源明 誠 107
Study on water freezing with lignocellulose nanofibers and their surface
modification toward functional materials
National Institute of Advanced Industrial Science and Technology Keita Sakakibara 108
Giant Magnetic Resistance on Single-Electron Transistor
Tokyo Institute of Technology Yutaka Majima 109
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 110
新規細胞内取込誘導タンパク質の同定
名古屋大学 桑田 啓子 111
マクロピノサイトーシスによる細胞内取込様式
慶應義塾大学 前川 大志 112
原子レベル平坦表面ダイヤモンドを用いた量情報科学研究
金沢大学 徳田 規夫 113※ 国際共同利用・共同研究－vi－

2021-114

量子センサの高感度化に向けたダイヤモンド合成と量子技術開発研究
産業技術総合研究所 牧野 俊晴 114
2021-115 Functional analysis of non-canonical strigolactones as plant hormones androot-derived signals
Meiji University Yoshiya Seto 115
2021-116 光励起に伴うシクロパラフェニレン酸化体の芳香族性・反芳香族性のスイッチング
大阪大学
藤塚 守 1162021-117 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 117
2021-118 Coupling of concentration fluctuation and orientation fluctuation in mixture ofnematic liquid crystal and solvent
Japan Women’s University Ryoko Shimada 118
連携・融合促進型共同研究
2021-119※ Determine the three-dimensional structure of 13C labeled α-synuclein(61-95)
in the Langmuir-Blodgett film and supported phospholipids bilayers by
p-MAIRS FT-IR
Middle Tennessee State University Chengshan Wang 119
2021-120※ Modulation of in-cell protein-protein interactions using mid-sized peptides
Tokyo University of Phermacy and Life Sciences Yoshio Hayashi 121
2021-121※ Instead of the 16th International Workshop for East Asian Young Rheologists
Osaka University Tadashi Inoue 123
施設・機器利用型共同研究
2021-122※ Micro- and Nano-structural characterization by advanced transmission electron microscopyof novel functional materials for battery development
Chiang Mai University Torranin Chairuangsri 126
2021-123※ Tackling the Electronic Instability of Charge-Density Waves by Electron
Energy-Loss Spectroscopy
National Taiwan University Ming-Wen Chu 1272021-124※ High-pressure synthesis of potential multiferroic oxides
University of Edinburgh Kunlang Ji 128
2021-125※ Synthesis and Characterization of Novel Group 16 Element Compouds
Rikkyo University Mao Minoura 129
2021-126 固体NMRを駆使した有機結晶および有機薄膜の分析
大阪大学
家 裕隆 1302021-127 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
島根大学 宮本 光貴 131
2021-128 希土類共ドープナノ粒子の寿命制御
九州大学
斉藤 光 1322021-129 単結晶X線構造解析を用いた、含フッ素共役分子の結晶構造におけるフルオラス相互作用の解明
茨城大学 吾郷 友宏 133
2021-130 Synthesis and Structural Characterization of Halostannylenes
Kindai University Tsukasa Matsuo 134
2021-131 Theoretical design of planar silicene nanoribbons and search for new
operating principles
Tohoku University Masae Takahashi 135※ 国際共同利用・共同研究－vii－

2021-132
2021-133

Synthesis and structures of cationic aromatics bearing thiopyrylium units
Fukuoka University Noriyoshi Nagahora 136
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
京都工芸繊維大学 布施 泰朗 137※ 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
・6th International TADF Workshop

139

・10th Aquatic Virus Workshop (AVW10)140

シンポジウム・研究会
・第 5 回 MAIRS ワークショップ

145

・第 42 回生体膜と薬物の相互作用シンポジウム

147

149

３．成果発表論文（令和 4 年 2 月までに刊行された論文で、平成 22－令和 2 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)* Ultra-high dynamic range quantum measurement retaining its sensitivity, Nat. Commun., 12,306 (2021).
2)* Mixed lead-tin perovskite films with >7 μs charge carrier lifetimes realized by maltol
post-treatment, Chem. Sci., 12, 13513–13519 (2021).
3) Discovery of Self-Assembling Small Molecules as Vaccine Adjuvants, Angew. Chem. Int.
Ed., 60, 961–969 (2021).
4) Fused-Nonacyclic Multi-Resonance Delayed Fluorescence Emitter Based on
Ladder-Thiaborin Exhibiting Narrowband Sky-Blue Emission with Accelerated Reverse
Intersystem Crossing, Angew. Chem. Int. Ed., 60, 20280–20285 (2021).
5) Synthesis of Carbazole-Fused Azaborines via a Pd-Catalyzed C-H Activation-Cyclization
Reaction, Bull. Chem. Soc. Jpn., 94, 21–23 (2021).
6) Amino-Functionalized Cage-Opened C60 Derivatives, Org. Lett., 23, 9586–9590 (2021).
7) Reductive Decarbonylation of a Cage-Opened C60 Derivative, Org. Lett., 23, 9495–9499(2021).
8) Synthesis and Oligomerization of CpM(CO)2, ACS Omega, 6, 34137–34141 (2021).
9) Water-Mediated Thermal Rearrangement of a Cage-Opened C60 Derivative, ChemPlusChem,
86, 1559–1562 (2021).
10) Cage-Expansion of Fullerenes, J. Am. Chem. Soc., 143, 12450–12454 (2021).
11) Pressure-induced annulative orifice closure of a cage-opened C60 derivative, Chem. Commun.,57, 5322–5325 (2021).
12) Precise Fixation of an NO Molecule inside Carbon Nanopores: A Long-Range
Electron–Nuclear Interaction, Angew. Chem. Int. Ed., 60, 2866–2870 (2021).
13) Morphology-Dependent Coherent Acoustic Phonon Vibrations and Phonon Beat of Au
Nanopolyhedrons, ACS Omega, 6, 5485–5489 (2021).
14) Determinants of crystal structure transformation of ionic nanocrystals in cation exchange
reactions, Science, 373, 332–337 (2021).

－ix－15) Gold Nanocluster Functionalized with Peptide Dendron Thiolates: Acceleration of the
Photocatalytic Oxidation of an Amino Alcohol in a Supramolecular Reaction Field, ACS
Catal., 11, 13180–13187 (2021).
16) Near-Zero Azimuthal Anchoring of Liquid Crystals Assisted by Viscoelastic Bottlebrush
Polymers, ACS Appl. Polym. Mater., 3, 2618–2625 (2021).
17) SOMO-HOMO Conversion in Triplet Carbenes, Org. Lett., 23, 4955–4959 (2021).
18) Evidence for Polarity-and Viscosity-Controlled Pathways in the Termination Reaction in the
Radical Polymerization of Acrylonitrile, Macromolecules, 54, 4497–4506 (2021).
19) 1,3-Diradicals Embedded in Curved Paraphenylene Units: Singlet versus Triplet State and
In-Plane Aromaticity, J. Am. Chem. Soc., 143, 7426–7439 (2021).
20) Shallow NV centers augmented by exploiting n-type diamond, Carbon, 178, 294–300(2021).
21) Low current driven vertical domain wall motion memory with an artificial ferromagnet, J.
Mag. Soc. Jpn., 45, 6–11 (2021).
22) High thermal stability and low driven current achieved by vertical domain wall motion
memory with artificial ferromagnet, Appl. Phys. Exp., 14, 023001 (2021).
23) Spin wave resonance in perpendicularly magnetized synthetic antiferromagnets, J. Mag. Soc.
Jpn., 45, 25–29 (2021).
24) Investigation of the upper critical field in artificially engineered Nb/V/Ta superlattices, J. J.
Appl. Phys., 60, 060902 (2021).
25) Estimation of Angular Momentum Compensation Temperature in GdFe Film by mMagnetic
Compton Scattering, J. Mag. Soc. Jpn., 45, 1–5 (2021).
26) Field-driven domain wall creep motion in ferrimagnetic Tb/CoFeB/MgO microwires, J. J.
Appl. Phys., 60, 020902 (2021).
27) Change of longitudinal spin Seebeck voltage with annealing in Y3Fe5O12 films formed bydensely packed nanocrystals, J. Magn. Magn. Mater., 535, 168093 (2021).
28) Interfacial Dzyaloshinskii-Moriya interaction and dampinglike spin-orbit torque in[Co/Gd/Pt]N magnetic multilayers, Phys. Rev. B, 103, 104409 (2021).
29) Observation of nonreciprocal superconducting critical field, Appl. Phys. Exp., 14, 073003(2021).
30) Positive correlation between interlayer exchange coupling and the driving current of domain
wall motion in a synthetic antiferromagnet, Appl. Phys. Lett., 119, 032407 (2021).
31) Control of antiferromagnetic resonance and the Morin temperature in cation doped
α-Fe2-xMxO3 (M = Al, Ru, Rh, and In), Appl. Phys. Lett., 119, 032408 (2021).
32) Dzyaloshinskii–Moriya interaction in noncentrosymmetric superlattices, npj Comput. Mater.,
7, 129 (2021).
33) Inhomogeneous magnetic properties characterized by simultaneous electrical and opticaldetection of spin-torque ferromagnetic resonance, Appl. Phys. Lett., 119, 192409 (2021).
34) Influence of the Dabcyl group on the cellular uptake of cationic peptides: short oligoargininesas efficient cell-penetrating peptides, Amino Acids, 53, 1033–1049 (2021).
35) Synthesis and structural confirmation of calibagenin and saxosterol, Tetrahedron, 91, 132194(2021).

－x－36) Arabidopsis PLDζ1 and PLDζ2 localize to post-Golgi membrane compartments in a partiallyoverlapping manner, Plant Mol. Biol., 108, 31–49 (2021).
37) Discovery of a Vitamin D Receptor-Silent Vitamin D Derivative That Impairs Sterol
Regulatory Element-Binding Protein in Vivo, J. Med. Chem., 64, 5689–5709 (2021).
38) Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence
Emitters with Near-Unity Photoluminescence Quantum Yields, J. Org. Chem., 86,11531–11544 (2021).
39) Effect of a twin-emitter design strategy on a previously reported thermally activated delayed
fluorescence organic light-emitting diode, Beilstein J. Org. Chem., 17, 2894–2905 (2021).
40) Acceleration of Reverse Intersystem Crossing using Different Types of Charge Transfer
States, Chem. - An Asian J., 16, 1073–1076 (2021).
41) Formation of trans-Poly(thienylenevinylene) Thin
Isomerization, Chem. Mater., 33, 5631–5638 (2021).

Films

by

Solid-State

Thermal42) Progress in recycling organic-inorganic perovskite solar cells for eco-friendly fabrication, J.
Mater. Chem. A, 9, 2612–2627 (2021).
43) Near-Ultraviolet Transparent Organic Hole-Transporting Materials Containing Partially
Oxygen-Bridged Triphenylamine Skeletons for Efficient Perovskite Solar Cells, ACS Appl.
Energy Mater., 4, 1484–1495 (2021).
44) Starburst Carbazole Derivatives as Efficient Hole Transporting Materials for Perovskite Solar
Cells, Solar RRL, 6, 2100877 (2021).
45) Deuterium and helium desorption behavior and microstructure evolution in beryllium during
annealing, J. Nucl. Mater., 544, 152686 (2021).
46) Facile Synthesis Sandwich-Structured Fe/NrGo Nanocomposite
High-Performance Lithium-Ion Batteries, Crystals, 11, 1582 (2021).

as

Anodesfor47) Synthesis of a Mechanically Planar Chiral and Axially Chiral [2]Rotaxane, Org. Lett., 23,
8678–8682 (2021).
48) Iron-catalysed enantioselective carbometalation of azabicycloalkenes, Chem. Commun., 57,
6975–6978 (2021).
49) Iron-catalyzed cross-coupling reactions tuned by bulky ortho-phenylene bisphosphine ligands,
Bull. Chem. Soc. Jpn., 94, 1125–1141 (2021).
50) Substitutional tuning of electronic phase separation in CaFe3O5, Phys. Rev. Mater., 5, 024406(2021).
51) Colossal Barocaloric Effect by Large Latent Heat Produced byIntersite-Charge-Transfer Transition, Adv. Funct. Mater., 31, 2009476 (2021).

First-Order52) Integrated sensing array of the perovskite-type LnFeO3 (Ln˭La, Pr, Nd, Sm) to discriminate
detection of volatile sulfur compounds, J. Hazard. Mater., 413, 125380 (2021).
53) Tuning magnetic anisotropy by continuous composition-gradients in a transition metal oxide,
J. Appl. Phys., 129, 183902 (2021).
54) 3D to 2D Magnetic Ordering of Fe3+ Oxides Induced by Their Layered Perovskite Structure,
Inorg. Chem., 60, 8027–8034 (2021).
55) Giant multiple caloric effects in charge transition ferrimagnet, Sci. Rep.,11, 12682 (2021).
56) Spin reorientation in tetragonally distorted spinel oxide epitaxial films, Phys. Rev. B, 104,
014422 (2021).

－xi－57) Ultrafast demagnetization in NiCo2O4 thin films probed by time-resolved microscopy, Appl.
Phys. Lett., 119, 102404 (2021).
58) Scaling of the anomalous Hall effect in perpendicularly magnetized epitaxial films of theferrimagnet, Phys. Rev. B, 104, 134407 (2021).
59) Slow oxidation of magnetite nanoparticles elucidates the limits of the Verwey transition, Nat.
Commun., 12, 6356 (2021).
60) Multi-k spin ordering in CaFe3Ti4O12 stabilized by spin-orbit coupling and further-neighborexchange, Phys. Rev. Research, 3, 043208 (2021).
61) Oxygen Release and Incorporation Behaviors Influenced by A-Site Cation Order/Disorder in
LaCa2Fe3O9 with Unusually High Valence Fe3.67+, Chem. Mater., 34, 345–350 (2022).
62) Donor-Acceptor Polymers Containing 4,8-Dithienylbenzo[1,2-b:4,5-b’]dithiophene via
Highly Selective Direct Arylation Polymerization, ACS Appl. Polym. Mater., 3, 830–836(2021).
63) Tracing the incorporation of the “ninth sulfur” into the nitrogenase cofactor precursor withselenite and tellurite, Nat. Chem., 13, 1228–1234 (2021).
64) High-order harmonic generation in graphene: Nonlinear coupling of intraband and interband
transitions, Phys. Rev. B, 103, L041408 (2021).
65) Spectral characterization of the Rashba spin-split band in a lead halide perovskite single
crystal by photocurrent heterodyne interference spectroscopy, Phys. Rev. B, 103, L081201(2021).
66) On the progress of ultrafast time-resolved THz scanning tunneling microscopy, APL Mater.,
9, 060903 (2021).
67) Determination of localized surface phonons in nanocrystalline silicon by inelastic neutron
scattering spectroscopy and its application to deuterium isotope enrichment, Phys. Rev.
Mater., 5, 066003 (2021).
68) Eukaryotic virus composition can predict the efficiency of carbon export in the global ocean,iScience, 24, 102002 (2021).
69) Quantitative Assessment of Nucleocytoplasmic Large DNA Virus and Host Interactions
Predicted by Co-Occurrence Analyses, mSphere, 6, e01298-20 (2021).
70) Draft genome sequence of medusavirus stheno, isolated from the tatakai river of Uji, Japan,
Microbiol. Resour. Announc., 10, e01323-20 (2021).
71) Discovery of Viral Myosin Genes With Complex Evolutionary History Within Plankton,
Front. Microbiol., 12, 683294 (2021).
72) RNA sequencing of medusavirus suggests remodeling of the host nuclear environment at an
early infection stage, Microbiol. Spectr., 9, e0006421 (2021).
73) Year-round dynamics of amplicon sequence variant communities differ among eukaryotes,
Mimiviridae, and prokaryotes in a coastal ecosystem, FEMS Microbio. Ecol., 97, fiab167(2021).
74) ReCGBM: a gradient boosting-based method for predicting human dicer cleavage sites, BMC
Bioinformatics, 22, 63 (2021).
75) Weighted minimum feedback vertex sets and implementation in human cancer genes
detection, BMC Bioinformatics, 22, 143 (2021).
76) Uncovering and classifying the role of driven nodes in control of complex networks, Sci.
Rep., 11, 9627 (2021).
－xii－77) ILearnPlus: A comprehensive and automated machine-learning platform for nucleic acid andprotein sequence analysis, prediction and visualization, Nucleic Acids Res., 49, e60 (2021).
78) DeepVF: A deep learning-based hybrid framework for identifying virulence factors using thestacking strategy, Brief. Bioinform., 22, bbaa125 (2021).
79) DeepBL: A deep learning-based approach for in silico discovery of beta-lactamases, Brief.
Bioinform., 22, bbaa301 (2021).
80) Computational identification of eukaryotic promoters based on cascaded deep capsule neuralnetworks, Brief. Bioinform., 22, bbaa299 (2021).
81) Probabilistic critical controllability analysis of protein interaction networks integrating
normal brain ageing gene expression profiles, Int. J. Mol. Sci., 22, 9891 (2021).
82) Anthem: A user customised tool for fast and accurate prediction of binding between peptides
and HLA class I molecules, Brief. Bioinform., 22, bbaa415 (2021).

４．参考資料165
169

4-1.令和３年度公募要領
4-2.令和３年度採択課題一覧－xiii－

－xiv－

1．共同研究成果報告2021-1
アスペクト比の制御された金ナノらせん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】貴金属ナノ構造体はサイズや形状に依存した特異な光学特性を示すことから盛んに研究されている。しかしながら、複雑なナノ構造の作製は容易ではなく、多くの課題が残されている。そこで、先行研究により見出した、分子集合体を鋳型とするらせん状金ナノワイヤーの合成法を発展させることで、簡便かつ多様なナノ構造を作製可能な手法を確立する。さらに、得られた種々のナノワイヤーの光学特性を比較することで、ナノ構造と機能の関係について検討する。
【方法】分子集合体の存在下で塩化金(III)酸を L-アスコルビン酸を用いて還元し、らせん状金ナノワイヤーを合成した。次に、超音波処理およびグロース処理により長さと直径の異なるナノワイヤーを調製した。合成した各ナノワイヤーの分散液について、紫外可視-近赤外（UV-vis-NIR）吸収および円偏光二色性（CD）スペクトルを測定した。さらに、種々の直径および長さを有するナノワイヤーについて、走査型透過電子顕微鏡によるエネルギー損失スペクトル（STEM-EELS）測定を行った。
【結果と考察】らせん状金ナノワイヤーのNIR 領域の吸収スペクトルは直径の増大および長さの減少によりブルーシフトした。
EELS 測定（Fig. 1）の結果から、光吸収スペ
クトルの変化はナノワイヤーのアスペクト比の減少による長軸モードの表面プラズモ
ン共鳴の周波数変化に対応することがわかった。ワイヤー径の変化による UV-vis 領域の吸収スペクトルの変化はわずかであったにもかかわらず、同領域の CD スペクトルは大きく変化し、一部反転、増大した。以上の結果から、らせん状金ナノワイヤーの光吸収および円偏光特性はアスペクト比とワイヤー径などのワイヤーの形状を制御することで、別々に調節できる可能性が示唆された。

Figure .1 (a) A STEM image and EELS maps of asingle gold nanowire. (b) Plots of EELS peak
positions vs. aspect ratio of gold nanowires.

【成果報告】M. Nakagawa, R. Kakehashi, N. Tokai, H. Kurata, T. Kawai, Tuning the Structure
and Chiroptical Properties of Helical Gold Nanowires Synthesized Using Supramolecular
Templates, , 2021 International Chemical Congress of Pacific Basin Societies (Virtual congress),
18/Dec/2021, 3413516.

－1－2021-2
蓄積リングのための位置感度型アクティブ標的の開発
山口由高

理化学研究所【目的と研究方法】
本研究の目的は、蓄積リングを用いたビームリサイクル技術を確立する上で必要な要素の一つである、位置感度型アクティブ標的を開発することである。内部標的を備えた蓄積リングで稀少なRIビームを周回させ、標的を通り抜けても再び標的に入射、核反応が起きるまで回し続ける、これがビームリサイクル技術の特徴である。従来の大強度RIビームを標的に１回入射して核反応研究を行う手法に比べ圧倒的に高効率である。しかしながら、内部標的の通過を繰り返す度にRIビームはエネルギーを失い、さらにエネルギー分散や角度分散が生じて、たちまち蓄積リングのアクセプタンスから外れ周回できなくなってしまう。それらを補償する装置が特別に必要だが、まず補償装置にRIビーム情報をフィードバックする必要がある。本研究では、核反応のための内部標的を、周回する個々のRIビー
ムの情報源として利用するアクティブ標的のプロトタイプを製作し、その特性を調べた。
【研究内容、結果、今後の課題】
薄膜標的をビームが通過する際に放出する二次電子を、周回するRIビームの邪魔にならないように検出器まで輸送し、標的通過の時刻と位置を特定する信号を取り出す仕組みである。RIビーム進行方向に飛び出した二次電子は静磁場と静電場の中で、加速・偏向され検出器(MCP)まで輸送され、標的上の像がMCP上に転写される。MCPではアノード信号と、
ディレーラインによる読み出しをすることで時刻と位置の情報が取得される。
図1（左写真）は本研究で試作したアクティブ標的である。特性試験のために、RIビー
ムに代わり241Amからのα線を使用した。標的にはAl蒸着マイラーフィルム（厚さ15m）を用いた。位置情報の分解能、転写画像の歪みを測定するため、標的には格子状の点に小さな穴を開けたマスクを用いた。図１の右図はそのマスク画像がMCP上に映された像を示している。詳細解析とパラメータ最適化など調整は今後引き続き行うが、当初の目標であった標的からビームの時刻と位置情報を取り出すことは可能であることが実証された。

図 1. 試作したアクティブ標的－2－

2021-3
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. In the course of a screening experiment, Rhizobium sp. strain
MTP-10005 was isolated from natural river water. Enzymological and genetic studies showedthat the translational 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 have collaborated 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 pathway of γ-resorcylate are currently unknown. The X-ray 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,and used for crystallization. Thin plate-shaped crystals were obtained using a crystallization
solution consisting of 3 M NaCl and 0.1 M citric acid buffer pH 3.5. Diffraction experiments
were performed on beamline BL-5A, Photon Factory, KEK, Japan. The crystal was mountedwith a cryoloop and cooled with a cold stream of nitrogen. Diffraction data were collected up
to 1.8 Å resolution. The crystal belonged to space group P21, with unit-cell parameters of a =34.31 Å, b = 80.90 Å, c = 43.38 Å, and β = 107.36°. The structure was determined using themolecular replacement method, while the starting model was prepared with homology
modeling. The orientation of the model was determined by calculating rotation functions. The
translational position of the rotated model was found via R-factor search accompanied bysimulated annealing refinement. The solution model was subjected to automatedmodel-building followed by iterative model-building and refinement. The structure was refinedto R-factor and Rfree of 16.6 and 20.2 %, respectively.
In the present crystal, one homodimer GraE molecule exists in an asymmetric unit and each
subunit binds chloride ions. The polypeptide chain of the protein has 112 amino acid residues.
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
β-sheets from the two subunits against each other. The putative active site is located in the cleft
made of an α-helix α1 and two β-strands β2 and β3 from one subunit and C-terminal loop fromthe other subunit. The chloride ion in the putative active site binds to the side chains of arginine
and tyrosine residues. The conserved histidine residue is positioned in the putative active site.
These residues may be involved in substrate binding or catalysis.
－3－2021-4
プリパルス付与による高変換 TNSA イオン加速機構実証
砂原淳

大阪大学

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に先行してプレパルスを適切なタイミングでターゲット照射することにより,加速イオンのエネルギー,
粒子数共に著しく増大できる可能性が理論的に見出されており,京都大学化学研究所（受け入れ若杉教授）のレーザー施設を用いて実験配置で実証実験を行なった. 図 1 に示すように 10μm 厚ポリエチレン（CH）ターゲット上のアルミニウム 1000Åのコーティング有無、及びプリパルスレベルを五段階に強度変化(条件 1→条件 5)させた φ3.7x2.9um(FWHM), 40fs(FWHM), 430mJ
AL11µm+CR39
中性
条件で TNSA イオン加速を行い、CR39 encircled 50%とすると、 ~4.1x10 W/cm ピンホール
直径100μmレーザー
磁場中性を用いて発生するプロトンのエネ
イオン
10°
ルギー分解計測を行なった。実験結
800nm (Ti:sapphire)
果はアルミコートの有無で加速さ prepulse(PP)
100mm
50mm
~10 W/cm
52mm 1れたプロトンエネルギースペクトtim eエ ネルギール（図 2）が大きく変化した.アルミ
アルミ コ ート (1000Å) ポリ エチレン 10µm or 分散方向
コート無し（図２下）では(条件 3)
ポリ エチレン 薄膜10µmのプリパルス(PP)レベルを超える 図 1 実験配置と TNSA イオン加速が抑制されるの小に対し,(図 2 上)に示したアルミコ
条件1
条件2
Alコ
ート
ートを施したターゲットではプロ
条件3
CH薄膜
条件4
トンの数、最大エネルギー共にプリ
条件5
大パルスの増大に伴って単調に増大To
pEnergyPPレ ベル増で 加速特性向上 d a ta !
している. このことは透明ターゲ
Al11umで覆われている部分
原点ット TNSA 加速におけるプリパルス
条件1 小のシャインスルー制御の重要性を
条件2
条件3
プロトン
CH薄膜
示している.本実験により、プリプ
1mm間隔
条件4
ラズマを付与による高効率 TNSA イ
条件5 大オン加速（加速プロトン数、最大エEnergyネルギーの増大）の実験的な実証デ原点 PPレ ベル増で 条件3 を 境に加速特性が悪化
0.85
4 3 2
1
ータが得られた.プリパルスによるEnergy [MeV]
誘電体の電離過程、プラズマ化、レ6.1 7.0 8.6
12.3 13.3 Distance [mm]ーザーとターゲットの相互作用の
図 2 測定されたプロトンの energy spectrum
観点から目下データ解析中である.
19

4 0 fs12

0.6 ns－4－22

2021-5
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
小平聡

量子科学技術研究開発機構

通常の放射線治療で用いる照射線量率（0.03 Gy/s 程度）に比べて 1000 倍以上の極端に高い線量率（>40 Gy/s）で照射する超高線量率放射線がん治療（FLASH）では、腫瘍への治療効果を維持しつつ、周囲の正常組織への副作用の低減が期待される新しい治療照射法である。FLASH 照射効果は細胞や動物を用いた生物実験によって確認されており、放射線が生体中（水）で生成する放射線
分解生成物同士の再結合や反応過程における溶存酸素量低下と考えられている、実験的なエビデン
スは得られていない。本研究では照射線量率に対する水の放射線分解生成物の収率依存性の実測による作用機序の解明を目的としている。最終的には、治療計画時の臨床効果を推定するシミュレー
ションコードへの実装を通じ、我が国における FLASH 治療の進展に貢献したいと考えている。
これまで、水中に生成したヒドロキシルラジカル（OH ラジカル）と反応し蛍光を呈する 3-クマリン酸-カルボン酸（C3CA）水溶液系を用いて、30-60 MeV の陽子線と 130 MeV/u の炭素線の高線量率照射による溶存酸素量低下やラジカル再結合が示唆されるデータが得られてきている。これはOH ラジカル収率の変化ではなく、C3CA が OH ラジカルを捕捉して生成する蛍光性の 7-ヒドロキ
シ-クマリン-3-カルボン酸（7OH-C3CA）の収率が周囲の酸素量に依存することを利用している。本
研究課題では、京大化研において開発・整備が進められている電子線加速器を用いて、数 10MeV の
電子線の高線量率照射による放射線分解生成物の収率測定に向けた準備を進めている。
2022 年 3 月 9 日から 11 日かけて電子線加速器における照射実験系の確立と放射線分解生成物の測定試験を予定しており、本報告書では実験データを示すことはできないが、準備状況について報告する。京大化研の加速器で得られる電子線を用いて放射線化学収率を定量測定するためには、①電子線の吸収線量測定、②照射線量の制御、③照射野平坦度測定が必要である。①吸収線量測定には、放射線治療の品質評価標準であるアドバンストマーカス電離箱（PTW・型式 34045）を用い、その出力電荷は電位計（ケースレー・型式 6517B）により計数する。この電離箱と電位計の組み合
わせに対する線量校正をコバルト 60 線源を用いて実施した（日本医学物理学会・標準測定法 01 に準拠）。照射線量のビームモニターとして、大口径（有効直径 170mm）の大気開放型並行平板電離箱（応用技研・型式 AE-175）を用い、出力電荷をデジタルカレントインテグレータ（ORTEC・Model439）
によりモニターカウントとして計数する。照射試料位置でのマーカス電離箱の水吸収線量値を用いてビームモニターカウント値を校正し、照射線量を制御する予定である。照射野の平坦度測定は試料への均一照射に重要であり、直径 30mm 程度内の照射線量が±5%以内が望ましい。照射野形成の確認は ZnS 蛍光板、定量測定にはラジオクロミックフィルム（Ashland・型式 EBT3）を用いる予定である。2022 年 3 月の実験では、まず電子線の照射野形成と線量測定・ビームモニターの動作・
運用確認を行う。その後、C3CA 水溶液を用いた 7OH-C3CA 収率の測定試験を行う予定である。

－5－

2021-6ナノ構造を持つ ISOL 用標的の開発
大西哲哉 理化学研究所[目的] 不安定核生成法の一つである ISOL 法では、標的に高速の粒子を照射し、標的内で生成した不安定核を、標的を高温(～2000℃)にすることで取り出している。そのため、高温でも蒸気圧が低くかつ融点も高い、炭化物が標的として用いられることが多い。しかし、これまでの研究によって、炭化物標的の寿命が約一週間程度であることが分かっている。これは、高温環境下では炭化物の焼結が進むため、標的内部の隙間が小さくなり、不安定核が出てこなくなるためである。解決策として、近年カーボンナ
ノチューブを用いた炭化物標的が提案されるが、ナノ構造を持つが故に燃焼しやすく、取り扱いには専用の設備が必要である。本研究の目的は、カーボンナノチューブやグラフェン等のナノ構造をもつ新たな炭化物を用いて、取り扱いやすい ISOL 用標的を開発することである。
[実験手法] 対象とする元素の化合物(酸化物など)を炭素材料と混合し、高圧をかけ、厚さ 1 mm、直径 20 mm 程度の円板標的を作成する。作成した標的は真空チェンバー内で高温に加熱し、炭化物へと変換する。作成した炭化物標的は、電子顕微鏡を用いて、そのナノ構造を調べる。その後、電子ビーム
もしくは陽子ビームを照射し、不安定核生成量の変化から標的寿命や生成効率などを調べる。
本年度は、グラフェンを用いた円板標的の取り扱い方法に関する開発及び環境整備を行った。昨年度の結果から、炭化物の燃焼速度が予想していたよりも非常に速いことが判明した。そこで安全性を考慮
し、標的取り扱い法や作業環境の整備を先に行うこととした。炭化作業及びイオン源でのテストのしやすさを考慮し、作業場所としては理化学研究所仁科加速器科学研究センター E21 実験室内 RTM 前室のフードとした。
[結果] 作業環境の整備として、RTM 前室フード周りの環境整備しつつ、フード内に真空引き対応のガス置換型グローブボックスを導入した。大きさとしてフード内に収まり、かつ、標的関係の作業ができるものを選んだ。(写真 1a) 参照。) 置換ガスには窒素ガスを用いている。作業時には、標的入り小型
真空容器と必要な道具をあらかじめグローブボックス内に入れ、真空引きによるガス置換を行う。その際、十分に酸素濃度を下げる必要があるため、ガス置換を三回行うことで、酸素濃度が 10-4 %以下になることを担保した。炭化標的を用いた作業、具体的には標的槽の載せ替え、を行いながら、グローブボッ
クスを使用したときの作業手順の確認及びマニュアル作りを行った。作業の様子は写真 1b) を参照のこ
と。

a)

b)

c)

写真 1: a) フード内グローブボックスの様子。 b) グローブボックス内での標的作業。標的槽間での移し替え作業を示している。c) リモートハンドリング用標的槽に載せられた炭化ウラン標的。標的円板が43 枚載せられている。
現在は、炭化標的を昨年度制作したリモートハンドリング用標的槽に移し替え(写真 1c)参照)、イオン
源にセットし実際に電子ビームによる照射実験(不安定核生成実験)を準備している。
[考察] 今年度の整備の結果、炭化標的を安全に取り扱う環境が整備された。来年度は照射後の放射化した標的の取り扱いについて、手順を検討しつつマニュアル作り及び環境整備を行う予定である。
その後、炭化標的の製作を条件を変えて製作を行っていく予定である。
[成果報告] 特になし。
－6－

2021-7（国際）Electronic Structure of Biomimetic [Mo3S4Fe] Clusters and its
Relation to the catalytic N2-Reduction: A Computational Study
W. M. C. Sameera

Hokkaido University

The development of transition metal clusters is one of the main themes of inorganic
chemistry. Quantitative details of the electronic structure of the transition metal
complexes and clusters and their relations to catalytic activity cannot be rationalized
from the experimental results alone. Density functional theory (DFT) can provide
quantitative insights into the electronic structure and function relationships.
Objectives: Determine the electronic structure of the N2bound [Mo3S4Fe] clusters; [{Cp*3Mo3S4Fe}2(μ-N2)]2– (a),[CpXL3Mo3S4Fe(N2)]–

(CpR

=

CpXL

(b),

and

([CpXL3Mo3S4Fe(N2SiPh3)] (c).
Computational methods: Geometries of the possible spinstates of a, b, and c transition metal clusters were optimized
using DFT and standard basis sets.
Results and discussion: According to DFT calculations, theground state of a, b, and c transition metal clusters is S = 0.
Structural parameters of the optimized ground state structures are in agreement with
the X-ray structures and spectroscopic properties. Electronic structure analysis
indicated that the oxidation state of Fe in all three systems is Fe(II) but slightly
reduced.
Publications: Two joint publications were made from this project in this FY.
(a) W. M. C. Sameera, Y. Takeda, Y. Ohki, “Transition metal catalyzed cross-coupling
and nitrogen reduction reactions: lessons from computational studies”, Advances in
Organometallic Chemistry, 78, 2022.
(b) 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,“Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes”, 12 May 2021,
PREPRINT(Version1)

available

https://doi.org/10.21203/rs.3.rs-477541/v1

－7－

at

Research

Square2021-8（国際）Development and device evaluation of new D-π-A emitters based on
fluorinated triarylborone acceptors
Todd 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 perpendicular to its plane. Triarylboranes have been
employed for a number of applications 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. In applications, electronic or steric protection of boron atom is necessary to reduce
reactivity of the boron center toward nucleophiles. We and others have recently reported
methodologies to enhance the accepting properties as well as the stability of boron by the
introduction of ortho-trifluoromethylaryl moieties. Recently, we computationally designed a seriesof D-π-A TADF emitters with fluorinated triarylboron acceptors. The synthesized emitters showed
blue to red emission 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 effectiveness of our design
strategy for triarylboron-based TADF emitters based on accurate theoretical descriptions of thelocal and charge-transfer states. However, their TADF performance in host materials and device
efficiencies have not yet been characterized. Thus, a series of selected D-π-A TADF emitters (theemission wavelengths in 1% PMMA were 477, 568, and 598 nm) with fluorinated triarylboron
acceptors were synthesized in sufficient quantities (227 – 700 mg) by the Würzburg group whichwere sent to the Kaji group in Kyoto who subsequently constructed OLED devices from thesecompounds and examined their properties.
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 having carried out the chemical
synthesis of the chromophores and the Kaji
Figure 1. Fabricated OLEDs by Kaji group
group carrying out the photophysicalusing our designed materials.
measurements, device fabrication andtesting (Figure 1). We found that our designed molecules exhibited efficient RISC with the rate
constant exceeding 106 s−1. This has also led to suggested design features for new compounds
which we plan to prepare and evaluate in the coming year. We anticipate that a breakthrough in
OLED performance can be achieved by continuing our collaborative work, and this is highly
desired in both the academic and industrial communities.

－8－

2021-9（国際）Gas sensing properties research of metal oxides
Haichuan Guo

Chinese Academy of Sciences

Introduction
The perovskite-type oxides are widely used to detect organic gases because of highsensitivity and excellent stability, which demonstrates excellent application potential in
the field of gas sensors. Doping of perovskite oxide usually change the crystal structure
as well as the electronic structure, thereby effecting the gas sensing properties. Herein,
we succeeded in doping Lu on B-site of perovskite oxide LaFeO3, and significantly
improve the gas sensing performance for ethanol.
Experiments and results
LaFe1-xLuxO3 (x = 0, 0.1) were synthesized by the citrate sol-gel method using metal
nitrates. As-prepared oxide powders were dispersed in deionized water and drop-coatedon alumina ceramic substrates with comb-type Au electrodes. The ceramic chips were
calcined at 300oC for 1 h to strengthen the stability and repeatability. Gas sensing
properties were measured using an intelligent gas sensing analysis system by the static
volumetric method. The response value is the ratio of resistance of sample measured in
100 ppm organic gas to that measured in air.
As the XRD patterns shown in Fig.1, all the peaks shift to low angles slightly after
the partial substitution of smaller Fe3+ (radius: 0.65 Å) on B-site by larger Lu3+ (0.86 Å).
Although the response for acetone nearly keep constant after doping, the improvement of
the gas sensing performance for ethanol is obvious (Fig.2). The response increase from56.2 for LaFeO3 to 756.0 for LaFe0.9Lu0.1O3. The lattice expansion should not the only
reason of the dramatic change. The local lattice distortion and the change of band structurecausing by d0 Lu3+ doping can also be considered.

Response

800.0
600.0
400.0
200.0
0.0
LaFeO3

Fig.1 XRD patterns of LaFe1-xLuxO3

acetoneethanol

LaFe0.9Lu0.1O3

Fig.2 Gas sensing performance for organic gases－9－2021-10（国際）Design and Tailoring Advanced Functional Materials:
Symmetry Operation and High Pressure Synthesis
Wei-tin Chen

National Taiwan University[Introduction] In modern condensed matter sciences, the exploration of novel functionalities
and exotic physical phenomena is motivated by fundamental scientific understanding andpotential technology applications. High pressure synthesis techniques are one of most importantand effect methods to prepare such novel materials. With previously supported project, we havesuccessfully demonstrated the effectiveness and powerfulness of high-pressure synthesis, andthis project proposes to continue the utilization of such unique techniques for novel materials
exploration. It is targeted to design and investigate, for instance, ferroelectric, magnetic or
multiferroic compounds, which usually contains unusual high valence state or showing exotic
structural/charge/orbital/spin phase transitions. With the 6-8 two-stage Kawai-type 111 geometry
and cubic anvil DIA-type high-pressure apparatus equipped at Advanced Solid State Chemistry
Laboratory (Shimakawa lab), extreme pressure and temperature synthesis conditions wererealized for novel materials synthesis, and further high resolution synchrotron x-ray diffraction
experiments were conducted at Taiwan with joint research beamtime.
[Results and discussion] The joint research remains difficult with the situation of pandemic inyear 2021. Nevertheless, high pressure experiments were conducted Prof. Shimakawa lab, andhigh resolution SXRD data were collected at Taiwan Photon Source, NSRRC. For example, thecolossal barocaloric effect by large latent heat produced by first order intersite charge transfer
transition in NdCu3Fe4O12 quadruple perovskite, showing potential application in efficient
refrigeration. [1] A series of AMn7O12 quadruple perovskite solid solutions were designed toinvestigate the long-standing conundrum of colossal magnetoresistance in manganite perovskites.
With high resolution SXRD and NPD with detailed symmetry operation analysis, alternatingordered-insulating and disordered-conducting electron stripes arrangement forms a new state ofmatter (Fig. 1). [2] Magnetic structure and spin reorientation
behavior was observed and studied in B-site disordered
PrFe0.5Cr0.5O3 perovskite, [3] further investigation on
praseodymium-containing perovskites are ongoing. We arecontinuing further exploration of novel functional oxidematerials with exotic physical behaviors.
[References]
1. Y. Kosugi et. al., Adv. Funct. Mater., 31, 2009476 (2021)
2. W.-T. Chen et. al., Nat. Commun., 12, 6319 (2021)
3. C.-W. Wang et. al., JMMM, 538, 168273 (2021)－10－

Fig. 1 Compositional phase diagram andorbital orderings of AMn7O12
quadruple perovskites.

2021-11（国際）Investigating iron nitrides prepared by new high-pressure synthesis with
Mössbauer spectroscopy
Simon D. Kloß University of Edinburgh

Transition metal nitrides are an important class of materials with applications as abrasives,semiconductors, superconductors, Li-ion conductors, and thermoelectrics. However, nitrogen-richtransition metal nitrides in high oxidation states were notoriously difficult to prepare owing to thechemical inertness of N2 and the positive electron affinity of nitrogen leading to elimination of N2
at elevated temperatures. The research group in Edinburgh found a versatile synthesis route using
azide-mediated oxidation under pressure that is used to prepare the highly oxidised ternary nitride
Ca4FeN4 containing Fe4+ ions. In the joint research program we investigated new multinary ironnitrides with unprecedented physical and chemical properties. A key step in the investigation ofthese compounds is the assignment of the iron oxidation state with 57Fe Mössbauer spectroscopy,
which is often non-trivial owing to complicated structures.
We found that this nitridometallate features trigonal planar [FeN3]5− anions with low-spin
Fe4+ and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterisedby neutron diffraction, 57Fe-Mössbauer and magnetisation measurements. Azide-mediated highpressure synthesis opens a way to the discovery of highly oxidised nitrides.

Fig. Crystal structure (right) and 57Fe Mössbauer spectra at 10 K (left) of Ca4FeN4.
References
1. S. D. Kloß, A. Haffner, P. Manuel, M. Goto, Y. Shimakawa, & J. P. Attfield, Preparation ofiron(IV) nitridoferrate Ca4FeN4 through azide-mediated oxidation under high-pressure,
Nature Communications, 2021, 12, 571.

－11－

2021-12（国際）－12－2021-13（国際）Development of Unsymmetrical π-Electron Systems of Heavier Main
Group Elements and Elucidation of Their Property
Takeaki Iwamoto

Tohoku University

Objectives: π-Electron systems containing multiple bonds of heavier main group elements have beenstudied as prospects for advanced materials and reagents for small molecule activation. We aimed atdeveloping unsymmetrical π-electron systems containing a double bond between group-14 and group13 elements, which remain scarce compared to other heavier π-electron systems.
Experimental Methods: Dialkylborasilene 1 (Chart 1) was synthesized by the lithium-naphthalenide
reduction of the corresponding (chlorosilyl)chloroborane obtained from an isolable dialkylsilylene
with TMP-substituted dichloroborane (TMP = 2,2,6,6-tetramethylpiperidyl).
Outcomes: Novel dialkylborasilene 1 was isolated as red crystals in 74% yield. Preliminary X-ray
single crystal diffraction (XRD) analysis revealed that in the solid state 1 adopts a non-planar structurewith the sum of the angles around the three-coordinate silicon atom of 327°. Borasilene 1 reacted with
4-(dimethylamino)pyridine (DMAP) to provide a formal dearomative [2+2]-cycloadduct 2 as yellow
crystals. It should be noted that 1 reacted with H2 at ambient pressure at room temperature to provide(hydridosilyl)hydroborane 3 as a major product, and it suggests borasilene 1 can activate other small
molecules.
Analysis: Borasilene 1 and its DMAP adduct 2 were fully characterized by a combination of NMR
spectroscopy, elemental analysis, and XRD analysis.
Chart 1.

This project was done in collaboration with Professors Norihiro Tokitoh (ICR Partner Researcher) and
Shigeyoshi Inoue (International Collaborating Researcher, Technical University of München,
Germany).
Publications: S. Abe, T. Iwamoto, “Synthesis and Property of Silicon-Boron Doubly-Bonded
Compounds Containing an Unsaturated Silicon Atom Substituted by Two Alkyl Groups or(Alkyl)(Amino) Groups”, the 102nd annual meeting of the Chemical Society of Japan, March 25, 2022.

－13－

2021-14（国際）C−H Borylation and Silylation under visible-light enabled
Fe-catalysis
Alakananda Hajra

Visva-Bharati University

Objective: Fe-catalyzed sp2-C−H borylation and silylation of alkenes andimidazo[1,2-a]pyridines under visible light mediated photoredox catalysis
Visible-light photocatalysis has become an impressive tool in organic
synthesis. In this realm, the merger of transition metal catalysis and visible light
photoredox catalysis offers an exciting opportunity to perform the organic
transformations in mild conditions. Organosilicon compounds are one of the vitalsynthetic 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. Imidazopyridine, an important class of nitrogencontaining heterocycles, shows a wide range of biological activities. Presently weare 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 latestage modification of the compound.

－14－2021-15（国際）－15－2021-16（国際）Iron-Catalyzed Asymmetric Carbozincation and Ring-Opening
Reactions of Oxabicyclic Alkenes
Laksmikanta Adak

Indian Institute of Engineering Science and Technology

The transition-metal-catalyzed carbometalation of alkenes has attracted considerable interest
among synthetic organic chemists, as it offers a useful pathway for the efficient and selective
construction of carbon-carbon bonds. Because of the importance of asymmetric reaction forthe synthesis of pharmaceuticals and natural products, significant efforts have been made to
develop catalytic enantioselective carbometalation reactions of olefins. Palladium, rhodium,copper, and iridium-catalyzed asymmetric transformations of oxa- and azabicyclic alkenes
have been extensively studied, where enantioposition-selective addition of oxygen, nitrogen,and carbon nucleophiles brings about subsequent ring-opening reactions provide access toenantioenriched compounds bearing multiple stereocenters. Only one example was found forthe catalytic asymmetric addition of terminal alkynes to oxabenzonorbornadienes without thering opening, which was achieved by use of a chiral phosphine-cobalt catalyst system.
Although the use of iron catalysts in organic synthesis are attracting increased attention due
to its economic and ecological points, but there application in enantioselective
carbometalation has been limited to only highly strained cyclopropene derivatives. In thisstudy, we have developed an iron-catalyzed enantioselective carbometallation: The screeningof reaction conditions for iron-catalyzed enantioselective carbozincation of azabicyclic alkene
with arylzinc reagent were performed. Various chiral ligands and metal salts were used for thescreening and optimization of reaction condition. As shown below, it was found that thecatalytic combination of FeCl3 and (S,S)-Chiraphos provided the best result for theenantioselective carbometalation reaction.

Publications:(1) “Iron-catalysed enantioselective carbometalation of azabicycloalkenes” Adak, L.; Jin, M.;
Saito, S.; Kawabata, T.; Itoh, T.; Ito, S.; Sharma, A. K.; Gower, N. J.; Cogswell, P.; Geldsetzer,
J.; Takaya, H.; Isozaki, K.; Nakamura, M. Chem. Commun. 2021, 57, 6975‒6978.

－16－2021-17Synthesis of ferrocenyl-phosphines and their application in the preparationof Fe clusters
Masamichi Ogasawara Tokushima University
Phosphaferrocenes are by far the most investigated among the various heterometallocenes
reported to date. Since the phosphorus atom in a phosphaferrocene retains a lone pair on it,
phosphaferrocenes have been used as P-donor ligands for transition metals. In the joint
research project of this fiscal year, our research team collaborated with the Ohki group of ICR,
Kyoto University, to establish a versatile method to prepare monophosphaferrocenes. This
work was published in a scientific journal this year.[1]A previously reported protocol for preparing monophosphaferrocenes requires two
equivalents of [(mesitylene)FeCp][PF6] (A), which reacts with a mixture of phospholide anions
and phenyllithium generated by the reductive cleavage of the exocyclic P-C bond in
P-phenylphospholes with metallic lithium (Figure 1). In this study, we attained a 50%
reduction of required A by the use
2 equiv.

of inexpensive aluminium chloride
as a phenyllithium scavenger andEt3N for trapping Lewis acidic
triphenlylalminiumLiP

phospholide and complex A was

Li (excess)PPhproposed to proceed via the initial
nucleophilic
negatively

attackcharged

of

A

PF6–

Fe

phosphorus

Our next plan is to applyP––1) AlCl3 (1/3 equiv.)
P Li+
P Li+ 2) Et3N (excess)++
1/3 Ph3Al-NEt3
PhLi[(mesitylene)FeCp]PF6 (A)1 equiv.

theatom to the iron(II) center in A.

Fe

Figure 1. A known protocol reported by Roberts & Wells (1986).

byproduct(Figure 2). The reaction between a–+ PhLi
P Li+

Fe +

P

72%
Figure 2. A modified and versatile method to prepare monophosphaferrocenes. An example to furnish 3,4-dimethylphosphaferrocene
is shown.

monophosphaferrocenes as supporting ligands for Fe-based metal-cluster complexes.
Publication from this joint project:[1] Kakeru Masaoka, Manami Ohkubo, Haruka Taue, Masayuki Wakioka, Yasuhiro Ohki, andMasamichi Ogasawara, “Synthesis of Monophosphaferrocenes Revisited”, ChemistrySelect 2022, 7,
e202104472.

doi: 10.1002/slct.202104472.

－17－2021-18極低温強磁場対応 THz-STM の開発
立崎武弘 東海大学

現代物性物理学における最先端の関心である非平衡量子系の動的挙動を実験的に解き明かすため、ピコ秒時間分解能とナノメートル空間分解能、1 meV エネルギー高分解能を達成する計測技術の確立を目指している。この技術はテラヘルツ（THz）パルス
をトンネルバイアスに利用したピコ秒の時間分解能を有する走査トンネル顕微鏡（STM）でによって実現される。本研究では化学研究所

金光研究室において、THz-

STM に関わる以下 4 点の開発を行い、低温強磁場 THz-STM として必要な機能を備えた原子像の観察が可能な装置を確立できた。
［１］高安定駆動機構を備えた極低温対応 STM ヘッドを改良し、冷凍機外からレー
ザービームを導入して探針先端を光学観察可能な STM ヘッドを開発した。本光学系を利用することで、試料表面における 100 m スケールの微細構造と探針先端を外部より観察可能となった［図 1(a)］。
［２］超電導マグネット内に設置した STM ヘッドへ探針と試料を搬送する機構と、真空内で試料を劈開してクリーンで平坦な試料表面を得るための機構を備えた真空チ
ャンバを構築した［図 1(b)］。また、超電導マグネットは 10 T 磁場が印加可能であることを確認し、強磁場 STM 計測が可能な装置を構築できた。
［３］液体ヘリウム貯め込み式冷凍機内に設置した STM を制御するエレクトロニク
スを最適化し、ノイズフロア≲10 fA の低ノイズ測定系を構築した［図 1(c)］。電源起因のノイズが 60 Hz と 300 Hz で 10 fA を越えているが、このノイズレベルであれば安定
して原子像を得られる。
［４］高配向性熱分解グラファイト（HOPG）表面を、白金イリジウム（PtIr）探針で計測した結果、HOPG 表面原子を計測できることを確認できた。

図 1

成果

(a) 顕微望遠鏡によって観察した試料表面と探針先端の光学像 (b) 構築した真空チャンバと試料搬送機構、試料表面処理機構の外観
スペクトル(c) 開発した装置の電気ノイズ(d) HOPG 表面観察像■成果：論文発表[1] T. Tachizaki, Kan Hayashi, Yoshihiko Kanemitsu, and Hideki Hirori, APL Materials 9,060903 (2021).
－18－

2021-19
微弱な分子振動モードと結合させた極薄膜半導体における励起子発光の変調
桐谷乃輔

大阪府立大学

本研究は、帯電環境におけるデバイ長程度の厚みしか持たない二次元半導体に対して、隣接し電子相互作用をした分子の振動モードを変調させることで、結合・連動した二次元半導体の電子状態の変調を巨視的に起こすことを目的に研究を進めている。
微弱な振動モードから、半導体の電子状態を変調するという新たな物質操作法の開拓に繋がると期待している。当初、分子振動モードと分子の電子状態に強い相関関係を持つ酸化還元活性分子に対して、検討を進めた。振動モードを制御するため光共振器と分子種の結合を試みた。種々の分子溶液の濃度を調整して、結合を試みたが非常に高い濃度の分子溶液環境が必要となることが判明した。さらに検証を進めるためには、
分子/二次元半導体界面を効果的に検証するための低濃度化が必要となるものと考えている。あわせて検証を進めた他の分子種として、強いプロトン供給能を有する超酸分子と二次元半導体界面について研究を行なった。超酸分子種においては、分子接合によりフォトルミネッセンス光を数百倍に定量的に上昇させることが可能であるが、そのメカニズムを検証した。分子種の二次元半導体表面への接合が鍵となることを明らかとした。このことは、分子種の状態（振動モードなど）に二次元半導体の巨視的な光学物性が強く変調を受けることを意味している。今後、分子内振動モードに強制的な変調を加えることができれば、特定の相互作用や酸化状態を誘起し、界面で相互作用をした二次元半導体の光学特性が連動して変動・振動するなど、極微弱な分子振動の情報を巨視的な観測量（半導体の状態変化）として表出できると期待している。
学会発表：
1. T. Nakahara et al., " Organic-Polymer Coated Superacid-Treated Tungsten
Disulfide with Air-Stable Strong Photoluminescence", 2021 MRS Fall Meeting &Exhibit (virtual conference), 2021, 11, 6 (Oral).
2. 中原隆宏, 吉村武, 藤村紀文, 桐谷乃輔, パラフィン被覆による WS2 発光強度向上のメカニズムの考察, 第 82 回応用物理学会秋季学術講演会, 2021 年 9 月.

－19－

2021-20
高強度テラヘルツパルスを駆使したマルチフェロイック物質におけるマ
グノン・フォノン励起佐藤琢哉

東京工業大学【目的】
強誘電性と（反）強磁性を併せ持つマルチフェロイック物質は次世代の機能的スピン
トロニクス材料として注目されている。マルチフェロイック特性を室温で示す唯一の物質であり、電場による磁性制御、磁場による電気分極制御が実現されている。過去にラマン散乱や赤外吸収によってフォノンやマグノンがテラヘルツ帯に存在することが報告されている。申請者は、これまで近赤外フェムト秒光パルスを用いて、NiO、CoO、
YMnO3、ガーネット、BiFeO3 等のフォノン、マグノンをコヒーレントに励起し、その時
空間ダイナミクスを観測する研究を行ってきた。また、そのメカニズムを光パルスの電場成分によるインパルシブ誘導ラマン散乱に基づいて解明してきた。本研究では、
高強度テラヘルツ励起によって、非線形なマグノン励起を伴う物性制御の確立を目指
して実験装置の開発を行った。
【実験方法】
マグノンを強力なテラヘルツ磁場で励起するために、フェムト秒パルスレーザーのLiNbO3 結晶中での光整流効果を用いた高強度なテラヘルツパルス発生の光学系の構築を共同研究者（廣理、金光）と協力して行った。さらに、発生させた高強度テラヘルツ
磁場により磁性体の磁化変化を測定するための光ファラデー回転およびカー回転測定のための光学実験系を構築した。
【実験結果】
フェムト秒パルスレーザーによって発生させたテラヘルツパルスの最大電場強度は１
MV/cm を超えており、極めて大きな磁化変化を誘起することが期待できる。実際に、反強磁性体試料中（HoFeO3）のテラヘルツ帯にあるマグノンを励起し観測することに成功した。とくに、励起磁場強度とともにマグノンのピーク周波数が大きくレッドシフト
しており、大振幅のマグノン励起を実現したことを確かめることができた。
【考察】
観測された反強磁性体におけるマグノン振動を理論的に説明するためにランダウ・リ
フシッツ・ギルバート方程式による解析を行った。低強度の励起磁場領域ではこの理論モデルによっておおよそ再現された。一方で、高強度な励起磁場領域では、周波数変化や時間波形の非対称性など理論モデルでは再現できない現象があることが分かった。これまでに、このような極端に非線形なマグノン振動を観測した例はなく、非線形振動領域での新たな理論モデルの構築を促す結果を得ることに成功したといえる。

－20－

2021-21－21－

2021-22－22－

2021-23
Development of collaborative reaction fields based on dinuclearization ofmononuclear complexes
Yoshitaka Yamaguchi Yokohama National University
A tridentate pincer-type ligand is often used to provide an appropriate steric and electronic
environment around the metal center and thus pincer-type complexes have received significant
attention. We have already reported the synthesis of a series of pincer-type nickel(II) complexes
utilizing a combination of -aminoketonato or -diketiminato frameworks with a third donorsuch as phosphino or amino group. Our study on
nickel(II) complexes revealed that the modificationONof the ligand framework has a significant influence

Ni

Cl

N

Ni

N

N

O
Cl

N

Ni

Cl

N

Ni

Cl

on the catalytic performance such as in the biaryl

PPh2

NEt2

PPh2

NEt2

Ni-ONP

Ni-ONN

Ni-NNP

Ni-NNN

cross-coupling reaction (Dalton Trans. 2018, 47,-aminoketonato-type-diketiminato-type

8003.; Eur. J. Inorg. Chem. 2019, 126.). We have recently demonstrated that (i) Ni-ONP serves
as a catalyst in the highly Markovnikov-selective hydroboration of vinylarenes withbis(pinacolato)diboron (B2Pin2) (Org. Lett. 2020, 22, 4033.) and that (ii) Ni-ONN shows highcatalytic activity for the synthesis of alkyl aryl ethers via the cross-coupling of aryl halides withprimary and secondary aliphatic alcohols in the presence of B2Pin2 and KOtBu (Adv. Synth. Catal.
2021, 363, 1625.). We have continuously focused our attention on catalytic transformations
promoted by well-defined these nickel(II) complexes.
The hydrosilylation of alkenes is one of the most important processes to produce organosiliconcompounds. Platinum-catalyzed alkene hydrosilylation is industrially the most frequently
conducted catalytic processes. However, recently, the economic and environmental concerns
associated with precious metal catalysts have led to considerable interest in replacing them withcatalysts based on earth-abundant first-row late-transition metals. We were interested indeveloping the hydrosilylation reaction of vinylarenes using our nickel(II) complexes as
catalysts. We found that Ni-ONP shows high catalytic activity for the hydrosilylation of styrene
derivatives with 1,1,3,3-tetramethyldisiloxane (TMDS), which acts as a highly efficientsurrogate for Me2SiH2, in the presenceof NaOMe as a base. These reactions
proceeded in a regioselective manner

Ar

+

Si
H

O

Si
H

TMDS (3.0 equiv)

under mild conditions and afforded the

Ni-ONP (5 mol%)
NaOMe (1.0 equiv)
dioxane
25 °C, 24 h

SiMe2HAr

H

up to 90% isolated yieldhigh Markovnikov-selective

corresponding Markovnikov products in high yield [1].
[1] Hashimoto, T.; Shiota, K.; Ishimaru, T.; Yamaguchi Y. “Hydrosilylation of Alkenes Using a
Hydrosiloxane as a Surrogate for Me2SiH2 and Catalyzed by a Nickel-Pincer Complex”, Eur. J. Org.
Chem. 2021, 5449.
－23－2021-24
磁性微粒子を用いたウルシオール塗膜の機能発現
橘洋一

京都市産業技術研究所【目的】
近年，電子機器の精密化・高性能化が進み，電子機器の誤作動，混信，健康被害といった電磁波
による障害を回避するため，これまで以上に電磁波遮蔽の技術が求められている。電磁波遮蔽材料
は，電気絶縁性を持ったバインダーと電磁波を吸収する添加剤を組合せて作製される。天然樹脂である漆は，電気絶縁性があり，環境に優しい電磁波遮蔽材料のバインダーとして期待が持たれる。
そこで，電磁波吸収の添加剤として，磁性を持った鉄フェライトを混合した漆塗膜を作製し，電磁波遮蔽の性能について検討を行った。
【実験】
初めに天然の漆に対し，粒径が 40 µm より小さい鉄フェライト（以下，F40 と記す）
，40 µm 以上
かつ 75 µm より小さい鉄フェライト（以下，F75），比較対象として磁性を持たないベンガラ（以下，B）を所定の割合（0, 1, 5, 10, 25 wt%）で混合し，フーバーマーラーにて 1 分間撹拌することで添加物を混合した漆を得た。さらに，得られた漆を 20 oC/60%の条件下で乾燥させ，漆塗膜を形成させた。塗膜の膜厚は，濡れ膜厚で 50 m とした。同時に，乾燥時間の測定を行い，得られた漆塗膜を電磁波測定器 RT-100（ERICKHILL 社製）により電磁波遮蔽性の評価を行った。
【結果】
初めに，乾燥時間の測定を行った（図 1）。鉄フェライトを添加した塗膜では，乾燥時間が短縮する傾向が見られた。これは，フェライト中に含まれる鉄イオンが漆と反応しているためと予想される。続いて，電磁波遮蔽性の評価として，簡易的に電界強度にて評価を行った。今回の測定では，電界強度が 30 V/m 以下の塗膜において，電磁波遮蔽性を有する。その結果，粒径の細かな鉄フェ
ライト F40 を 25 wt% 添加した漆塗膜において，10 V/m という高い電磁波遮蔽性が確認された。

F40

F75

B

4
2
0

0

1
5
10
additive amount (wt%)

80electric field (V/m)

draying time (hour)

6

F75

B

60
40
20
0

25

F40

0

1
5
10
additive amount (wt%)

25

図 2. 作製した漆塗膜の電磁波遮蔽性

図 1. 作製した漆塗膜の乾燥時間－24－2021-25
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.
Organic phosphenium ions (R2P:+) are attractive intrinsically extremely reactive
species, which would exhibit possible ability of working as effecting oxidation scavengers.
Isolable stable phosphenium ions remain scarce, and in most hitherto reported examples, thephosphenium center is stabilized by electron-donating substituents (e.g., heteroatoms such as
nitrogen), which results in electronic perturbation. We have been interested in the chemistry ofredox-active phosphenium ions with carbon-based substituents such as ferrocenyl groups.
Furthermore, we have designed a ferrocene-based phosphenium ion with “reversible”
intramolecular donor coordination, [Fc*FcPP]+, Fc* = 2,5-(3,5-tBu2-C6H3)2-1-ferrocenyl, FcP =1’-dicyclohexylphosphino-1-ferrocenyl). The FcP group ascribes both stability and reactivity
for the phosphenium ion center with its “switchable” donor coordination caused by the rotationof the cyclopentadienyl moiety Accordingly, the well-designed phosphino-phosphonium ion
incorporated within [2]ferrocenophane framework “Switchable” Masked Phosphenium ion
built in [2]Ferrocenophane architecture
was synthesized as an air-stable phosphenium ion as
FeFea potential “bottleable” oxidation scavengers. We
are grateful to Prof. Wakamiya (ICR, Kyoto Univ.),
P
P
Fe
Fe
Prof. Yoshida (Nagoya Univ.) and Prof. Tsuchiya
P
P
Cy
Cy Cy
Cy
(Kitasato Univ.) for their support on the research,stablereactiveand fruitful discussions.
Cy = cyclohexyl
“ON”

1.

2.

“OFF”

Nakamura, T.; Yakumaru, S.; Truong, M. A.; Kim, K.; Liu, J.; Hu, S.; Otsuka, K.;
Hashimoto, R.; Murdey, R.; Sasamori, T.; Kim, H. D.; Ohkita, H.; Handa, T.; Kanemitsu,
Y.; Wakamiya, A. Nature Communications 2020, 11, 3008.
Zhang, T.; Lee, V. Y.; Morisako, S.; Aoyagi, S.; Sasamori, T. Eur. J. Inorg. Chem. 2021,
2021, 3988-3991.

－25－

2021-26
Development of heteroacenes with excellent photophysical andelectrochemical properties
Koichi Mitsudo

Okayama University

Thienoacenes, which are acene molecules incorporating thiophene rings, are known to
exhibit excellent semiconductor properties and are used as active materials in organic
field-effect transistors (OFETs) and organic photovoltaic cells (OPVs). Therefore, this field has
been studied intensively, and various thienoacenes have been synthesized to validate their
physical properties. Meanwhile, thiophene ring is an electron-rich donor aromatic ring,whereas thiophene-dioxide, which is obtained by oxidizing the thiophene ring, loses its
aromaticity and behaves as an electron-deficient acceptor molecule. In recent years, some
π-conjugated molecules incorporating thiophene-dioxide have been reported to have uniqueluminescent properties, and have begun to attract attention. However, there have been few
reports on the synthesis of thienoacene derivatives containing multiple

O O
S

thiophene-dioxides, even though they are expected to have interesting properties,
and little is known about their physical properties. In this study, we focused onsynthesisofthienoacenes

which

have

benzo[1,2-b:4,5-b′]dithiopheneS
O O
BDT tetraoxides

1,1,5,5-tetraoxide (BDT-teraoxides) as a key skeleton.
Even though BDT is one of the most common skeletons in thienoacenes, there have been
few reports on the synthesis of their oxides. We therefore set out to develop a synthetic method
for the BDT tetraoxides. Treatment of 4,8-dioctylbenzo[1,2-b:4,5-b′]dithiophene (1) with NBS
took place bromination to afford dibromominated BDT 2 regioselectively. Thus obtained 2
could be oxidized with mCPBA to afford dibromoinated BDT tetraoxides 3.

We applied thus-obtained dibrominated BDT tetraoxides 3 to addition–elimination
reactions and found that the desired substitution reaction proceeded smoothly. For instance, thereaction with benzenethiol gave BDT tetraoxides 4 quantitatively which has two
phenylsulfanyl units. The studies on photophysical properties of the substituted BDT
tetraoxides and further transformation of them are ongoing in our group.

－26－

2021-27（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. Prediction and classification of cancer subtypes have been a major topic
both in biomedicine and bioinformatics. For that purpose, various machine learning
methods have been developed to better analyze mRNA expression data and improvethe classification accuracy. However, most of current studies focus on specific cancer
types, and thus it is needed to explore mechanisms across multiple cancer types. To
address these issues, we have been collaborating with Professor Akutsu in ICR. In
this proposal, we will continue our collaboration to extend our previous approach toinclude other kinds of omics data, such as PPI and metabolic networks as well as PPI
modules. We will also study deep learning-based methods for identifying interaction
sites of protein kinase inhibitors because protein kinases play important roles invarious diseases including cancers.
Results. In this year, we focused on identification of interaction sites of protein kinase
inhibitors. We developed the Prediction of Interaction Sites of Protein Kinase
Inhibitors (PISPKI) model [1], which is a graph convolutional neural network (GCN)
to predict the interaction sites of protein kinase inhibitors. The core of the PISPKI
model is the WL Box, which was newly designed based on the well-known
Weisfeiler-Lehman algorithm. The most important feature of the WL Box is that it
assembles multiple switch weights to effectively compute graph features. The PISPKI
model was evaluated by testing with shuffled datasets using 11 kinase classes. The
resulting accuracy varied from 83 to 86%, demonstrating superior performancecompared to two baseline models. Furthermore, the importance of each component
was analyzed via the ablation study, and the result suggests that the WL Box module
is critical.
Publication[1] F. Wang, Y‑T. Chen, J‑M. Yang, T. Akutsu: A novel graph convolutional neuralnetwork for predicting interaction sites on protein kinase inhibitors, Scientific
Reports, vol. 12, Paper ID. 229, 2022.

－27－

2021-28（国際）Developing Data-driven Deep Learning Approaches for Accurate
Identification of Protease Specific Substrate Targets and Cleavage
Sites
Jiangning SongMonash University

Objective. It is important to understand the mechanisms of regulation of proteolysis
by proteases for elucidation of cellular processes. For that purpose, it is highly
desirable to develop high-throughput, cost-effective computational methods that canbe used to accurately identify the target substrates for a specific protease. I have beenworking on this important problem with Prof. Akutsu at ICR. In this project, building
upon our successful collaborations, we continue and extend our development of nextgeneration bioinformatics methods for improved prediction of protease-specifictarget substrates and their cleavage sites. We will also study other related
bioinformatics problems in sequence analysis and structural informatics.
Results. As a result of this project, we have developed several bioinformatic
methods/tools for analysis of protein and nucleotide sequence data, which include,
iLeanPlus: a general purpose tool for analyzing protein and nucleic acid sequence [1],
DeepVF: a deep learning-based tool for identifying virulence factors from protein
sequences in bacterial pathogens [2], and Anthem: a bioinformatic tool for predictionof binding between peptides and HLA class I molecules [3].
Publications[1] Z. Chen, P. Zhao, C. Li, F. Li, D. Xiang, Y. Z. Chen, T. Akutsu, R. J. Daly RJ, G.
I. Webb, Q. Zhao, L. Kurgan, J. Song. iLearnPlus: a comprehensive and automatedmachine-learning platform for nucleic acid and protein sequence analysis, prediction
and visualization. Nucleic Acids Research, vol. 49, Paper ID. e60, 2021 (17 citations).
[2] R. Xie, J. Li, J. Wang, W. Dai, A. Leier, T. T. Marquez-Lago, T. Akutsu, T. Lithgow,
J. Song, Y. Zhang. DeepVF: a deep learning-based hybrid framework for identifying
virulence factors using the stacking strategy. Briefings in Bioinformatics, vol. 22,
Paper ID. bbaa125, 2021 (10 citations).
[3] S. Mei, F. Li, D. Xiang, R. Ayala, P. Faridi, G. I. Webb, P. T. Illing, J. Rossjohn,
T. Akutsu, N. P. Croft, A. N. Purcell, J. Song. Anthem: a user customised tool for fast
and accurate prediction of binding between peptides and HLA class I molecules.
Briefings in Bioinformatics, vol. 22, Paper ID. bbaa415, 2021 (4 citations).

－28－

2021-29（国際）Unveiling the genomic contents of ecologically important marine giant
viruses
Tom O. Delmont CNRS
Large double-stranded DNA viruses of phylum Nucleocytoviricota are a group of eukaryotic
viruses that are highly diverse and abundant in marine environments. This group of viruses hascomplex genomes with sizes of up to 2 Mb that are even larger than small cellular organisms.
However, the discovery of giant viruses has mainly been driven by the co-cultivation with amoebae
or algal hosts. Consequently, the number of viruses and functions are primarily underestimatedcompared to the metagenomics-driven viral signals detected in the ocean. Thus, in this study, we(Tom O. Delmont et al.) investigated metagenomic data set from the sunlit ocean, built comprehensive
marine giant virus genomes, and analyzed their genetic repertoires.
We first developed a phylogeny-guided framework to generate the giant virus genome databaseusing a single hallmark gene, a subunit of DNA-dependent RNA polymerase, as a compass [1]. In
total, 697 Nucleocytoviricota genomes were reconstructed. Along with the genomes from previous
marine metagenomic surveys and isolated references, a total of 1817 non-redundant genomes were
included in the final database. We then performed a phylogenetic analysis and surprisingly found twomonophyletic deep-branching clades, Proculviricetes and Mirusviricetes. Mirusviricetes lacks
several hallmark genes critical to particle morphogenesis but are enriched with some unique functions.
A comparative functional analysis provided a result consistent with the monophyly of Mirusviricetes.
In addition, we discovered myosin homologs in the database and revealed that these viral myosins
formed a monophyletic group and had multiple origins [2].
The diversity of giant viral lineages draws attention to discovering new viral genomes. However,previous works might have overlooked putative lineages diverging from the traditional core genebased definition of Nucleocytoviricota. Our phylogeny-guided framework has shown the efficiency
in characterizing previously unknown lineages. The discovery of two conspicuously new lineages,
Proculviricetes and Mirusviricetes, reminds us that we have not grasped the full diversity of giant
viruses. Mirusviricetes is a major, functionally divergent class that implies a probability of an
enigmatic viral lifestyle. Finally, the environmental genomic database for Nucleocytoviricota willcontribute to future endeavors exploring the ecology and evolution of giant viruses.
Publication:[1] GaiaM., Meng L., Pelletier E., Forterre P., Vanni C., Fernendez-Guerra A., Jaillon O., Wincker
P., Ogata H., Delmont T.O. Discovery of a class of giant virus relatives displaying unusual functional
traits and prevalent within plankton: the Mirusviricetes. bioRxiv doi.org/10.1101/2021.12.27.474232(2021).
[2] Kijima S., Delmont T.O., Miyazaki U., Gaia M., Endo H., Ogata H. Discovery of viral myosin
genes with complex evolutionary history within plankton. Front. Microbiol. 12, 683294 doi:
10.3389/fmicb.2021.683294 (2021).

－29－2021-30（国際）Revealing associations between giant viruses and eukaryotes in the global
ocean through community networks inference and mining
Samuel Chaffron

CNRS

Large double-stranded DNA viruses are a monophyletic group of eukaryotic viruses,
corresponding to the phylum Nucleocytoviricota, which is highly diverse and abundant in marine
environments. Giant viruses have a broad range of eukaryotic hosts, from unicellular eukaryotes toanimals. However, the number of viruses isolated in the laboratory represents a small fraction of viralsignals detected in the ocean. The interactions between giant viruses and eukaryotes and factors
driving these interactions remain poorly known. In this study, taking advantage of the recent largescale marine metagenomics census, we used in silico approaches to investigate the global
biogeography of marine giant viruses and their associations with eukaryotes.
First, using recently published environmental genomic databases for Nucleocytoviricota andeukaryotes, we built co-occurrence networks of metagenome-assembled genomes (MAGs). We thenused a phylogeny-informed filtering method, Taxon Interaction Mapper (TIM), to refine theseassociations by integrating co-evolution information and improve the prediction of virus-host pairs.
To further validate these predictions, we conducted a series of genome-based analyses, such as
pairwise gene alignment and Giant Endogenous Viral Elements (GEVEs) detection, using eukaryotic
MAGs and reference genomes.
We observed a total of 2,083 virus-eukaryote associations in the network, involving 787 viralMAGs that are widespread in the Nucleocytoviricota phylogenic tree. After TIM enrichment, wefound two documented virus-host pairs, Prasinovirus and Mamiellophyceae, and Coccolithovirus andHaptophyta. Three other predicted hosts, Thalassiosirales, Isochrysidales, and Chaetocerotales,
showed a large number of signals of giant viruses and virophages (parasites of giant viruses)
insertions. Additionally, we leveraged a published Chaetoceros muellerii genome and found that the
GEVE in C. muellerii and the giant virus clade, which were predicted to infect with Chaetocerotales,
are congruent in the phylogenetic tree. Moreover, we demonstrated that the virus-host network was
highly structured along the latitudinal gradient of temperature from the equator to the poles.
Focusing on the associations between giant viruses and eukaryotes in the global ocean, thisproject has demonstrated that network-based approaches are efficient hypothesis generators in giant
virus-host prediction [1]. Genome-resolved networks provide genomic information improving theinterpretability of host predictions. Using the new marine Nucleocytoviricota genome database, we
could confirm that these associations between giant viruses and eukaryotes are prevalent in the global
ocean and influenced by the environment, such as temperature. Overall, this project has thus
significantly contributed to further our understanding of the complex relationships between giant
viruses and eukaryotes.
[1] Meng L, Endo H, Blanc-Mathieu R, Chaffron S, Hernández-Velázquez R, Kaneko H, Ogata
H. 2021. Quantitative assessment of NCLDV–host interactions predicted by co-occurrence
analyses. mSphere, 6, e01298-20 (2021)－30－

2021-31（国際）A Study on Statistical Machine Learning for
Efficient Graph Structured Data Analysis
Masayuki Karasuyama Nagoya Institute of Technology
For a variety of scientific fields such as biology, chemistry, and materials science,
effective methodologies for analyzing their complicated data are strongly demanded. In
particular, the graph-based data representation enables us to handle a variety of data types
that is represented by interactions among multiple component objects. For example, achemical compound is often represented as a graph in which an atom is a graph-vertex
and a chemical bond is a graph-edge. Although graph is a versatile tool for data
representations, analyzing its statistical property is usually difficult because of its
combinatorial nature. In this study, we consider developing statistical machine learning
methods for efficiently analyzing graph structured data by combining several techniquesfrom data-mining, machine learning, and numerical optimization. For this interdisciplinary topic, we have worked with the researchers including prof. Mamitsuka in the
bio-knowledge engineering research laboratory of ICR.
We mainly focus on a task that statistically predicts a property associated with a given
graph. For instance, predicting toxicity of a compound is a well-known example in thistype of problems. We constructed an algorithm that identifies sub-structures of the graphstrongly contributing to the target property [1], which can provide insights about theunderlying correlation structure. Although a naïve approach to this problem causes
prohibitive amount of computations, our proposed method provides an efficientcomputational procedure by pruning unnecessary sub-structures while maintaining the
optimality guarantee. We further extend this method so that it can incorporate different
types of the loss functions and inexact (relaxed) matchings of substructures. As anotherimportant application of our predictive graph mining framework, we further studied
applying the same mining idea to a graph neural networks (GNN) explanation [2]. Recent
GNN techniques have been used for a variety of tasks including scientific data analysis,but providing explanations about its behavior is still an open problem. We developed a
local explanation approach based on the predictive graph mining surrogate by which a
sub-structure based explanation that is difficult to provide by other existing approaches
can be obtained.
[1] T. Yoshida, I. Takeuchi, and M. Karasuyama, Distance Metric Learning for Graph
Structured Data, Machine Learning, vol.110, no.7, 1765-1811, 2021.
[2] H. Asahi, and M. Karasuyama, Local Explanation of Graph Neural Network throughPredictive Graph Mining, IEICE technical report, vol.121, no.321, IBISML2021-23, 3744, 2022 (in Japanese).

－31－2021-32
Control and Analysis of Complex Networks via Probabilistic
Minimum Dominating SetsJose C. Nacher

Toho University

Objective. We have been studying structural controllability of complex networks
and developing theory and methods based on the minimum dominating set (MDS).
In particular, we developed a new concept, the probabilistic minimum dominating
set (PMDS), by extending the MDS for handling weighted networks. We willdevelop an efficient method for identifying three classes of nodes(critical/intermittent/redundant nodes) in the PMDS framework and apply it toanalysis of brain ageing mechanisms. We will also study the maximum matching(MM)-based model, which is another major approach to analysis of structuralcontrollability of complex networks.
Results. As for the PMDS-model, we developed an efficient integer linear
programming(ILP)-based

methodwith

pre-processing

toidentify

critical/intermittent/redundant nodes. We compiled the gene expression profiles offour normal brain regions from individuals aged 20–99 years, generated dynamic
probabilistic protein networks across their lifespan, and applied the ILP-based
method to the networks. The results show that the identified critical proteins weresignificantly enriched with well-known ageing genes collected from the GenAge
database [1]. As for the MM-model, we combined the concept of driven nodes(Pequito et al., IEEE Trans. Automatic Control, 2016) and the concept ofcritical/intermittent/redundant nodes. We developed an efficient ILP-based method
and applied it to analysis of a large number of biological networks. The results
indicate that the number of driven nodes is considerably larger than the number ofdriver nodes, not only in all examined complete plant metabolic networks but also
in several key human pathways [2].
Publications[1] E. Yamaguchi, T. Akutsu, J. C. Nacher: Probabilistic critical controllability
analysis of protein interaction networks integrating normal brain ageing gene
expression profiles, Int. J. Molecular Sciences, vol. 22, paper ID. 9891, 2021.
[2] Y. Shinzawa, T. Akutsu, J. C. Nacher: Uncovering and classifying the role ofdriven nodes in control of complex networks, Sci. Rep., vol. 11, ID. 9627, 2021

－32－

2021-33
Comprehensive analysis of viral succession during the transition of multiple
types of algal blooms
Keizo Nagasaki

Kochi University

Objectives:
In this study, we investigated the community dynamics of eukaryotes, prokaryotes and a majorgroup of large DNA viruses during 20 months in the Uranouchi Inlet, Kochi prefecture, to better
understand community dynamics of free living microbes inhabiting coastal seawater.
Experimental Methods:
Ten liters of seawater were sampled and sequentially pumped through filters with pore sizes of
3µm, 0.8µm, and 0.2µm. The different community compositions of 43 samples were thenanalyzed with amplicon sequencing of a conserved gene of the respective microbial group.
Experimental Results:
The amplicon sequencing yielded several million, bona fide, cellular and viral reads, which wereclustered to amplicon sequence variants (ASVs). Ecological analysis revealed a pronounced
seasonality of each microbial group. The ASV communities of eukaryotes, prokaryotes, and amajor group of large DNA viruses were compared and we discovered significant differences intheir dynamics.
Discussion
Here, we were the first to describe the seasonality of a major group of large DNA viruses. Thisviral seasonality was strongly linked to the other microbial communities. The comparison of
those communities showed that members of the viral community were less persistent andreoccurred less frequently than members of the eukaryotic community. The prokaryotic
community showed the longest persistence and highest recurrence of its members after one year.
The differences in community dynamics were interpreted as an ability of current communities toinfluence the formation of future communities, albeit with diminishing influence over time.
Publication
Year-round dynamics of amplicon sequence variant communities differ among eukaryotes,
Imitervirales, and prokaryotes in a coastal ecosystem.
Florian Prodinger, Hisashi Endo, Yoshihito Takano, Yanze Li, Kento Tominaga, Tatsuhiro
Isozaki, Romain Blanc-Mathieu, Yasuhiro Gotoh, Tetsuya Hayashi, Etsunori Taniguchi,
Keizo Nagasaki, Takashi Yoshida, and Hiroyuki Ogata.
FEMS Microbiology Ecology, (2022) - accepted－33－2021-34
Development of the method for the detection of coronavirus
diversity
Tokiko Watanabe

Osaka University

Coronaviruses can cause zoonotic diseases and have become a major public health problem.
Since bats are one of the natural reservoirs of coronaviruses, surveillance of bat coronaviruses
is important for predicting possible future zoonotic diseases. In this study, we aimed toestablish an RT-PCR method using degenerate primers designed through bioinformatics
analysis to detect coronaviruses comprehensively and with high sensitivity. Using
bioinformatics analysis, we designed 39 differentγδdegenerate primer pairs to detect conserved
coronaviral polymerase genes. The RT-PCR
conditions were verified using these primer pairsβand control coronaviruses, including SARS-CoV-2.
To examine whether this method is applicable tofield samples, we attempted to detect thecoronaviral genome using RNA extracted fromα
0. 3Novel bat alpha CoV

Fig 1. Phylogenetic tree of coronaviruses(whole genome)

bat organs collected in Sierra Leone. A coronaviral gene was detected in the intestinal tract of
one out of 26 bats. Subsequently, we determined the whole genome sequence of this virus byusing Next Generation Sequencing. Phylogenetic analysis revealed that this virus was a novel
bat alphacoronavirus (Fig. 1). By applying this method to surveillance of bat coronaviruses,
proactive measures can be taken against future outbreaks of coronavirus infections.
<Presentation>
Shichinohe S, Takada K, Hingamp P, Tomita Y, Maemura T, N'jai A, Kawaoka Y, Endo H,
Ogata H, Watanabe T. Use of RT-PCR and degenerate primers to comprehensively assess
coronavirus genomes, The 68th Annual Meeting of the Japanese Society of Virology, Kobe,
Japan, Nov., 2021. (Oral presentation)－34－

2021-35
効果的な分子ネットワーク解析方法の開発と医学・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、特に、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]－35－

2021-36（国際）Synthesis of inorganic molecules for elucidation of biosynthetic
pathways of iron-sulfur clusters
Markus W. Ribbe University of California
Nitrogenase catalyzes the reduction of N2 to NH3 at its cofactor site. Designatedthe M-cluster, the cofactor of Mo-nitrogenase is an [(R-homocitrate)MoFe7S9C]
cluster that is synthesized via formation of a [Fe8S9C] L-cluster prior to the insertionof Mo and homocitrate. Our previous study has led to the identification of a [Fe8S8C]
L*-cluster, which is highly similar to the L-cluster in the core structure but lacks the‘9th sulfur’ in the belt region. However, direct evidence for conversion of the L*cluster to an L-cluster upon insertion of SO32- as the ‘9th sulfur’, as well as themechanistic details of this reaction, remains elusive. Here we report characterizationof the ‘9th sulfur’ insertion using SeO32- and TeO32- as ‘labeled’ SO32- sources.
Biochemical, CW/pulse EPR and XAS/EXAFS studies suggest a crucial role of the‘9th sulfur’ in cluster transfer during cofactor biosynthesis while revealing theincorporation of SeO32- and TeO32- as Se2- and Te2--like species, respectively, in thebelt region of the L-cluster. DFT calculations further suggest an insertion mechanismof the ‘9th sulfur’ that involves cluster-facilitated in situ reduction of SO32- to S2-.
These results provide direct evidence for the incorporation of a ‘9th sulfur’ during
cofactor biosynthesis and establish an effective means to label the catalyticallyimportant belt region for future mechanistic investigations of nitrogenase.
This work was published as a scientific paper in Nature Chemistry:
Joint publication from this collaborative work:(team members are underlined)

Kazuki Tanifuji, Andrew J. Jasniewski, David Villarreal, Martin T. Stiebritz, Chi
Chung Lee, Jarett Wilcoxen, Yasuhiro Ohki, Ruchira Chatterjee, Isabel Bogacz,
Junko Yano, Jan Kern, Britt Hedman, Keith O. Hodgson, R. David Britt, Yilin Hu,
Markus W. Ribbe, “Tracing the incorporation of the “ninth sulfur” into thenitrogenase cofactor precursor with selenite and tellurite“
Nature Chem. 2021, 13, 1228-1234.

doi: 10.1038/s41557-021-00799-8－36－2021-37（国際）Development of new blue TADF emitters with horizontal molecularorientations
Eli Zysman-Colman

University of St Andrews

We have recently reported two collaborative studies between the Zysman-Colman and Kaji labs
involving a multichromophore thermally activated delayed fluorescence (TADF) molecular design [1,2] and their use in solution-processed TADF-OLEDs.
The first project built upon the previously published work on
ICzTRZ,[3] by developing a dimerized analog DICzTRZ (Figure1). The emission maximum ios 488 nm and the photoluminescencequantum efficiency (PL) is 57% in the 20 wt% doped CzSi film,
and we observed the presence of both prompt and delayed
fluorescence, confirming that DICzTRZ shows TADF. Polarization
and angle-dependent luminescence spectroscopy were used tomeasure the orientation factor, a, for the solution-processed films ofthe 20 wt% DICzTRZ in CzSi, which yielded an anisotropy factorof 0.53 that disappointingly implies that the emitter presents astrongly vertical orientation, thus leading to blue-green devices with
EQEmax value of 8.4% with EL of 494 nm, corresponding to CIE of(0.22, 0.47).
The second project disclosed 2 dual and 1 treble core TADF Figure 1. Molecular structures
emitters, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN (Figure of DICzTRZ.
2). The three emitters exhibited nearly quantitative PL in toluene,of 98%, 96%, and 99%, with an emission maximum of 494 nm, 485 nm, and 483 nm, for p-di2CzPN,
m-di2CzPN, and 1,3,5-tri2CzPN, respectively, while those of reference material, 2CzPN are only
28% and 475 nm, respectively. All materials exhibited TADF. Solution-processed devices for 1,3,5tri2CzPN were then fabricated, which showed sky-blue emission at EL of 500 nm with CIE of (0.22,0.44) and EQEmax of 7.1%.
Further collaboration between the University of St Andrews and Kyoto University is evidenced in
the work from Tsuchiya et al.,[4] where we presented exact solution to model the exciton decay
kinetics of TADF materials.

Figure 2. Molecular structures of p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN.

References(1) Crovini, E.; Zhang, Z.; Kusakabe, Y.; Ren, Y.; Wada, Y.; Naqvi, B. A.; Sahay, P.; Matulaitis,
T.; Diesing, S.; Samuel, I. D. W.; Brütting, W.; Suzuki, K.; Kaji, H.; Bräse, S.; Zysman-Colman,
E. Beilstein J. Org. Chem. 2021, 17, 2894–2905. doi:10.3762/bjoc.17.197(2) Chen, D.; Kusakabe, Y.; Ren, Y.; Sun, D.; Rajamalli, P.; Wada, Y.; Suzuki, K.; Kaji, H.;
Zysman-Colman, E. J. Org. Chem. 2021, 86 (17), 11531–11544. doi:10.1021/acs.joc.1c01101(3) Zhang, Z.; Crovini, E.; dos Santos, P. L.; Naqvi, B. A.; Cordes, D. B.; Slawin, A. M. Z.; Sahay,P.; Brütting, W.; Samuel, I. D. W.; Bräse, S.; Zysman-Colman, E. Adv. Opt. Mater. 2020.
doi:10.1002/adom.202001354(4) Tsuchiya, Y.; Diesing, S.; Bencheikh, F.; Wada, Y.; dos Santos, P. L.; Kaji, H.; Zysman-Colman,
E.; Samuel, I. D. W.; Adachi, C. J. Phys. Chem. A 2021, 125 (36), 8074–8089.
doi:10.1021/acs.jpca.1c04056－37－2021-38（国際）－38－2021-39（国際）Development of hole transport materials for tin-perovskite
and device characterization
Akinori Saeki Osaka University
The outstanding nature of organic-inorganic metal halide perovskites has made thesematerials most suitable for optoelectronic applications such as perovskite solar cells (PSCs)
and light-emitting diodes. The highly efficient perovskite material used in these devices iscomposed of an ABX3 type three-dimensional (3D) structure, where A is an organic cation(such as methylammonium, MA; formamidinium, FA), an inorganic cation (such as cesium,Cs), or a mixture of both; B is a lead (Pb) cation; and X is a halogen anion (Cl, Br, I, or a
mixture). The power conversion efficiency (PCE) of PSCs almost reaches that of crystalline
silicon solar cells, and their applicability in the roll-to-roll solution process and fabrication on a
flexible substrate are other notable advantages of PSCs over conventional inorganic solar cells.
However, the use of toxic Pb, albeit in small amounts, as well as insufficient long-term stability
against environmental conditions (moisture, oxygen, hot/cold) are critical issues forcommercialization.
Along
these
lines,
thecompositionof
Ruddlesden-Popper two-dimensional (2D) perovskites
described as R2An–1BnX3n+1 (n = 1, 2, …, Fig. 1), form
an immensely important part of PSC because theinsulating layer introduced by R, bulky organic cations
n=1
n=2
such as n-but ylammonium cation (BA) andn = ∞ (3D)n=32-phenyl-ethylammonium cation (PEA), can preventthe intrusion of oxygen and moisture, thus improving Fig. 1. 2D and 3D perovskite structures.
the environmental stability compared to traditional 3D
perovskites. By sacrificing enhanced stability, 2D
perovskites have greater exciton binding energy owing
to the formation of quantum wells, resulting inanisotropic charge transport paths. These situations
lead to a strict requirement on the orientation andgradient of the 2D/3D component to achieve balanced
PCE and improved stability of the PSC.
Fig. 2. Schematic of annealing: NTA andWe report the effect of top thermal annealing (TTA) TTA.
on the PSC photoconductivity and performance, where
TTA is a process that exposes heat from the top side (rather than the bottom (substrate) side innormal annealing) to form the perovskite layer after anti-solvent treatment (Fig. 2). The
anisotropic photoconductivity in the in-plane and out-of-plane directions was evaluated, whichsuggested a vertical gradient of 2D/3D phases with a 3D-rich component on the surface.
[1] R. Shimono, R. Nishikubo, F. Ishiwari, A. Saeki, J. Photopolym. Sci. Technol. 2021, 34, 263.
[2] S. Hu, M. A. Truong, K. Otsuka, T. Handa, T. Yamada, R. Nishikubo, Y. Iwasaki, A. Saeki, R.
Murdey, Y. Kanemitsu, A. Wakamiya, Chem. Sci. 2021, 12, 13513.

－39－2021-40
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体を構築し、超分子構築におけるユニット分子としての役割を明らかにしてきた。動的平衡過程を有する
自己集合性ボリルピリジンには、ゲスト誘起の自己集合という、誘起適合の分子認識の実現が期待される。また非交互系のアズレン骨格を導入したボリルピリジンが集合した超分子には、動的挙動にキラリティーや分子間相互作用によるキラルな高次構造が誘起されるなら、その光学活性を活かした機能性材料への応用が期待される。本研究では化学研究所の大木靖弘教授と共同し、これら新たなボリルピリジン類の設計、合成と基本的性質の検討に取り組んだ。
【結果と考察】本研究で研究対象としたボリルピリジンは、化合物 1，2 である。1 の合成は対応する臭素体から n-BuLi とEt2OMe を用いフローマイクロ法により 85％の高収率で達成することができた。
化合物 1 は各種スペクトル測定、VPO から、環状 3 量体と 4 量体の平衡混合物を生じている。3量体の比率は溶媒の極性を上げると、42%（重ベンゼン中）から 76%（重アセトン中）に増加した。
3 量体の双極子モーメント（3.5D）が 4 量体のそれ（1.3D）に比べ大きいことに起因すると考えられる。1 のベンゼン溶液とヘキサンとの蒸気拡散平衡法（7 ℃）により析出した単結晶を X 線結晶構造解析すると、環状 4 量体 14・(C6H6)2 が得られた (Figure 1)。ベンゼン 1 分子が CH/π 相互作用により包接され、もう 1 分子のベンゼンは結晶の隙間を埋めている。1 の多量体間の平衡は濃度を上げると 4 量体側に片寄ることから、4 量体を主として含む濃厚溶液から 4 量体が優先して結晶化した結果と考えられる。
次に、ホウ素原子との配位結合に関わっていないピリジン窒素原子との相互作用を期待し包接実験を行った。メタノール、安息香酸などの添加実験においては、1H NMR スペクトルに全く変化は認められなかった。これらの化合物とホウ素から離れたピリジン窒素の α 位水素との立体反発のためと考えられる。一方、白金錯体やホウ酸との反応では、単量体との錯体が得られ、環状構造を保持したままでの金属イオンの配位は困難であることが示唆された。
【成果報告】若林成知，脇岡正幸，大木靖弘，宅見正浩，永木愛一郎，第 31 回基礎有機化学討論会，2P007，筑波（オンライン），2021.

－40－

2021-41
ジベンゾフェナジンを電子アクセプターとするスルースペース電荷移動型熱活性化遅延蛍光材料の創製
武田洋平

大阪大学

目的：本研究課題では、研究代表者（武田）がこれまでに独自に展開してきた熱活性化遅延蛍光（thermally activated delayed fluorescence: TADF）材料研究（総合論文）：Chem. Commun. 2020, 56, 8884）を飛躍的に発展・深化させるために、武田の得意とする電子アクセプター合成技術を活用して、共同研究者である梶らが得意とする
スルースペース電荷移動（through-space charge transfer: TSCT）型 TADF 材料設計
指針ならびに光物性評価技術を融合させ、高効率な新奇 TADF 材料を創製し、有機 EL
発光素子へと応用することを目的とした。
実験方法：研究代表（武田）が独自に開発した含窒素芳香環分子を電子アクセプター（A）として採用し、適切な距離（3.7 Å）を保つことのできるπリンカーを介して、トリアリールアミン骨格を有する電子ドナー(D)と連結した分子を設計し、有機合成化
学的手法を用いて合成し、基礎的な光物性を調査した。
実験結果および考察：市販されている化合物から６ステップでドナー及びπリンカーを有するユニットの合成ルートの確立を成功した。さらに、これと電子アクセプター
ユニットとを、Pd 触媒を用いるカップリング反応により連結させ、目的分子を良好な収率で合成することに成功した。1H NMR スペクトルを測定したところ、D ユニットおよび A ユニットの一部の水素核が単独のユニットよりも高磁場側に観測されたことか
ら、溶液中に置いて D 及び A 平面が対面して重なり配座をとっていることが示唆された。また、様々な極性を持つ有機溶媒中における吸収・発光スペクトルを調査したところ、吸収スペクトルは極性に依存することなく重なりの良いスペクトルを示したのに対して、発光スペクトルにおいては、溶媒極性の増大に伴って顕著に発光波長の長波長化およびスペクトルのブロード化が観測されたことから、本発光は空間を通じた電荷移動により生じた励起状態からの輻射であることがわかった。以上のように、本研究では、新規な TSCT 型分子の合成に成功し、その基礎的な光物性を明らかにした。
今後、詳細な時間分解分光測定及び有機 EL 素子による評価を行って行く予定である。
成果報告：特になし。

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2021-42
Chiral Silica with preferred-handed helical structure via chiral transfer
Tomoyasu Hirai Osaka Institute of Technology
Chiral silica has attracted considerable attention in the various kinds of fields such as catalysis,
templating, chiral recognition and so on. These materials are generally prepared by sol-gel
transcription using an organic chiral molecule as a template. This process, however, requires
tedious reaction steps. To overcome this problem, we focused on stereoregular polymer withpolyhedral oligomeric silsesquioxane (POSS) side chain.
We designed and synthesized novel isotactic POSS-containing polymethacrylate (it-PMAPOSS)
using living anionic polymerization method1. To control the secondary structure, it-PMAPOSS
thus obtained was mixed with (R) or (S)-binaphthol derivatives (R or S-BN). Figure 1a shows avibrational circular dichroism (VCD) spectrum of it-PMAPOSS with enantiomeric BNs.
Specific split-type and mirror-image VCD signals were observed in it-PMAPOSS withenantiomeric BN at 1730 cm-1 corresponding to carbonyl stretching in the ester group of
PMAPOSS. Though several IR peaks ranging from 1000 to 1250 cm-1 overlapped, clear splittype Cotton effects on C-O-C (1050-1250 cm-1) and asymmetric Si-O-Si (1000-1240 cm-1)
vibrations could be observed. This result suggests that it-PMAPOSS formed preferred-handed
helical conformation.
Based on this knowledge, we calcinated the mixture of it-PMAPOSS and enantiomeric BNs at
600°C under air atmosphere and the residue thus obtained was evaluated using VCD.
Interestingly, the split-type Cotton effect could still be observed on the Si-O-Si vibration region
and was more striking than that of theunannealed one, indicating that silica with
opticalactivity

could

be

successfully

prepared. Figure 1b shows the transmission
electron microscopy (TEM) image of thecalcinated sample. A helical structure with thepreferred handedness was clearly observed ineach calcinated samples. We prepared chiralsilica using polymer with well-controlledstereoregularity as a template.
Achievements:

Figure 1 a) VCD spectrum of it-PMAPOSS withenantiomeric BNs. b) TEM image of chiral silica
prepared from it-PMAPOSS with (R)-BN.

1. JACS Au, 2021, 1, 375.
2. ACC. Mater. Surf. Res., 2021, 6, 132.
3. J. Polym. Sci., 2022, in press. DOI: 10.1002/pol.20210761－42－2021-43
高効率光電変換を志向した非対称型有機半導体分子の開発
鈴木充朗

大阪大学

【研究⽬的】
有機太陽電池（OPV）材料の分子設計に関し、非対称性を適切に導入することにより電荷キャリアの再結合が低減され、光電変換効率（PCE）の向上につながる可能性が指摘されている。しかし、非対称型 OPV 分子について系統的に評価した報告例は極めて限定的であり、広く適用可能な分子設計指針はいまだ確立されていない。そこで
我々は、高効率光電変換を実現するために必要な分子構造要件の明確化を目指し、現在、「非対称性」を鍵とする新規有機半導体分子の設計と評価に取り組んでいる。本研究ではその端緒として、diketopyrrolopyrrole（DPP）のダイマーを中心骨格とする 2 種類のアクセプター分子について比較評価を行った。
【実験と結果】
O

評価対象とするアクセプタ
ー分子 1 および 2（Figure 1）は、
対 応 す る DPP ダ イ マ ー のmonoformyl 体および diformyl

H

S
OD

N

1

N

OD

O

O

CN

S

CN
2

NC

S

CN

(OD: 2-octyldodecyl)

OD

N

N

2

OD
S

O

CN
2

CN

Figure 1. Chemical structures of DPP-based acceptor compounds 1 and 2.

体と malononitrile との脱水縮合により合成した。実験–3.3

的に見積もった HOMO/LUMO 準位は、化合物 1、2 で–4.2

それぞれ –5.6/–4.2 eV、–5.8/–4.5 eV となり、いずれもOPV 中でアクセプター材料として機能するために十分低い LUMO 準位をもつことが確認された（Figure 2）。
実際に P3HT をドナー材料とするバルクヘテロ接合型
OPV を作製し性能を評価したところ、非対称型分子 1

LUMOs
–4.5

–5.0
HOMOs
P3HT

–5.6
1

–5.8
2

Figure 2. Frontier orbital energy levels.

を用いた場合の方が対称型分子 2 を用いた場合に比べて約 1.8 倍高い短絡電流密度（JSC）を示した。一方で、解放電圧（VOC）と曲線因子（FF）は対称型分子 2 を用いた場合の方が高く、結果として PCE は二つの素子でほぼ等しい値となった。
【考察】
化合物 1 の方が 2 よりも高い JSC を与えたことから、短絡条件では電荷キャリアの生成から取り出しまでのトータル効率において前者のほうが優れると考えられる。しかしながら、VOC や FF は 2 を用いた場合の方が高いことから、分子構造の非対称化がキャリア再結合の抑制につながったとは必ずしも言えない。今後、光電変換プロセスの素過程を切り分けて解析し、非対称化の効果を詳細に評価する予定である。

－43－

2021-44
ソルバトクロミズムを示さないπ共役双性イオンの合成と物性
清水章弘

大阪大学

【目的】HOMO と LUMO のエネルギー差 (ΔEHL) の小さな分子は興味深い光学的・電気化学的特性を示す。我々は高い HOMO 準位をもつ電子ドナー性のアニオンと低い LUMO 準位をもつ電子ア
クセプター性のカチオンから構成されるπ共役双性イオン 1 と 2 を設計・合成し、比較的小さな
π電子系でありながら、ΔEHL が約 1 eV と非常に小さく、1000 nm 以上に吸収を有することを明らかにしている (J. Org. Chem. 2021, 86, 770–781.)。興味深いことに、1 がπ共役双性イオンに特徴
的な、大きな負のソルバトクロミズムを示すのに対し、2 はソルバトクロミズムを示さないことを見出した。本研究では、この原因を明らかにすることを目的として、3 および 4 を合成し、電子状態と物性を明らかにした。

【結果と考察】3, 4 を合成し、X 線結晶構造解析等により同定した。3 と 4 の電子ドナー性のア
ニオン部位と電子アクセプター性のカチオン部位の二面角はそれぞれ 57°、68° であり、2 (53°) より大きいことから、アニオンとカチオンの相互作用が弱いことが示唆された。3, 4 はラジカルカチ
オンへの酸化とラジカルアニオンへの還元に対応する両性の酸化還元特性を示し、酸化電位と還元電位の差から、ΔEHL は 2 (0.87 eV)、3 (0.69 eV)、4 (0.54 eV) の順に小さくなることがわかった。これは、二面角が大きくなって相互作用が弱くなることにより、ΔEHL が小さくなるためであると考えられる。
UV-vis-NIR スペクトルを測定したところ、ジクロロメタン中における吸収波長は、2 (1068 nm)、
3 (1277 nm)、4 (1637 nm) の順に長くなることがわかった。また、様々な極性の溶媒中 (トルエン、クロロベンゼン、ジクロロメタン、ジメチルスルホキシド) で測定を行ったところ、2 と同様に、
3 と 4 の吸収波長もほとんど変化しなかった。ソルバトクロミズムを示す 1 の結晶構造における二面角は 69° であり、ほぼ同じ大きさの二面角を有する 4 がソルバトクロミズムを示さないことから、二面角以外の影響が大きいことが実験的に明らかになった。今後、この原因について、量子化学計算等も用いて明らかにする予定である。

－44－

2021-45
Host-Guest Complexation of Cyclohexa-2,7-anthrylene Ethynylene
Derivatives with [n]CPP
Kenji Kobayashi Shizuoka University
Recently, we have successfully synthesized macrocycle 1a and found that 1a exists as amonomeric form and size-specifically encapsulates a cyclic p-phenylene 9-member [9]CPP
that matches the internal pore size of 1a (Fig. 1a, b). In this study, we synthesized a macrocycle
2a in which two of the six acetylene bonds of 1a at the diagonal position are replaced by
butadiyne bonds, and a macrocycle 1b in which the bulkiness of the side chain is slightly
smaller than that of 1a (Fig. 1a). Here, we report the properties of 2a and 1b.
The absorption and emission maxima of 2a were red-shifted slightly than those of 1a(max(abs) = 4 nm, max(em) = 7 nm), due to -conjugate expansion of 2a. In addition,
unlike 1a, 2a was found to encapsulate [10]CPP in a size-specific manner (Fig. 1c, Ka = 3,170
M–1 in CDCl3 at 298 K).
Unlike 1a and 2a, which behave as monomers, 1b was found to self-assemble into a

-stacked dimer (1b)2 (Fig. 2). The 1H NMR signals of the -stacked dimer (1b)2 andmonomer 1b did not average, the signals of (1b)2 were shifted upfield than those of monomer
1b, due to its own shielding effect. The self-association constant of (1b)2 was estimated to be
Ka = 3,560 M–1 in CDCl3 at 298 K. The -stacked dimer (1b)2 also encapsulates [9]CPP, andeach Ka value of the four equilibrium states at 318 K was calculated (Fig. 2). The Ka of (1b)2
was found to increase substantially in the presence of [9]CPP (Ka(4)/Ka(1) ≈ 42.8), and the[9]CPP inclusion association constant of (1b)2 was found to increase substantially more thanthe Ka of the monomer 1b (Ka(3)/Ka(2) ≈ 42.7).

－45－2021-46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】高分子は潤滑油の添加剤として使用され、その多くは直鎖状構造である。また、直鎖状高分子であるため、潤滑油の粘度を増加させてします。共振ずり測定は、高分子ブラシの潤滑性やゲルの表面粘弾性など、高分子材料の特性評価に用いることができる。本研究では潤滑油の基油に PAO401 用いて、潤滑油の添加剤としての超分岐構造高分子の特性を明らかにすることを目的とした。また、分岐構造が潤滑性に及ぼす影響について，直鎖状構造との比較により検討した。
【方法】直鎖状および超分岐構造高分子は制御された
ラジカル重合により合成された（共同研究者の登阪准Uout: 検出電圧
(振幅・位相)等色次数干渉縞
表面間距離
分解能0.1 nm
Uin: 入力電圧
バネ
: 正弦振動

教授の担当）。合成した高分子は PAO401 に溶解させた。
雲母表面の間に閉じ込められた潤滑油の特性は，共振ずり測定によって評価した（Fig. 1）。

白色光【結果】合成した高分子の PAO401 への溶解性は、紫Fig. 1 共振ずり測定装置の模式図。

外可視分光光度計を用いて評価した。直鎖状および超分岐構造高分子は、室温では PAO401 に溶解しなかっ(a)

たが、40 ℃以上では完全に溶解した。Fig. 2 は、高分子添加剤を溶解させた潤滑油の様々な荷重（L）におけ

MC (no slip)

る共振ずり測定の結果を示している。空気中で雲母同士が接触している状態（MC、摺動なし）を基準ピーク

L = 2.5 mNとしたとき、ピーク振幅 (Uout/Uin) は試料の潤滑性を

L = 0.01 mN

L = 4.0 mN

L = 1.4 mN評価するために使用することができる。MC ピークに対する振幅比について、直鎖状高分子と超分岐構造高分子を比較すると、超分岐構造の方が小さい値であっ(b)

MC (no slip)

た。これは、超分岐構造の方が直鎖状に比べ優れた潤滑性を有していることを示す。さらに、潤滑油の溶液
粘度を共振ずり測定に基づいて開発した超微量粘度計
L = 2.5 mNで測定をした。超分岐構造高分子の PAO401 溶液の粘L = 4.0 mN

L = 1.4 mN

度は、直鎖状高分子のそれに比べわずかに低く、L = 0.01 mN

PAO401 単独の粘度とほぼ同じであった。これらの共振
ずり測定結果は，超分岐構造高分子が直鎖状高分子よりも潤滑性が高く，低粘度であることを明らかにした。
【研究成果】これらの研究成果については、第 71 回高分子学会年次大会にて発表予定である。

－46－

Fig. 2(a) 超 分 岐 構 造 お よ び(b) 直鎖状高分子を溶解した潤滑油の共振ずり測定の結果。

2021-47（国際）Trace metal elemental and isotopic composition in the North Pacific Ocean:sources and internal cycling (2)Tung-Yuan Ho

Academia Sinica

Objectives:
The major objective of this joint study is to investigate the sources and internal cycling of
dissolved and particulate trace metals in the water column of the Northwestern and subarctic
Pacific Ocean and to evaluate the impacts of lithogenic and anthropogenic aerosols originatingfrom East Asia on the processes. My host at ICR, Kyoto University, is Prof. Yoshiki Sohrin.
Methods:
My laboratory has 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.
Seawater and particulate samples in the oceanic regions were taken on the cruises. Both dissolved
and suspended particulate samples were collected for trace metal elemental and isotopic
composition analysis. Elemental and isotopic composition of trace metals were determined by
HR-ICPMS and MC-ICPMS, respectively. The detailed information of the sampling andpretreatment are described in the following two published papers.
Result and Discussions:
The details of the results and discussions are described in the following two papers. Chih-Chiang
Hsieh, my Ph.D. student, has already finished the measurement of Fe isotopic composition in
the samples and is preparing a manuscript. In brief, although we have observed lighter Fe isotopic
composition in the suspended particles, the quantitative c ontribution of anthropogenic aerosol
Fe is smaller than what we expected in the oceanic region (Hsieh et al. in prep).
Publications:
Again, due to the impact of Covid-19, it was pity that I could not visit ICR, Kyoto University in
2021. However, Prof. Sohrin’s and my laboratory members have still kept close interaction in
the research topics. During the past year, we have published the following two papers. One paper
is under review (Takano et al. Marine Chemistry, minor revision); two more papers are underpreparation.
Liao, W.-H., S. Takano, H.-A. Tian, H.-Y. Chen, Y. Sohrin, and T.-Y. Ho* (2021) Zn elemental
and isotopic features in sinking particles of the South China Sea: Implications for its sources andsinks. Geochimica et Cosmochimica Acta doi: 10.1016/j.gca.2021.09.013
Zheng*, L., T. Minami, S. Takano, T.-Y. Ho, and Y. Sohrin (2021) Sectional distribution patternsof Cd, Ni, Zn, and Cu in the North Pacific Ocean: relationships to Nutrients and importance ofscavenging.Global Biogeochemical Cyclesdoi: 10.1029/2020GB006558.
－47－2021-48（国際）－48－2021-49（国際）Development of simulation scheme for wall-slip of polymers
Giovanni Ianniruberto Università degli Studi di Napoli “Federico II”
Wall-slip of polymers is a long-standing and challenging problem in polymer science andindustry. In industrial polymer processing, there are a lot of practical problems induced by thewall-slip, such as the shark-skin. While extensive studies have been made, the capability of
conventional theoretical/computational methods is rather limited at present. Due to the huge
computational cost, it is difficult to use molecular dynamics simulations for practical wall-slip
problems. On the other hand, while the mean-field theories (e.g., the tube model) have attained
success in polymer rheology, these theories have fundamental difficulties to address interfacial
phenomena. In summary, there is no practical method to predict/reproduce the wall-slip forindustrial polymers.
In this project, we will attempt to develop a mesoscopic multi-chain model to reproduce
polymer dynamics at the interface between polymeric liquids and the solid wall under fast
shear flow. Furthermore, to construct a practical simulation method for wall-slip of polymers,
we will incorporate the mesoscopic model into the macroscopic fluid simulation method, i.e.,the smoothed particle hydrodynamics (SPH). The team members have been separately
developing mesoscopic models for bulk polymers and attained success to reproduce therheological properties. We have been working on modeling entangled polymer dynamics [1].
The Masubuchi group at Nagoya University has been working on several multi-chain
simulation methods for entangled polymers. On the other hand, Takeshi Sato in the molecularrheology group at ICR has been working on the development of the SPH technique.
In this year, due to the difficulty related to the COVID19, our group and the molecularrheology group have independently conducted the research activity while sharing information.
We have developed the multi-chain slip-link model to address the wall-slip of entangled
polymers in collaboration with the Masubuchi group [2]. In this model, the effect of thewall-slip is artificially incorporated into the multi-chain slip-link model originally developed toreproduce entangled polymer dynamics (without the wall-slip). The results obtained by thismodel are in qualitative agreement with experimental results. Our ICR partner Takeshi Sato has
improved the simulation code of SPH for efficient flow simulations. In the future, we hope tounify these models for the further understanding of the wall-slip of polymers.
References:[1] Y. Masubuchi, J. Takimoto, K. Koyama, G. Ianniruberto, G. Marrucci, and F. Greco, J
Chem. Phys., 115, 4387 (2001).
[2] Y. Masubuchi, D. Vlassopoulos, G. Ianniruberto, and G. Marrucci, J. Rheol., 65, 213(2021).
－49－

2021-50（国際）High Frequency Response of Polymeric Liquids:
Rheology and Dielectric Relaxation
Sathish K. Sukumaran Yamagata University
The response of polymeric liquids to imposed fields is investigated using experiments typically
performed under isothermal conditions. It is assumed that the imposed field does not affect thesystem temperature, which continues to remain uniform throughout the system. The theoreticalanalyses correspondingly employs isothermal response functions. If thermal equilibration ishindered due to the imposed field, the assumptions of constant and uniform temperature might
become invalid. This might be the case for the response at high frequencies/short times. In thiscase, the adiabatic response functions might be more appropriate. To investigate this problem,the experimental and theoretical expertise of ICR (Sato, Watanabe, Matsumiya), and thecomputational, theoretical and experimental expertise of international (Ramirez, Madrid;
Tassieri, Glasgow) and domestic (Masubuchi, Nagoya) researchers have been combined toform a collaboration between ICR and several international and domestic research partners.
The effect of imposing isothermal and adiabatic conditions on the linear rheology of anunentangled (short chain) polymer melt was investigated. For simplicity, the polymer chainswere modelled as beads connected by springs and their motion simulated using molecular
dynamics (Kremer-Grest model). The isothermal simulations were performed by controlling
the temperature using a Langevin thermostat (NVT). In the adiabatic simulations, the system
was decoupled from the thermostat thereby preventing energy exchange and thermal
equilibration. Oscillatory shear deformation, with an amplitude sufficiently small for the
response to remain in the linear regime, was imposed at several frequencies. We found that theobtained storage modulus, G’, and the loss modulus, G’’, under both the isothermal and theadiabatic conditions were rather close to each other. This implied that the imposed conditions
had negligible effect on the relaxation times or equivalently, the dynamics of the polymer
chains, at least in the linear regime investigated here. Under adiabatic conditions however, thesystem temperature progressively increased with time and the temperature increase under highfrequency 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.
For instance, the system might undergo a change in state due to the heat generated by theimposed oscillatory shear deformation. We are currently investigating the response when theshear (oscillatory and step) is applied for longer times. Based on these results, we plan toinvestigate the more interesting but more difficult nonlinear response regime in the future.
－50－

2021-51（国際）Molecular understanding on the structures and dynamics of end-modified polymers.
Visit Vao-soongnern

Suranaree University of Technology

For high-cis linear polyisoprene (PI) head-modified with an associative metal-carboxylate (salt) group,
PI30-COOM with M = Li, Na, and K, we have conducted linear viscoelastic and dielectric measurements to
examine an effect(s) of the head-to-head association on the chain dynamics.1) The molecular weight of the
PI30-COOM chains was high enough (M = 30.5×103) compared to the entanglement molecular weight for PI(Me = 5.0×103), and their slow dynamics was governed by the entanglement relaxation. Those chains had
type-A dipoles so that their large-scale dynamics was reflected in both viscoelastic and dielectric data at low
angular frequencies . The salt groups associate and dissociate (without ionization) with a rate that changes
with the temperature T, as known for ionomers having non-polar backbones.2) Correspondingly, PI30COOM exhibited failure of the time-temperature superposition for both viscoelastic and dielectric data.
This failure was characterized through comparison with non-associative reference homo-PI, the PI30 unimer(a precursor of PI30-COOM), (PI30)2 dimer, and (PI30)6 star-type hexamer. The viscoelastic data of PI30COOLi at low and intermediate T (20 and 20C), respectively, were found to be close to those of the starhexamer and dimer data in the iso-frictional state (defined for monomeric segments), and a further increase of
T resulted in deviation from the dimer data toward the unimer data, as noted for the  dependence of thestorage modulus G'() data shown in Figure 1. This “crossover” was observed also for PI30-COONa andPI30-COOK but at lower T,1) which possibly reflected a barrier for the dissociation of the COOM groups
lowering in the order of COOLi > COONa > COOK. The decrease of the real part of dielectric permittivity
from the static state, '() = '(0)'(), and the imaginary part (dielectric loss), "(), measured for PICOOLi are shown in Figure 2. These dielectric data exhibit a crossover similar to that seen for G'() but at
higher T compared to the latter. This difference between the viscoelastic and dielectric behavior can be
related to the dynamic tube dilation mechanism that affects the viscoelastic data more significantly than the
dielectric data3) and also to the conformation exchange4) (motional coupling) among the PI30-COOLi chains
dynamically coexisting in different association forms, the unimer, dimer, and star-like multimers.1)
6-1

PI30-COOLi[PI]
Tr = 40Clog 'PI30-COOLi[PI]
Tr = 40C

-2

2

dimer
-1 0

star
unimer
3
2
2

T/C
‐20C
-20
0C0
20C
20
40C
40
60C
60

1

2

-1
log {a[PI]T /s }

3

1

2

3

4

5

6

3

4

5

6

-2

1

dimer
0

T/C
0C
0
20C
20
40C
40
60C
60

unimer

star

-3

4

log "log (G'/Pa)

5

4

-3

0

1

2

-1
log {a[PI]T /s }

Fig.1 Viscoelastic behavior of PI30-COOLi.

Fig.2 Dielectric behavior of PI30-COOLi.

References
1) Y. Matsumiya, H. Watanabe, N. Sukhonthamethirat, and V. Vao-soongnern, J. Soc. Rheol. Japan, 49, 181 (2021).
2) Z. Zhang, Q. Chen, and R. H. Colby, Soft Matter, 14, 2961 (2018).
3) Y. Matsumiya and H. Watanabe, Rubber Chem. Technol., 93, 22 (2020).
4) H. Watanabe, Y. Matsumiya, and Y. Kwon, J. Rheol., 61, 1151 (2017).

－51－

2021-52
光エネルギー変換に対する振電効果：固体 NMR と時間分解 EPR の連携による解明
小堀康博 神戸大学

序：本研究では、磁気共鳴分光法を主たる手法とし、有機系分子を中心とした次世代の光エネルギー変換材料の創成に向け、分子機構の解明が重要な有機薄膜系や連結系において、動的エキシトンによるスピン系相互作用をオングストローム領域の三次元映像で可視化し、三重項励起子や電荷分離立体構造による動的機構･電子状態を明らかにした。
梶らと連携して過渡種の運動性を特徴づけ、電子スピン分極の三次元画像から、時々刻々変化する励起子対、光電荷分離状態の立体配置、運動性による磁気的相互作用の変化を映像化すると共に、電子的カップリングを定量化している。1 結晶性と非晶性を併せ持つ
有機エレクトロニクス薄膜や有機光触媒のエントロピー効果と運動による電子的効果を用いるデバイス効率飛躍的向上化の知的基盤を獲得し、有機薄膜太陽電池や有機発光素子(OLED)開発で課題となっている超高効率化への指針を提示 1 することができるようになってきた。
実験方法・結果と考察：共同研究者の梶 弘典先生との研究
では、高効率な OLED 特性を示す、アクリダン-トリアジン
系の熱活性化遅延蛍光材料 MA-TA を対象とし、時間分解電子スピン共鳴（TREPR）法を用いて光照射直後に生成する励
起状態の観測と解析を行った。三重項励起子による電子ス
ピン分極の効果を解析することによって中間体励起子の立体構造を図 1 のように決定した。さらにスピン格子緩和時間に対する分子異方性の情報も得ることができた。これにより、アダマンチル基の結合軸回りに対する分子回転運動(図 1)による動的ゆらぎ効果を特徴づけることができた。

図 1. MA-TA の TREPR 計

測で明らかになった三重項励起子の立体構造

成果（論文、学会発表等）学会発表
1. Imahori, H.; Kobori, Y.; Kaji, H., Manipulation of Charge-Transfer States by Molecular Design:
Perspective from “Dynamic Exciton”. Acc. Mat. Res. 2021, 2 (7), 501-514. （査読あり）
2. 勝平譲治・日下部 悠・和田啓幹・菅野奈都子・Ren Yongxia・梶 弘典・小堀康博 “時間分解 EPR 法による熱活性化遅延蛍光分子の励起状態の解析” 2021 年光化学討論会
2021.9.14-16.
3. 勝平譲治・日下部 悠・和田啓幹・菅野奈都子・Ren Yongxia・梶 弘典・小堀康博 “時間分解 EPR 法による熱活性化遅延蛍光分子の励起状態の解析” 日本化学会第 102 春
季年会(2022) 2022.3.23-3.25.
－52－

2021-53
Effect of microplastics on 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, 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. 8, 9 and October 26 in 2021.
Water temperature, salinity and pH were measured on-site. All sea water samples were transferred to precleaned
LDPE Nalgene bottles. Unfiltered samples were directly collected from Niskin bottles to determine theconcentrations of total dissolvable trace metals (tdMs). Some portions of samples were filtered through PTFE
membrane filters with pore size 0.2 µm to determine the concentrations of dissolved trace metals (dMs). All thefiltered and unfiltered samples for trace metals were acidified with 20% HCl (Tamapure AA-10) to achieve a
final HCl concentration of 0.010 mol/kg (pH ~2.2). Nitrate, nitrite, phosphate, and silicic acid were determinedby autoanalyzer. Chlorophyll a was determined by high performance liquid chromatography. Fluorescent organic
matter (FDOM) was analyzed by three-dimensional fluorescence method.
The trace metals were preconcentrated using a chelating resin which ethylenediaminetriacetic and iminodiacetic
acids were immobilized (NOBIAS CHELATE-PA-1, Hitachi High-Technology). A high-resolution ICP-MS(HR-ICP-MS) equipped with a magnetic sector mass spectrometer (ELEMENT 2, Thermo Fisher Scientific).
The sample solutions for microplastics were filtered by PTFE membrane filters with pore size 5.0 µm. After
filtration, the samples with filters transferred to separatory funnel. A saturated NaI solution was added to theseparating funnel, and the microplastics were separated by the difference of density. After separation, the organic
matters remaining in the sample were decomposed by mixed acid (HNO3+HClO4+HF). Microplastics wereidentified by Microscopic Raman photoluminescence system (LabRam HR type, HORIBA, Ltd.,)
Results and discussions) The concentrations of microplastics in the Osaka Bay are 8.5 (0 m), 8.0 (10 m), and7.3µg/L (15 m), respectively. The types of microplastics at the surface (0 m) were polypropylene (19%),polystyrene (42%), and others (39%), respectively. The types of microplastics at 10 m were polypropylene (25%),
polystyrene (16%), polyethylene (6%), Nylone66 (3%), polyvinyl chloride (3%), respectively.
Achievement report) Nakaguchi, Y., Ikeda, Y., Sakamoto, A., Zheng, L., Minami, T., Sohrin, Y., 2021,
Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the East China Sea, Journal of
Oceanography, https://doi.org/10.1007/s10872-020-00577-z－53－2021-54
イオン液体含有高分子膜を用いた金属イオンの液膜輸送に関する研究
向井浩

京都教育大学【目的】 将来的な電気自動車の普及に伴い、リチウムイオン電池の材料であるリチウム、コバル
ト等の希少金属の安定供給のため、これらのリサイクルの必要性が高まることが予想される。リサイクル技術の一つとして、金属を溶解した酸性溶液から目的とする金属イオンを抽出する湿式精錬法があるが、抽出溶媒として有機溶媒の代わりに疎水性の液膜を用いる液膜輸送はその一種に位置付けられる。液膜輸送は、膜の反対側に第 2 の水相を設け、膜を介して一方から他方の水相へ金属イオンを能動輸送させることで、目的イオンの分離濃縮を達成しようとする方法である。液膜中を輸送するキャリアーとしてプロトン解離型の有機配位子であるキレート試薬を用いることで、2 つの水相間の pH 差に基づくプロトンと金属イオンの陽イオン交換反応を利用した金属イオン（Mn+）の能動輸送が可能である。本研究では、イオン液体（IL）を液相とした液膜輸送により、リチウム
イオンとコバルトイオンを相互分離することを目指し、その基礎的検討を行った。
【方法】 (1) イオン液体含有高分子膜の作成

キレート試薬 1-phenyl-3-methyl-4-benzoylpyrazol-5-

one (BMPP) を 0.05 mol kg-1 含む疎水性 IL 1-butyl-3-dodecylimidazolium bis(trifluoromethanesulfonyl)imide ([C4C12im][Tf2N]) 1.0 g に、tetrahydrofuran 5 g に溶かした polyvinyl chloride (PVC) 0.1 g を加え、内径 49 mm のガラス製シャーレ内に 3 日以上静置して円形の膜を作成した。(2) 液膜輸送

(1) の膜を PVC 製 U 字形液膜輸送セルの中央に挟み込み、膜の両側の容器に、HCl で pH を調節した供給相水溶液（[Mn+] = 2.0×10-5 mol dm-3, [CH3COONa] = 0.01 mol dm-3, [KCl[ = 0.1 mol dm-3, pH 5）と受容相水溶液（[CH3COONa] = 0.01 M, [KCl[ = 0.1 mol dm-3, pH 1 or 2）を、それぞれ 30 cm3 入れた。
両水相を 24 時間撹拌後、pH、体積、金属濃度を測定し、金属イオンの物質量と存在率を算出した。
【結果と考察】(1) イオン液体含有高分子膜の作成

imidazolium イオンの 1 位と 3 位の alkyl 基の炭素数が 1 と 6 の[C6C1im][Tf2N]、及び、1 と 8 の[C8C1im][Tf2N]を用いた膜は、硬く不透明で ILの含有率も低かった。一方、炭素数が 4 と 12 の[C4C12im][Tf2N]を用いた膜は、柔らかく透明で IL
含有率が約 90%と高かった。このため、[C4C12im][Tf2N]膜を液膜輸送に用いた。(2) 液膜輸送分離
Li+と Co2+を等量含む混合水溶液からの相互分離を検討した。Co2+のみを 34%の輸送率で受容相に輸送することが出来、Co2+の分離が達成できた。しかし、Li+と共に 29%の Co2+が供給相に留まったため、Li+のみを供給相に分離することは出来なかった。また、Co2+が液膜相中に残存し、これが輸送率と回収率を低下させる原因となった。(3) 輸送率向上の検討

Co2+の輸送率を向上させる試みとして、液膜相中に予め Co2+を錯形成により含ませた膜を調製し、液膜輸送に用いた。その結果、錯化容量の 45-68%の Co2+を含んだ膜で、Co2+の 97%以上が供給相から除かれ、かつ、受容相への輸送率が 100%以上となった。輸送率が 100%を超えるのは、膜中に予め含ませた Co2+の一部が受容相に溶離して合算されるためである。この結果は、供給相から受容相へのほぼ完全な輸送が達成されたことを示すものであり、Li+と Co2+の高い分離能が期待できる結果が得られたと言える。
【成果報告】
1. 向井浩, 安達智哉, 三嶋大侑, 宗林由樹,日本分析化学会第 70 年会講演要旨集, P3111 (2021).
－54－2021-55
硫黄系高分子薄膜材料における硫黄元素が構成するナノ構造の
空間不均一性評価
藤原明比古 関西学院大学

1. 緒言: SAXS-CT 法では、各投影角度において試料を y 方向に走査して SAXS 測定を実施する必要がある。測定により、各投影角（φ）における各試料位置（y）での SAXS 像が得られる。像内の任意の q 位置における散乱強度を選択することで、CT 像を再構成するためのシノグラムが φ に対する y のイメージとして得られる。しかしながら、試料と空気界面部分では、時として余計な散乱像が生じる要因ともなり得る。入射 X 線が試料の表面や、角部分に照射されることで、表面・界面での反射や散乱がストリークの起源になる。シグナル上にストリークの強度がオーバーラップしてしまうと、再構成した CT 像では強いアーティファクトの発現要因となる。そこで我々は、シノグラム上において、試料表面で発現した位置のストリーク強度をノイズと見なし、Tikhonov 正則化によりその除去を試みた。
2. 実験 : 代表的な結晶性高分子である高密度ポリエチレン（HDPE, Toshoh Coporation）を角柱状に成形した試料を測定に用いた。切削により試料サイズを制御することが容易であるため、本デモンストレーションを示す最適な試料として HDPE を選定し、測定用試料を成形した。
3. 結果 : 図 1 に、試料から得られた二次元 SAXS 像を示す。図 1 (a)では、リング上の q = 0.21 nm-1 近傍においてブロードなピーク（位置 A）が発現しており、この位置はラメラ構造間の周期長に対応している。一方で、入射X 線が試料の端部分に照射した時に得られる代表的な二次元像の図 1(b)では、中心位置から赤道線方向に非常に強いストリークが発現した。特に qy > 0 nm-1 方向でのストリークが強く、これは試料の片側表面において反射した X 線がこの方向に減衰せずに観察されていることを示している。逆側の試料表面で反射した時には、qy < 0 nm1

方向でのストリークが強く観察された（図 1(c)）。例え

Figure 1. (a) 2D SAXS image
without streak patterns. (b)-(d)Representative
2D
SAXS
imagescontaining
streakpatterns.

ば、図 1 のリングパターン上のピーク位置 qy = 0.17 nm-1
（図 1 内の A 部分）を選択し、各 φ と y に関する散乱強度を二次元上にプロットしたシノグラムイメージから再構成した CT 像は試料の四面部分において非常に強いアーティファクトが発現した（図 2(a)）。一方で、我々の開発した Figure 2. (a) Original CT images
Tikhonov 正則化によるフレームワークを使い、ノイズを除 reconstructed from the original
sinogram. (b) Improved CT
去したシグナル成分のシノグラムから CT 像を再構成する images reconstructed from thesinogramofthesignalと、輪郭部分のアーティファクトが除去されており、表面 components obtained after
noise elimination.
領域が明確に観察された（図 2(b)）。
－55－

2021-56
Structure analysis of polymer materials having sulfur atoms in a wet state byresonant small-angle scattering methods
Katsuhiro Yamamoto Nagoya Institute of Technology
Polymer structure analysis by the small-angle X-ray scattering method has become popular.
Utilizing tender X-rays (1-5 keV) enables us to analyze the distribution state in the structureelementally selectively for light elements such as phosphorus, sulfur, and sodium, which areimportant elements for living organisms and functional polymer materials. In particular, there
are almost no examples of analyzing these spatial structures and their distribution by the X-ray
scattering method in the tender region. The amount of structural information obtained by theresonance scattering method near the absorption edge of X-rays peculiar to an element increases
dramatically, and it becomes possible to analyze the chemical state of a specific element inaddition to the local structure of element and component selection. We aim to expand the use of
the tender X-ray region and perform scattering experiments in a more natural state, especially in
wet environments. This application will work on a detailed structural analysis of polymer
materials that are important in today's society, such as fuel cell membranes containing sulfur
elements, targeting sulfur elements. Developing a scattering method that utilizes the unused
wavelength region will open up a new path for structural analysis of multicomponent polymer
materials by a new analysis method that can directly extract buried structural information.
We made a special sample cell suited for an X-ray scattering experiment under a high vacuum
utilizing tender X-rays. The figure shows the energy-dependent SAXS profiles (X-ray energy of2479 eV is the adsorption K-edge of Sulfur) of poly(styrene sulfonic acid)-b-poly(2-ethyl hexyl
acrylate) (S2EA) thin film (20 m in thickness) swollen with water. The block copolymer forms
a microphase-separated structure. SAXS profiles of the microphase-separated structure in water
were slightly different from each other. That means that
sulfur atoms do not distribute uniformly in the PSSA
domain. If sulfur atoms were uniformly distributed, all
the SAXS profiles would be identical (shape) except for
SAXS intensity. We will continuously proceed with thedetailed structure analysis (distribution of watermolecules and sulfonic acid groups). A part of the study
was summarized to present an annual conference of theSociety of Polymer Science, Japan. Related work (water
distribution in polymer thin film) from our groups has
been published in Langmuir (K.Yamamoto et al.
Langmuir 37, 14550-14557, 2021).
－56－

2021-57
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[目的] 自然界の限られた資源を有効活用するためには、様々な元素を組み合わせて高性能な物質・材料を創造していくことが求められる。可視域に局在表面プラズモン共鳴(LSPR)吸収を示す材料の場合、周期表 11 族の単金属（Cu、Ag、Au）のみが使われてきた。しかし近年、京大化研の寺西研究室において、B2（塩化セシウム）型 PdIn ナノ粒子が可視域に LSPR 吸収を示すことが発見された。組成比や原子種を改変することで LSPR 吸収波長を制御できると期待される。
我々は、合金ナノ粒子の第一原理計算を行い、LSPR 特性を制御するための理論的指針を構築す
ることを目的として研究を進めてきた。これまで、B2 型合金の比較的疎な構造によって LSPR が発現することを明らかにしてきた。そこで本年度は、PdIn と同様に比較的疎な C1 型構造を持つ
PtIn2 に着目して、光学特性を解析した。
[計算手法] 本研究では、直径数 nm のナノ粒子の光電子物性を原子・電子のレベルで明らかにすることが求められる。そのために、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、光励起電子ダイナミクスのシミュレーションを行った。対象としたのは、
図 1 に示した C1 型構造を持つ PdIn2 のナノ粒子である。結晶構造から直径
約 3 nm の粒径の Pt249In432 を切り出して計算した。比較のために、同程度の大きさの Au561 についても計算を行った。

図 1. 対象とした
Pt249In432 ナノ粒子の結晶構造。黒がIn で灰色が Pt。

[結果と考察] 光吸収スペクトルを計算したところ、Pt249In432 は 2.8 eV 付近に Au561 の LSPR と類似のピークが見いだされた。そこで Pt249In432 について、2.8 eV の光によって誘起される電子ダイナミ
クスを解析した結果、電子の集団振動が励起されることが見いだされた。この結果から、Pt249In432
でも可視光で LSPR が励起されることが明らかになった。
[学会発表]
1. 飯田健二，「ナノ界面系の電圧や光に対する応答の理論的研究」京都大学福井謙一記念研究第311 回化学コロキウム，東京都立大，東京都八王子市，2021 年 12 月 17 日(招待講演)
2. 飯田健二，「不均一触媒の光や電圧に対する応答の理論計算研究」触媒・電池戦略研究拠点第18 回公開シンポジウム，オンライン開催，2021 年 11 月 15 日(招待講演)
3. 飯田健二，「ナノ界面系の光や電圧に対する応答の理論的研究」第 15 回分子科学討論会，オンライン開催，2021 年 9 月 18-21 日(招待講演)－57－2021-58
部分フッ素化両親媒性分子の膜物性・構造に対する Rf 鎖長依存性の解析
園山正史 群馬大学【目的】

私たちは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，パーフルオロアルキル基(Rf, CnF2n+1)を疎水鎖末端に部分的に導入した両親媒性分子が，Rf 鎖長依存的な際だった物性を示すことを明らか に し て 来 た 。 本 研 究 で は ， n = 5 お よ び 7 の Rf 基 を 有 す る ， リ ン 脂 質
Dimyristoylphosphatidylcholine（DMPC）の部分フッ素化アナログ分子 F5-DMPC および
F7-DMPC を新たに合成し，表・界面物性および分子構造を解析することにより，膜物性・構造の Rf 鎖長依存性の起源を明らかにす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部分フッ素化リン脂質 F7-DMPC を用いて，水面上単分子膜の表面圧−面積（π−A）等温曲線を 15℃および 25℃において測定した。
さらに，水面上単分子膜を基板に転写し，赤外反射吸収（RAS）スペクトルを測定した。
【結果と考察】25 ℃において測定した F7-DMPC 水面上単分子膜のπ−A 曲線を，

F6-DMPC および F8-DMPC とともに右図に示す。
F7-DMPC では F6-DMPC と同様に気体膜に特徴的なπ−A 曲線となり，分子間の強い相互作用により非圧縮時から分子が凝集し，液体膜の特徴を示す F8-DMPC とは大きく異なることがわかった。
長い Rf 鎖を有する化合物の場合，異なる結晶型を示す 15 ℃においても，F7-DMPC は同様の傾向を示した。さらに，RAS スペクトルにおいて
CF3 対称伸縮振動バンドが明瞭に観測されたことから，F7-DMPC の Rf 基は水面に対して垂直方向に配向している可能性が示唆された。この分子配向の特徴は F6-DMPC および F8-DMPC と同様であった。F5-DMPC のグラムスケールの合成は精製条件の最終検討の段階に入っており，間もなく完了する予定である。今後 F5-DMPC のπ−A 曲線および RAS スペクトルの測定を行い，二本鎖分子である部分
フッ素化リン脂質 Fn-DMPC の膜物性・構造において観測されている興味深い Rf 鎖長依存性の物理化学的起源を，長谷川らが提唱している階層双極子アレー（SDA）理論との関連から明らかにする。
【成果報告】
学会発表：中川原亜依ら 「一本の疎水鎖をフッ素化した新規部分フッ素化リン脂質の合成と熱物性」, 日本化学会第 102 春季年会 （2022 年 3 月 24 日（予定）），他 1 件。

－58－

2021-59
A spectroscopic analysis on bio-degradation processes of polymer thin film
surfaces
Takashi AOKI Kyoto Institute of Technology
1. Objectives
A spectroscopic study of the degradation process on the surface of polymers is verysignificant as pollution caused by plastics remaining in the oceans is attracting worldwide
attention. We focused on the surface of the poly(L-lactic acid) (PLLA) thin film where thebiodegradation initiates and measured the degradable process on its surface using
multiple-angle incidence resolution spectrometry (pMAIRS). The spectroscopic instrument
provides attractive information on the presence or absence of functional groups and theirorientation in polymer chains for amorphous samples, making it a very useful tool forunderstanding the reaction occurring near surfaces. This study was conducted under the
precious guidance of Prof. Takeshi Hasegawa of the Institute for Chemical Research, Kyoto
University.
2. Experimental methods
PLLA was dissolved in chloroform, and the PLLA thin film was coated on a silicon wafer
surface using a spin coater. The film thickness was measured by ellipsometry. The
PLLA-coated Si wafers were immersed in Tris-HCl buffer solution of Proteinase K (100g/mL) at 25C for a predetermined time, washed and dried, and then subjected to thepMAIRS measurement.
3. Results and Discussion
The thickness of the as-prepared PLLA film was 115 nm, and after immersion in Proteinase K
solution for 5 and 10 min, it was 104 and 81 nm, respectively. The overall absorbances in theregions between 4000 and 650 cm-1 of the spectra of pMAIRS also decreased with the time ofthe enzymatic reaction. The polyester was degraded by the enzyme, resulting in acorresponding decrease in the film thickness on the silicon wafer. The pMAIRS operation gives
us two components of the in-plane (IP) and out-of-plane (OP) spectra of the polymer against
the substrate surface. The intensity ratios of IP and OP spectra around 1760, 1185, and 1190
cm-1 were found to vary with the time of the enzymatic reaction. At present, additional
analytical approaches such as AFM and WAXD are being carefully carried out to ensure thatthe variations in the spectra can be accurately interpreted. In addition, as the orientation of thepolymeric chains in the thin film may be affected by the substrate, we are preparing films withdifferent thicknesses and also investigate the film thickness dependence of the IP and OP
spectra. Through several analyses, information such as the degree of orientation of any
functional group on the surface of PLLA will elucidate the degradation process.
－59－2021-60
Identification of an active gibberellin compound in the basal land
plant Marchantia polymorpha
Takayuki Kohchi

Kyoto University

A plant hormone gibberellin (GA) is a diterpene compound that regulates plant growth anddevelopment, including seed germination, cell elongation, and flower bud formation. Genome
analyses revealed that the biosynthetic pathway and signal transduction of GA were acquired in theland plant lineage during evolution. However, the function and ancestral form of GA in the basal land
plants are still unknown. The liverwort Marchantia polymorpha L. is a model of basal land plants tounderstand the molecular evolution of the mechanisms in plant development. The M. polymorphagenome encodes all genes necessary for the biosynthesis of GA12, a precursor for active GAs.
Furthermore, the mutants of GA biosynthetic genes showed pleiotropic phenotypes including growth
retardation and delayed sexual development. We have developed a bioassay system to elucidate thebioactive form of GA (GAx) in M. polymorpha. In collaboration with Dr. Shinjiro Yamaguchi (coresearcher) and Dr. Kiyoshi Mashiguchi (research collaborator), Institute for Chemical Research,
Kyoto University, we found that a specific fraction prepared by the combination of the two-phasepartitioning method and HPLC gradient program restored the defects of GA biosynthesis mutants. We
will determine the chemical structure of GAx by combining mass spectrometry and NMR.
Furthermore, it is crucial to identify the receptor for active GAs in M. polymorpha. The M. polymorphagenome does not encode GID1, a component of the typical receptor of GAs known in vascular plants.
The ligand-receptor co-evolution might have occurred during land plant evolution. A genetic approachhas been taken to identify the GA receptor in M. polymorpha. The mutant of MpSABATH2, which is
expected to encode an inactivating enzyme of GAx, showed severe phenotypes such as dwarfism andgrowth inhibition. We conducted the EMS mutagenesis to screen suppressors of the Mpsabath2 mutant.
The molecular genetic analysis of the obtained mutants is ongoing.
Shimokawa, E., Kawamura, S., Sun, R., Suzuki, K., Yoshitake, Y., Yasui, Y., Nishihama, R., Yamaoka,
S., Mashiguchi, K., Yamaguchi, S., and Kohchi, T. Screening of novel mutants affecting a gibberellinrelated methyltransferase function in Marchantia polymorpha. The 63rd Annual Meeting of theJapanese Society of Plant Physiologists. March 22-24, 2022.

－60－

2021-61
Glass Transition and Molecular Dynamics of Guest Low Mass Molecules in
the Clathrate of Polymer Crystals
Osamu Urakawa Osaka University
Syndiotactic polystyrene (sPS) forms co-crystalline structures with several guest molecules,
called δ-phase or ε-phase. The δ-phase accommodates each guest molecule in the isolated
space, while the ε-phase confines guest molecules in a channel-like one-dimensional space. We
found that dielectric measurements could detect the rotational relaxation of polar guest
molecules confined in both phases, where the guest dynamics were highly asymmetric [1-3].
The dynamics of spatially confined molecules is influenced by (1) the interaction with thecavity wall and (2) the physical confinement effect [4]. This study used polar guest molecules
such as benzonitrile, halobenzene, nitrobenzene, etc., which do not interact strongly with thecavity wall inside the sPS crystal. Therefore, simple confinement effects are considered todetermine the guest dynamics. Experimentally, therotational relaxation times τ of various guest
molecules in the δ phase correlate well with only theguest molecular length l (in the long axis direction),suggesting that the confinement effect governs theguest dynamics.
Fig.1 shows the temperature (T) dependence of τ forseveral guest molecules in the δ-phase. In the time
and temperature ranges examined, all the τ(T) obey

Fig.1. Crystalline structures of δ and ε phases.

the Arrhenius equation: τ  exp(Ea/RT), where Ea isthe activation energy. This behavior was the same in thecase of the ε phase. However, the τ and Ea of the same
guest molecule are shorter and lower in the ε phase thanin the δ phase. This means that the confinement of guest
molecules is weaker in the channel-like space of the εphase.
Fig.2 shows the l dependence of Ea for several guest
molecules in the δ-phase, indicating the excellent

Fig.2. l dependence of Ea.The solid line
represents the model prediction.

correlation between l and Ea.
[1] O. Urakawa, F. Kaneko, H. Kobayashi, J. Phys. Chem. B. 2012, 49, 14461.
[2] H. Kobayashi, O. Urakawa, Chem. Phys. 2016, 479, 122.
[3] H. Kobayashi, S. Akazawa, O. Urakawa. F. Kaneko, T. Inoue, Macromolecules, 2018, 51, 8611.
[4] F. Kremer, A. Huwe, M. Arndt, P. Behrens, W. Schwieger, J Phys Cond Matter, 1999, 11, A175.
－61－

2021-62（国際）Nonlinear Rheological Behavior of Telechelic Ionomer withDistribution of Ionic Stickers at the Ends
Zhijie Zhang

Chinese Academy of Sciences

Objectives

In our previous studies, we consider that the neighboring ions should exhibit
motional coupling if their distance is shorter than the Kuhn length so that the strand
between them becomes non-flexible. This idea is tested in our previous studies. (ACSMacro Letters, 2020, 9, 917-923). Based on the study explained above, we will continue
to examine nonlinear rheology behavior of this new type of telechelic ionomers.
Experimental methods

A new type of telechelic ionomers was synthesized through a two-steppolymerization utilizing a bifunctional initiator.
Experimental results and Discussion

The damping function h() of the TPiBA-m samples of m = 0.54-0.98 and rTPiBA
are compared in Figure 1. For comparison, the damping behavior of unentangled linear
chains, entangled linear and star-shaped chains reported by Watanabe and coworkers areadded (gray squares and spheres). In our opinion, this difference of damping behavior isowing to the different damping mechanisms: Besides, we find that using peak as thehorizontal axis normalizes h() reasonably, and h() drops significantly at peak > 1,
both features suggest the damping of the current samples are mainly due to the straininduced dissociation.

Figure 1: (a) The damping function of TPiBA-m and the reference sample rTPiBA obtained from step-strain
relaxation experiments. (b) The damping function of TPiBA-m and rTPiBA plotted against normalized strain peak.

Outcome reports

This study investigated the non-linear rheology properties of a newly designed typeof telechelic ionomers. The damping of the current samples is mainly attributed to thestrain-induced dissociation.

－62－

2021-63（国際）Role of PX-PH-type Phospholipase Ds in Plant Intracellular
Membrane Traffic
Yohei Ohashi

MRC Laboratory of Molecular Biology

Objectives: Phospholipase D (PLD), which hydrolyzes glycerophospholipids to produce
phosphatidic acid (PA), is involved in dynamic cellular processes, including membrane traffic,
signal transduction, and cytoskeletal reorganization through molecular functions of PA. PLD isrequisite for plants in their development according to the genetic program and responses toenvironmental stimuli. However, particular cell biological processes that PLD promotes for
those phenomena largely remain elusive partly because subcellular loci where PLD functions
for each phenomenon remain unknown. In this collaboration research, we performed
comparative analysis for subcellular localization patterns of PLDζ1 and PLDζ2,
eukaryote-general PX-PH-type PLDs of Arabidopsis thaliana, for a clue as to their functions incell biological processes.
Experimental Methods: Transgenic Arabidopsis lines, which expressed fluorescence protein
fusions of PLDζ1 and PLDζ2, and their N-terminal partial proteins, were constructed, and thencrossed with lines expressing various fluorescence markers for intracellular localization. Rootcells of those constructed transgenic lines were observed by confocal laser-scanningmicroscopy.
Results and Discussion: Own promoter-driven fluorescence protein fusions of PLDζ1 and
PLDζ2 were detected in various types of cells and only mature lateral root cap cells,
respectively. In mature lateral root cap cells, fluorescence protein fusions of PLDζ1 localized tothe entire trans-Golgi network (TGN) while that of PLDζ2 localized to the tonoplast andpunctate structures including a part of the TGN and multi-vesicular bodies. These localization
patterns were reproduced using their N-terminal partial proteins containing PX-PH domains.
An inducibly overexpressed fluorescence protein fusion of the PLDζ2 partial protein first
localized to the punctate structures, and then accumulated predominantly on the tonoplast.
Further domain dissection analysis revealed that the N-terminal moiety preceding the PX-PH
domain of PLDζ2 was required for the tonoplast-predominant accumulation while either
PLDζ1 or PLDζ2 PX-PX domain alone is able to localize to punctate structures. These findings
suggest that PLDζ1 and PLDζ2 play partially overlapping but nonetheless distinctive roles in
the post-Golgi membrane trafficking from the TGN to the tonoplast.
Publication: Shimamura, R., Ohashi, Y., Yamamoto, Y. Y., Kato, M., Tsuge, T., and Aoyama, T.
(2022) Arabidopsis PLDζ1 and PLDζ2 localize to post-Golgi membrane compartments in apartially overlapping manner. Plant Mol. Biol. 108:31-49.

－63－2021-64（国際）Role of Phosphoinositide Signaling in Pollen Development
Sheng Zhong

Peking University

Objectives: Phosphatidylinositol 4,5-bisphosphate [PtdIns(4,5)P2], a minor phospholipid
component of eukaryotic membranes, is involved in the regulation of various intracellular
events, including actin cytoskeletal organization and membrane trafficking, through theinteraction with its effector proteins. The spatiotemporal existence of PtdIns(4,5)P2 is a criticalfactor for its signaling function, and established basically via its metabolization. Although themetabolic pathways of phosphoinositides are elaborately linked to one another,
phosphatidylinositol 4-phosphate 5-kinase (PIP5K), which produces PtdIns(4,5)P2 byphosphorylating PtdIns(4)P, is thought to be a key enzyme responsible for the spatiotemporal
pattern of PtdIns(4,5)P2 in higher plants, in which some of the phosphoinositide metabolic
pathways found in animals and fungi are missing. The model plant Arabidopsis thaliana has 11
PIP5Ks, which are classified into type A (PIP5K10 and 11) and type B (PIP5K1–9) based on
the absence and presence of membrane occupation and recognition nexus (MORN) repeats attheir N-termini, respectively. In this collaboration work, we investigated functions of PIP5K
and PtdIns(4,5)P2 in pollen development and pollen tube growth. We prepared a series of
PIP5K loss-of-function mutants. Starting with these, we identified a set of PIP5K genes
required for pollen development and pollen tube growth.
Experimental Methods: T-DNA or transposon tagging mutant lines of PIP5K genes wereobtained from public organizations of biological resources. Null alleles for each type-B PIP5K
genes were established and crossed with one another to obtain multiple mutant lines. Single
and multiple mutant lines of the PIP5K genes were examined for their phenotypes in pollen
development and pollen tube growth.
Results and Discussion: Using the multiple mutants pip5k4pip5k5, pip5k4pip5k6, andpip5k5pip5k6, which were constructed previously, we confirmed that the PIP5K4–6 genes
redundantly function in pollen tube growth. Consistent with this, either YFP-fused PIP5K4–6
transgene could rescue the sterility of pip5k4pip5k5pip5k6 triple mutant pollens. In transgenic
plants heterozygously harboring the PIP5K6-YFP transgene under the pip5k4pip5k5pip5k6
triple mutant background, pollens without and with the YFP fluorescence were apparently thesame in their morphology. However, the former could not germinate at all in vitro whereas thelatter normally germinated. Phylogenetic analysis of angiosperm type-B PIP5Ks revealed thatthe clade containing PIP5K4–6 is conserved in angiosperms, and that PIP5K6 orthologs
constitute a distinct subclade from that containing PIP5K4/5 orthologs in core eudicots. These
facts suggest that the common ancestor of the PIP5K4–6 genes evolutionally differentiated tofunction in pollen development and/or pollen tube growth, and then further functional
differentiation occurred between PIP5K4/5 and PIP5K6 orthologs.
－64－2021-65（国際）Self-Assembling Adjuvant-Built-In Vaccines for Cancer Immune
Therapy
Yan-Mei Li Tsinghua University
The Uesugi group of ICR recently discovered cholicamide, a self-assembling smallmolecule vaccine adjuvant that potentiates innate immune responses through its interaction
with toll-like receptor 7 (TLR7) [Angew. Chem. Int. Ed., 2021]. During the course of thecholicamide study, the Uesugi group observed its induction of IL12p70, a cytokine thatplays a major role in cancer immunosurveillance and promotes immune responses of CD8
T-cells and natural killer (NK) cells. This observation encouraged us to explore the utilityof cholicamide in cancer immune therapy.
In FY2011, we examined the anti-tumor activity of cholicamide together with an
antigen peptide. However, cholicamide exhibited cytotoxicity in bone-marrow-derived
dendritic cells (BMDC), which encouraged the Uesugi group to further optimize thestructure of cholicamide. Evaluation of 12 new derivatives led to the discovery of C7,
which was found to be three times more immunostimulating than cholicamide in BMDC.
Importantly, C7 showed almost no cytotoxicity in BMDC up to 80 µM. The toxicity of C7
was also evaluated in mice. No increase in ALT, AST, and ALP (indicators ofhepatotoxicity) and UREA and CREA (indicators of nephrotoxicity) was observed evenwhen 500 µg of the compound was administered to the mice.
The potent immunostimulating activity and low toxicity of C7 encouraged us to
examine its ability as an adjuvant for cancer vaccines. After constructing the melanoma
tumor-bearing mice, we evaluated cancer volumes, survival rate, and mice weight. Whilethe control group and the group receiving only C7 showed an increase in cancer volume
and all mice died within 15 days, the group receiving the antigen-peptide and C7 showeda marked suppression of cancer volumes and a 21-day survival rate of 80%. In contrast,
the group receiving only antigen peptide showed a slight inhibition of cancer volume
growth, but the 21-day survival rate was only 20%.
The reason why C7 exhibits low cytotoxicity but potent immune activation remains
unclear. Dynamic light scattering experiments suggest that the assemblies of C7 arethermodynamically more stable than those of cholicamide. The stable C7 assembly may
play a role in its excellent property as a cancer vaccine adjuvant.

－65－

2021-66（国際）Site-Selective Protein Acetylation by a Small Molecule
Lu Zhou

Fudan University

Post-translational modifications (PTMs) play essential roles in regulating a myriad of cellular
processes in mammalian cells, including signal transduction, metabolism, and genetranscription. Among protein modifications, acetylation and phosphorylation represents themost critical PTM. In FY2021, we continued our collaboration with the Uesugi research groupin ICR to design small molecules that specifically acetylate or phosphorylate cellular proteins.
 Acetylation of cGAS. The presence of DNA in the cytoplasm is normally a sign ofmicrobial infections and is quickly detected by cyclic GMP-AMP synthase (cGAS) to elicit
anti-infection immune responses. Chronic activation of cGAS by self-DNA leads to severe
auto-immune diseases. It has been reported that Lys acetylation of cGAS inhibits its
activation to impair cGAS-mediated immune responses. Exogenous control over theacetylation status of cGAS may provide a potential therapy for treating DNA-mediatedautoimmune diseases. To discover a small molecule that selectively acetylates cGAS, we
exploited the structure of RU521, a known cGAS inhibitor, as a starting point. Introductionof an acetyl ester group to the structure at varied positions led to a series of candidate cGASacetylation compounds. We found one compound we named F108-1 that potently
acetylated cGAS and thereby inhibits its enzyme activity.
 Development of small-molecule kinases. Our preliminary investigations found a nitrobenzyl phosphate group as a donor of UV-induced phosphate transfer reactions. In FY2021,
we conjugated a nitro-benzyl phosphate group to a number of different molecules. For the
proof of the concept, we designed and synthesized a hybrid compound (Q1), in which a
nitro-benzyl phosphate group is conjugated with biotin. Co-crystal structure of the avidinQ1 complex revealed that the phosphonic acid group of Q1 formed a hydrogen bond with
Ser112. However, UV irradiation failed to transfer phosphate group to serine residue. The
possible explanation is that reactive intermediate “metaphosphate anion” is too active tophosphorylate serine residue.
 Others. Our group also collaborated with the Uesugi group for the proteomic discoveryof covalent enzyme inhibitors. Our findings exemplify that activity-based proteomic
screening with a cysteine-reactive probe can be used for discovering covalent inhibitorsthat react with non-cysteine residues. The collaboration has now been accepted for
publication in ACS Chem. Biol.

－66－

2021-67（国際）Orbitronics with new material systems
Sanghoon Kim University of Ulsan
Atom itself becomes a magnet because electron has properties such like a top. Because of thereason materials like Fe, Ni, Co and etc. can be magnets lies here. Countless atoms’ spins in amaterial interact with each other! These interactions create that all spins attempt to align inthe same direction. In nature, common metals have crystal symmetry, where an arrangementof atoms is uniform and periodic. In the case of specific materials, the symmetry is broken, which
creates special energy causing spins to twist (see the illustration in Fig. 1(a)). This is called as
Dzyaloshinskii-Moriya interaction. Twisted spin structure has received immense attentions
recently in modern physics. These small magnetic particles can create skyrmions and can bethermally stabilized and will enable the development of high density, high efficiency memory
devices. Therefore, it is important to find materials that have the Dzyaloshinskii-Moriya
interaction which is needed to make twisted spin structure.

Figure 1. (a) Schematic illustration of spin alignments with symmetric (top) and asymmetric(bottom) systems. (b) The ABC-type structure in this study. (c) Dzyaloshinskii-Moriya interactionenergy in terms of the unit-layer-structure numbers.

The research team of Professor Teruo Ono, Kyoto University, Professor Sanghoon Kim,
University of Ulsan proposed and experimentally verified the fact; when multiple layers of
atomic layer structure artificially prepared is asymmetric as shown in Fig. 1(b), spins have
Dzyaloshinskii-Moriya interaction energy (see Fig. 1(c)), which means artificial superlatticewith crystal asymmetry can create twisted spin structures. This study leads that material
studies to create subsequent twisted spin structures can be extended to a combination of various
materials which does not have to be limited to elements present in nature. This study was
published in npj Computational Materials [7: 129 (2021)].

－67－

2021-68（国際）Study of characteristics of spin wave in magnetic insulator
Kab-Jin Kim

KAISTObjective:
The aim of the research is to study the characteristic properties of spin wave in magnetic
insulators.
Experimental methods:
For this study, we prepared magnetic insulators, such as YIG, TmIG, and GdIG. The YIG is
selected as a control sample, because the spin wave of YIG is already well known in thecommunity. TmIG was selected because it shows spin reorientation from perpendicular magnetic
anisotropy to in-plane magnetic anisotropy above room temperature. GdIG was used because itshows compensation point where the total magnetization becomes zero. To measure the spinwave, we developed the antenna measurement setup with vector network analyser. In addition,
quantum imaging by means of NV center is also adopted.
Experimental results:
We first investigated the spin wave in YIG as a control experiment. The spin wave profile was
successfully imaged using NV center, indicating that our quantum measurement is well operated.
We also investigated the magnon (quantum of spin wave) and phonon in TmIG, and found thatthe magnon and phonon exhibit a non-equilibrium under the thermal gradient. As for GdIG, theexperiment is on-going (currently, we are confirming the material properties of GdIG by using
XRD and MPMS).
Discussion:
The spin wave experiment in ferrimagnetic insulators is a challenging topic, which requires along time. Therefore, in this year we focused on the development of the experimental setup as
well as the characterization of the magnetic insulators. Although it is in the beginning stage, we
obtained several positive results, including the successful quantum imaging, evidence ofmagnon-phonon in-equilibrium. As this is a long-term project, we would like to continue ourspin wave research next year. We lastly note that it was impossible to visit the ICR directly due
to the Covid-19. We look forward to collaborating through direct exchange next year.

－68－2021-69（国際）Application of ferrimagnets for spintronics devices
Alexander Samardak

Far Eastern Federal University

The main purpose of this study is to construct a new field called "ferrimagnetic spintronics" byclarifying the universality and diversity of the behavior of ferrimagnets as "antiferromagnets
with magnetization", and to develop them for device application. In this study, we prepare andstudy thin-film ferrimagnet CoTb alloy, which "behaves as an antiferromagnet withmagnetization".
A series of samples of the composition W(4)/Co56Tb44(x)/Ru(2 nm), x from 1.5 to 7 nm, wasprepared by magnetron sputtering on Si/SiO2 substrates. To study the magnetic transport
properties, the Hall bar structures were prepared by photolithography and ion plasma etching.
Decreasing thickness brings the sample to the Co-rich state: the magnetic moments of Co atoms
areoriented

along

the

external field, while Tb isantiparallel. The passage ofcurrent pulses through theHall bar structure in thepresence of a constant inplane field Bx leaded to areversible switching of themagnetization orientation in
the structure from the up to
the down due to the spinorbit torque effect. It was
found that the efficiency of
current exposure had acomplexdependence,

determined both by the
thickness of the FIM layer
and by the value of thesaturation magnetization.

Fig. 1. (a) Composition of the investigated structure,
thickness in nm. (b) Image of the Hall bar structure withorientation of the external field in the plane. (c) Hysteresis
loop obtained by the current propagation through the Hallbar structure. (d) Saturation magnetization and switchingcurrent versus CoTb layer thickness.

We lastly note that it was impossible to visit the ICR directly due to the Covid-19. We lookforward to collaborating through direct exchange next year.

－69－2021-70（国際）Highly efficient red thermally activated delayed fluorescenceemitters with sterically hindered donor skeleton
Jang Hyuk Kwon Kyung Hee University
In the organic light emitting diodes research field, thermally activated delayed
fluorescence (TADF) materials have received tremendous attention due to their ability toachieve internal quantum efficiency (IQE) of 100%. A number of blue and green TADF
materials with external maximum efficiency (EQEMAX) of over 30% have been proposed,
while an advance of highly efficient red TADF materials has been hampered by the energy
gap law. To overcome this problem, rigid electron donor and acceptor unit are promising.
This is because the rigid molecular structure can reduce molecular vibration and rotation
related to non-radiative decay. Recently, we reported a new 10,15-dihydro-5H-diindolo[3,2a:3′,2′-c]carbazole (i.e., diindolocarbazole) donor for efficient TADF materials (J. Mater.
Chem. C, 2018, 6, 1343-1348; Nat. Photon., 2019, 13, 540-546). The diindolocarbazole
donor has a rigid π-extended molecular structure and resulting shallow HOMO energy level,
which is suitable for the donor of red TADF emitters with a small HOMO-LUMO energy gap(Eg). Using this donor, Kaji group designed a new red TADF emitter with a rigid and πextended acceptor based on quantum chemical calculation. Therefore, the diindolocarbazole
synthesized by our group was sent to the Kaji’s group.
This past year, Kaji’s group has
succeeded in the synthesis of thedesignedredemitter.

Fromphotophysical measurements, small
Eg of 2.34 eV and red emission
with the maximum peak emission
wavelength

of

646

nm

were

observed. (Figure 1A). In addition,adelayedfluorescencewasobserved for the red emitter doped

Figure 1. Photophysical characteristics of the new red
TADF material. (a) PL spectrum in solution state and(b) transient PL decay curve in a film state.

in mCBP film suggesting the TADF characteristics. For electroluminescence properties, the
new material-based OLEDs exhibited relatively low external quantum efficiency with orangered emission. Kaji’s group is now working to improve the device performance by using otherhosts and optimizing device configurations.

－70－2021-71（国際）Developments of highly efficient and high color purity
organic electroluminescent devices based onthermally activated delayed fluorescent materials exhibiting
ultrafast reverse intersystem crossing process
Lian Duan

Tsinghua University

To develop highly efficient and high color purity organic light-emitting diode (OLED) devices,utilization of emitter molecules with a narrow spectral width is necessary. As an alternative strategy
instead of thermally activated delayed fluorescence (TADF)-based OLEDs that generally shows broad
spectral widths, hyperfluorescence (HF)-based OLEDs have attracted great attention. In the HF-based
OLEDs, electrically generated triplet excitons are up-converted into singlet excitons by the TADF
molecule used as an assistant dopant. The singlet excitons are finally transferred to a lowest excited
singlet state of a terminal emitter (TE) molecule by Förster-resonance energy transfer (FRET)
mechanism. Therefore, the color purity of the HF-based OLEDs strongly depends on spectral featuresof the TE molecules. Recently, we reported an ultrapure-green fluorophore (tPhBODIPY) based on aboron-dipyrromethene (BODIPY) skeleton, which exhibited the spectral feature with a small full
width at half maximum (fwhm) of 28 nm and high photoluminescence quantum yield (PLQY) of 97%(Adv. Optical Mater. 2020, 8, 2000483). Utilization of tPhBODIPY as the TE molecule can be
expected to afford the highly efficient and high color purity OLEDs.
Toward the highly efficient and high color purity OLEDs, Kaji’s group has planned fabrications of
the HF-based OLEDs using tPhBODIPY as the TE. As the assistant dopant, TpAT-tFFO with a large
rate constant (107 s-1) for a reverse intersystem crossing process was used. Overlap between absorption
spectrum of tPhBODIPY and emission spectrum of
TpAT-tFFO was found to be sufficient to generate
the energy transfer by the FRET mechanism.
Solution-processed HF films composed oftPhBODIPY, TpAT-tFFO and CzSi (host) showednarrow PL spectrum with fwhm of ~28 nm and high
PLQY (~93%). From transient PL measurements,
obviously shortened decay curves were obtained asshown in Figure 1. By analyzing the transient PL
decay curves, we estimated a rate constant for the
FRET process (kFRET) to be 4.6 × 107 s-1. These
results indicate that efficient energy transfer from
Figure 1. Transient PL decay curves of the
TpAT-tFFO to tPhBODIPY occurred in the HF
doped films w/wo the TE molecule.
films. The fabrications of the HF-based OLEDs arein progress.

－71－2021-72（国際）Structural and functional analysis of the surface polysaccharides ofouter membrane vesicles released by bacteria
Maria Michela Corsaro University of Naples Federico II
Objectives: The aim of this research has been the characterization of the capsularpolysaccharides (CPS) isolated from both the cells and the outer membrane vesicles(OMVs) secreted by the bacterium Shewanella vesiculosa HM13. The group of the ICR
partner researcher (Prof. Tatsuo Kurihara) has furnished both the samples, and thecharacterization has been performed by NMR spectroscopy.
Experimental: Dried cells (4.43 g) and OMVs (202 mg) of S. vesiculosa HM13
(rifampin-resistant mutant) were extracted with phenol/chloroform/light petroleum
method (Galanos et al 1969) and the crude lipooligosaccharide (LOS) was precipitated asalready reported (Di Guida et al. 2020). The phenolic phases were dialyzed against water(cut-off 3500 Da) and lyophilized, to obtain 161 mg and 37.4 mg from cells and OMVs,
respectively. Each sample was subjected to a mild acid hydrolysis with 1% CH3COOH(100 °C, 3 h). The resulting mixture was centrifuged (4 °C, 7500 rpm, 45 min), and thesupernatants were fractionated on a Bio-Gel P-10 column (Sigma, 110 × 0.75 cm, flowrate 12.7 mL/h, fraction volume 2.5 mL) eluted with water. The CPS fractions (CPScells
16.4 mg and CPSOMV 9.9 mg) were analysed by chemical analysis and 1H NMR
spectroscopy. Finally, the monosaccharide composition was obtained after derivatizationas acetylated methyl glycosides (AMG) and analysis by GC-MS.
Results: The cells and the OMVs of S. vesiculosa HM13 were extracted by PCP method.
After the precipitation of the LOSs, the residual phenolic phases were dialyzed against
water. The isolation of the CPS from both cells and OMVs was achieved by mild acidhydrolysis, followed by purification on a size exclusion gel chromatography column. The
obtained pure CPS fractions (CPScells and CPSOMV) were analysed by 1H NMR revealing
the same polymer from both cells and vesicles. The GC-MS analysis of themonosaccharides derivatized as AMG disclosed the presence in both cases of rhamnose(Rha), glucose (Glc), and 2-amino-2-deoxy-glucose (GlcN).
Galanos, C. et al. Eur. J. Biochem. (1969), 9, 245-249.
Di Guida, R. et al. Marine Drugs (2020), 18, 231.

－72－

2021-73（国際）Construction of heterologous protein secretion system at low
temperatures by using cold-adapted microorganisms
Xianzhu Dai

Southwest University[Objectives] Shewanella vesiculosa HM13, a psychrotrophic bacterium isolated by thegroup of the ICR partner researcher (Prof. Tatsuo Kurihara) from fish intestine, secretesa large number of spherical particles called extracellular membrane vesicles (EMVs) at
low temperatures. These vesicles carry an S-layer protein-like protein, P49, as a single
major cargo protein. This highly selective cargo transportation mechanism is expected to
be useful for vesiculation-mediated heterologous protein production. In this study, toelucidate the P49-selective secretion mechanism via vesiculation, the involvement ofgenes coding for functionally unknown proteins found in the vicinity of the P49 gene in
the cargo transportation was analyzed.
[Experimental methods] Genes coding for subunit homologs of type II secretion system(T2SS) widely conserved in Gram-negative bacteria, GspDEFGK, and functionally
unknown proteins (HM3352, HM3353, HM3355, HM3356, and HM3357) were found in
the upstream region of the P49-coding gene (hm3347). To delete these functionally
unknown genes, two-step single crossover homologous recombination using a pyrFbased gene-knockout plasmid, pKKPH, and a pyrF-deleted strain, ∆pyrFHM13, wasconducted. The gene-deletion mutants were cultured at 18 °C, and the localization of P49
in the EMVs was analyzed by western blotting with an anti-P49 antibody. Protein
structure prediction programs, I-TASSER and AlphaFold2, were used to predict thefunction of the functionally unknown proteins.
[Experimental results and discussion] Whole-genome sequence of S. vesiculosa HM13
showed that the P49-coding gene was found in the downstream region of a gene cluster
including the genes coding for subunits of T2SS and functionally proteins, suggestingthat these proteins including functionally unknown proteins form a non-canonical T2SS
and play a role in the secretion of P49 to EMVs. Deletion of hm3353, hm3355, hm3356,
and hm3357 caused disappearance of the EMV-localized P49, and P49 was enriched in
the cell fraction of the mutants. In silico structure prediction of these functionally
unknown proteins suggested that the structures of HM3355, HM3353, and HM3352 aresimilar to those of subunits of T2SS, minor pseudopilin (GspJ) and inner membranecomponents (GspL and GspM), respectively. It was also predicted that
HM3356 and HM3357 form pseudopilin-like structures. These results revealed that thesefunctionally unknown proteins contribute to the transportation of P49 to EMVs as
subunits of the non-canonical T2SS.

－73－

2021-74（国際）Optimizing sampling devices and procedures to quantify sources ofmetals and microplastics in Metro Manila, Philippines’ water
resources
Abigail P. Cid-Andres Polytechnic University of the Philippines
Objectives. The main aim of this study was to determine the mechanisms of
microplastics and metals in the Philippine environment. The challenges that the
microplastics research are undergoing is the lack of devices for sampling andextraction. A device for microplastic sample collection was fabricated. Sampling,collection and extraction with minimal chemicals was optimized.
Experimental Methods. Samples were gathered from various rivers and shorelinein the Philippines for simple chemical analysis. Equipment and consumables werefrom Professor Yoshiki Sohrin of the Institute for Chemical Research through Global
Frontier and Interdisciplinary Research Core for Deepening Investigations andPromoting Collaboration in Chemistry-oriented Fields.
Results and Discussion. Site visits and analysis showed that many of the rivers andshoreline in the study sites were lower than the water quality standard for class C.
The Metro Manila bodies of water is gradually rehabilitated. Microplastic
mechanisms was not directly related to the concentration of metals in the water. Pb
which was formerly used on the pigment materials of plastic were not detected.
Outcome report. The results reported and other addition data will be published in a
Scientific Journal. Outreach projects for elementary school children may also be
conducted via online platforms. The equipment provided will be used for thecontinuation of the research.
Workshops. Two (2) Master of Engineering Students were trained using the water
quality multiparameter: John Helarch Antoni and Kalvin Campang
Acknowledgement. The authors would like to thank Dr. Yoshiki Sohrin of theInstitute of Chemical Research, Kyoto University. This work was supported by theInternational Collaborative Research Program of Institute for Chemical Research,
Kyoto University (grant 2021-74).

－74－

2021-75（国際）

(a)

(b)

－75－

2021-76（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 to develop novel polyetherbased

nanocomposite

materials

bycombiningtheepoxidepolymerization techniques of the PI and the surface initiatedpolymerization techniques developed by the ICR partner researcher,Prof. Ohno from Kyoto University. Experimental Methods. Initiators
were characterized by

1

H NMR spectroscopy. Polymers werecharacterized by size-exclusion chromatography (SEC), 1H and 13C
Figure

1.

DOSY

NMR

spectrum of P(ECH-stat-PS).

NMR

spectroscopy,

diffusionorderedspectroscopy(DOSY),

differential scanning calorimetry (DSC), rheometry, and small angle Xray scattering. Membranes were characterized by FTIR spectroscopy

and CO2 permeability and selectivity were measured in a custom built chamber. Experimental
Results. Previous results showed interesting ionic conductivity behavior when tuning polymer
dielectric constant. To further enhance ionic conductivity, functional copolymers of sulfur containing
polymers

were

copolymerization

synthesizedofpropylene

from

the

sulfidestatistical
(PS)

and

epichlorohydrin (ECH). A DOSY spectrum of thecopolymer can be seen in Figure 1, which suggests bothmonomers are present along a single backbone and thepresence of additional peaks suggests successful statisticalFigure 2. Membrane synthesis.

copolymerization. Statistical copolymerization of epoxides and PS has not been demonstrated
previously. Work is on-going for grafting the initiator to the surface of silica nanoparticles andpolymerizing these materials from them. As part of this work, a tetra-functional initiator was produced.
We have utilized this newly accessible architecture to create membranes for CO2 separation, as shownin Figure 2. CO2 selectivity and permeability measurements were undertaken which put ourmembranes close to the Robeson line. Publications. An article co-authored by PI Ferrier and Co-PI
Ohno entitled “Facile Synthesis of Epoxide-co-Propylene Sulphide Polymers with Compositional andArchitectural Control” was submitted to Polymer Chemistry in December and is currently in revision.
Another manuscript based on the membrane work is currently in preparation. My student, Dr.
Niloofar Safaie, presented this work at the April meeting of ACS, held virtually, with a talk entitled:“Aluminum-based initiators from thiols for epoxide polymerizations.” Another student, Dr.
Geetanjali Shukla presented the membrane work at ACS in August in Atlanta Georgia, with a talkentitled “Star shaped polyether-based cross-linked membranes for separation applications.”－76－2021-77（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 friction. 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, is described 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)
that have been developed by Professor Yoshinobu Tsujii, ICR, Kyoto University.
Results – A unique friction apparatus that enables direct measurements of the friction
force vector has been developed, termed Friction Vector Apparatus (FVA). Sliding tests
for 15 polymeric materials were carried out with the FVA. The counter surface was asmooth glass ball with a diameter of 10 mm. The misalignment angle was 0 to 60 degrees,
the normal load 6 N, and the drive speed 0.1 mm/s. For PET, the FVA measured thedistinct kinetics of friction, showing the friction vector rotation and slow slip in stick
phases, which directly supports the validity of the DS theory. However, before sliding
under the normal load, it measured an unexpected horizontal force along the principal
axis of stiffness of a double cantilever. For the PMMA-CPB swollen by an ionic liquid asa good solvent, the horizontal force at stationary contact disappeared even under the same
normal load, although the kinetics of friction was below the measurement range of the
FVA because of its ultralow friction.
Discussion – Comparing the results of PET and PMMA-CPB tells us that the horizontal
force was caused not by structural errors or measurement errors. It resulted from frictional
force even though it was in a stationary state before sliding, indicating that in reality, thestationary contact was subject to an undetectable slow slip. Although generating thehorizontal force is still unclear, it is definite that it is similar to the slow slip in the stick
phase described by the DS theory.
Outcome report – [1] K. Nakano, “The dynamic stiction mode as a different descriptionof macroscopic static friction”, Annual Meeting of the Japan Society of Vacuum and
Surface Science 2021, Online, 03 November 2021 (Invited).

－77－2021-78（国際）Development of semiconductor quantum dot solid films andtheir charge carrier dynamics
Yasuhiro Tachibana

RMIT University

Introduction
Semiconductor quantum dots (QDs) have been recognised as the most promisingmaterial for optoelectronic devices such as next generation photovoltaic devices owing
to their unique optical and electronic properties. Although their solar cells show relatively
high solar energy conversion efficiency, charge carrier dynamics of QD solid films were
not well understood. In this project, we develop visible light active semiconductor
quantum dots, and assess charge carrier dynamics to compare with their solar cell
performance. We have conducted this project with Professor Teranishi at the ICR.
Experimental
A transparent TiO2 nanocrystalline film (printed area: 0.25 cm2, film thickness: 6 μm)
was prepared by screen-printing the TiO2 paste (Solaronix SA, Ti-Nanoxide HT/SP) on
the FTO substrate. A CdS QD attached nanocrystalline film was prepared by using the‘‘successive ionic layer adsorption and reaction’’ technique. Transient absorption
spectrometers were employed to characterize TiO2 films [1] and QD/TiO2 films [2].
Results and Discussion
The charge recombination lifetime at the QD/TiO2 interface increases, as the QD size
increases. An absorbed photon to current conversion efficiency (APCE) of the QDSSC
increases, as the QD size increases. Therefore, we conclude that the APCE of the CdS
QDSSC is controlled by the interfacial charge recombination dynamics competing withdynamics of the hole transfer from the QD valence band to the reduced electrolyte [2].
Outcomes[1] H. Liu, M. Liu, R. Nakamura, Y. Tachibana, Appl. Catal. B-Environ., 296 (2021)
120226.
[2] S. R. Padmaperuma, M. Liu, R. Nakamura, Y. Tachibana, J. Photopolym. Sci.
Technol., 34(3) 271-278 (2021).

－78－2021-79（国際）Interdisciplinary Approach to Nanostructured Materials for Applications
Jean-Pierre Bucher

Université de Strasbourg

Here we summarize the discussions and first experimental steps that took place around thetwo main interdisciplinary projects for which Prof. T. Teranishi is our ICR contact.
1) Structural changes of nanoparticles under pulsed laser irradiation evidenced bymeans of HR-TEM. Teranishi's groups (Kyoto) successfully synthesized single crystalline
Pd nanocrystals (NCs) capped with phosphine or thiol ligands. These NCs are ready for theinvestigation by Banhart’s group (Strasbourg) of the phase change from crystalline Pd toamorphous PdPx or PdSx under a laser pulse by means of electron diffraction. Further
strategies and alternative materials are currently explored.
2) Self-organization of single molecule magnets (SMM’s) by means of macrocycle
networks and characterization by LT-STM. The synthesis of the SMMs takes place inStrasbourg (Ruben’s group). This compound is currently sent to Nagoya where it isincorporated in the synthesis of the 2D-crystal made of properly functionalized piconjugated macrocycles (Tanaka’s group). Next step consists in characterizing the
crystallized sample, by means of conventional techniques such as X-ray diffraction andoptical techniques. After drop casting on a Au(111) substrate (Nagoya), the 2D network will
be examined using low temperature (LT)-STM in Strasbourg (Bucher’s group) to study
locally the embedded TbPc2 SMM’s for their magnetic properties. A first check of the proper
growth of the 2D-network on Au(111) will be done in Nagoya by Onoe’s group by room
temperature STM.
Due to the Covid pandemics, no face-to-face workshops or meetings could be organizedin 2021 but a number of Zoom meeting were held during the period. The partners all took
part in a kick-off meeting on the 26th of April 2021. A follow-up Zoom-meeting with allparticipants took place on the 5th of October 2021. Zoom progress-meetings were held on
the 22nd of November 2021 and on the 25th January 2022 between Strasbourg and Nagoya(M. Ruben, J.P. Bucher, K. Tanaka, J. Onoe). Other bilateral discussions (phone calls) andmeetings took place, between participants.

－79－2021-80（国際）Novel strategy for intracellular delivery of nanomedicines
Sílvia PUJALSInstitute for Bioengineering of Catalonia

Nanomedicine arose 20 years ago with the promise of selectively delivering drugs totarget sites, thus increasing their effectivity while minimizing undesired side effects. However,despite the great promise behind nanomedicine for drug delivery, very few products have been
approved for patient use. This poor translation into clinic comes from different factors, some ofthem being a poor characterization of the nanomaterials or a simplistic model to evaluate them.
Poor cellular uptake efficacy of these nanomedicines is also a big obstacle. Our research group
has a speciality in preparation of nanoparticles being applied for nanomedicine. We also havestrong background of nanomaterials characterization and intracellular behavior using various
microscopic techniques (including electron microscopy and super resolution microscopy). On
the other hand, Professor Futaki at ICR, Kyoto University is an expert on intracellular deliveryof nanomedicines.
The successful cytosolic delivery of nanoparticles is hampered by their endosomal
entrapment and degradation. To push forward the smart development of nanoparticles we must
reliably detect and quantify their endosomal escape process. However, the current methods
employed are not quantitative enough at the nanoscale to achieve this. Nanoscopy is a rapidly
evolving field that has developed a diverse set of powerful techniques in the last two decades,
opening the door to explore nanomedicine with an unprecedented resolution and specificity. The
understanding of key steps in the drug delivery process – such as endosomal escape – would
benefit greatly from the implementation of the most recent advances in microscopy. Futaki andcoworkers developed delivery peptides potentially applicable to cytosolic delivery of
nanoparticles.1,2) Our group has formulated few batches of Poly(D,L-lactide-co-glycolide)(PLGA) nanoparticles. They are around 200 nm and have DiI (exc 550 nm) or DiO (exc 484 nm)
for visualization of their methods of cellular internalization. PLGA-based nanoparticles arebiodegradable and widely employed in drug delivery systems in various medical applications.
Methods in cellular uptake of these particles are now understudy in Futaki laboratory.
References
1) K. Sakamoto, M. Akishiba, T. Iwata, K. Murata, S. Mizuno, K. Kawano, M. Imanishi, F.
Sugiyama, S. Futaki, Angew. Chem. Int. Ed. 2020, 59, 19990-19998.
2) J. V. V. Arafiles, H. Hirose, Y. Hirai, M. Kuriyama, M. M. Sakyiamah, W. Nomura, K. Sonomura, M.
Imanishi, A. Otaka, H. Tamamura, S. Futaki, Angew. Chem. Int. Ed. 2021, 60, 11928-11936.

－80－

2021-81（国際）Structural and functional analysis of curvature-inducing peptides andapplication
Anne S. Ulrich

Karlsruhe Institute of Technology

Epsin-1 is a representative protein which induces the positive curvature necessary for theformation of clathrin-coated pits during endocytosis. Modulating the structural dynamics ofbiomembranes by inducing bilayer curvature and lipid packing defects has been highlighted as apractical tool to modify membrane-dependent cellular processes. Collaborative research of
Ulrich research group at KIT with Futaki research group at ICR, Kyoto University has alreadyshown that the N-terminus 18-residue peptide of epsin-1 (EpN18) possess curvature inducing
abilities of the parent protein. We also reported that EpN18 also promotes membrane remodelingincluding lipid packing defects in cell membranes [1]. However, a high concentration is required
to exhibit a pronounced effect. We therefore demonstrate a significant increase in the membraneremodeling effect of EpN18 by constructing a branched EpN18 homotrimer. Both monomer andtrimer could enhance cell internalization of octaarginine (R8), a cell-penetrating peptide. The
EpN18 trimer, however, promoted the uptake of R8 at an 80-fold lower concentration than themonomer. Analysis of the generalized polarization of a polarity-sensitive dye (di-4ANEPPDHQ) revealed a higher efficacy of trimeric EpN18 in loosening the lipid packing in thecell membrane. Circular dichroism measurements in the presence of lipid vesicles showed that
the EpN18 trimer has a higher α-helix content compared with the monomer. The stronger abilityof the EpN18 trimer to impede negative bilayer curvature is also corroborated by solid-state 31P
NMR spectroscopy. Hence, trimerizing peptides can be considered a promising approach for an
exponential enhancement of their membrane-remodeling performance [2]. In this study, we
aimed to study the relationship between the structural factors of EpN18, especially about thehelix forming propensity, the component amino acids, and the resulting effects on membrane
structures, and to obtain knowledge for the rational design of curvature-inducing peptides. We
found the critical contribution of some amino acid residues in EpN18 to enhancing membraneinteraction, helical structural formation, curvature induction and lipid packing.
[1] Pujals et al.ACS Chem. Biol. 2013, 8, 1894
[2] Hsu et al. Bioorg. Med. Chem. Lett. 2020, 30, 127190.

－81－2021-82（国際）Research toward stable NV centers at shallow region and spin dynamics
in diamond
Gopalakrishnan Balasubramanian Leibniz institute for surface engineering
Recently, NV centers (Figure 1) in diamond are
significantly interested as a candidate of a resource for quantum
sensing with nano-scale spatial resolution and ultra-highsensitivity. It is because that single spins can be coherently
controlled and the spin coherence time is significantly long evenat room temperature (RT) in the NV center. In other solidmaterials such as quantum dot, molecules, and silicon, those are

Fig. 1, The NV center in diamond.

realized only in extremely low temperature. By utilizing
nanoscale shallow NV centers, applications for nanoscale imaging [1] and nanoscale nuclear
magnetic resonance were demonstrated. Furthermore, NV centers were successfully integrated into
photonic and mechanical structures, and in electronic devices, which expands their versatility.
Toward these issues, Kyoto University group demonstrates the extension of the spin-coherencetime (T2), the stabilization of the charge state, and an improvement of the creation yield of NV centersformed by the ion-implantation technique at a depth of ~15 nm in phosphorus-doped n-type diamond[2]. We demonstrated the extension of T2, the stabilization of the charge state, and the improvementof the creation yield of the NV centers compared with those generated by the same ion-implantation
technique in non-doped diamond. As far as we know, the enhanced T2 is longer than in other reported
nanoscale shallow NV centers created by ion-implantation with similar depth. Additional significancestems from the usage of a diamond semiconductor to obtain the enhancements. The present result is
important for nano-fabrication of integrated devices, so it paves the way to the development andapplication of diamond-based quantum-information, sensing, and spintronic devices.
References[1] Balasubramanian, G., Chan, I., Kolesov, R. et al. Nanoscale imaging magnetometry with diamond spins
under ambient conditions. Nature 455, 648–651 (2008).
[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).

－82－2021-83（国際）Research of quantum controls in multi-qubit diamond quantum processors andquantum sensors
Marcus W. Doherty

Australian National University

Quantum communication and quantum computation are expected to establish a new paradigm
and advance our understanding of quantum mechanics. It is considered that they will provide
cryptography that can not be decoded and super parallel computation that is much faster than that ofordinary computers. Besides these, technical issues and intriguing questions concerning quantum
mechanical phenomena can be addressed. NV centers in diamond (Figure 1) are significantlyinterested as a candidate as a resource for demonstration and realization. It is because single spins
can be coherently controlled [1] at room temperature (RT).
We would like to develop this system further with multi-nuclear spin qubits in this project. We
discuss new architectures to enhance the speed and fidelity of quantum processors by using multiqubits NV centers in diamonds. We discuss the usage and production of isotopically engineered
diamonds to improve the speed and fidelity of quantum processors. It is considered that quantum
communication and quantum computation will, e.g., provide secure data encryption and super parallel
calculation that, in some instances, outperforms classical computers. The realization of them has astrong impact not only on science but also on industry and society.
We recently proposed a full model of multi-qubit diamond quantum processors and developed asemi-analytical method for designing gate pulses [2]. This method optimizes gate speed and delity
in the presence of random control errors and is readily compatible with feedback optimization
routines. We theoretically demonstrate indelities approaching ∼10−5 for single-qubit gates andestablished evidence that this can also be achieved for a two-qubit CZ gate. Consequently, our method
reduces the effects of control errors below the errors introduced by hyperne eld misalignment andthe unavoidable decoherence that is intrinsic to the processors. Having developed this optimal control,
we simulated the performance of a diamond quantum processor by computing quantum Fouriertransforms. We nd that the simulated diamond quantum processor can achieve fast operations withlow error probability. We continue to discuss the experimental demonstration of this method in thisproject.
References[1] P. Neumann, N. Mizuochi, F. Rempp, P. Hemmer, H. Watanabe, S. Yamasaki, V. Jacques, T.
Gaebel, F. Jelezko, J. Wrachtrup. Science, 320, 1326 (2008).
[2] Y. Chen, S. Stearn, S. Vella, A. Horsley, M. W. Doherty, New J. Phys. 22, 093068 (2020).

－83－2021-84（国際）Molecular mechanisms for the inactivation of a growth hormone in rice
Zuhua He

Chinese Academy of Sciences

Objectives: Gibberellins (GAs) are a class of diterpenoid carboxylic acids. They act as plant
hormones that control diverse developmental processes. Bioactive GAs play critical roles inpromoting growth, including internode (stem) elongation of rice. The elongated uppermost
internode 2 (eui2) mutant of rice shows a tall phenotype due to its elongated uppermost internode.
Because of this reason, this mutant has been utilized in hybrid rice breeding in 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 have previously characterized the rice euimutant and found that EUI encodes a cytochrome P450 enzyme that deactivates GAs via
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. Last year, incollaboration with Prof. Shinjiro Yamaguchi at ICR in Kyoto University, we found that EUI2
protein could in fact hydrolyze epoxy GAs in vitro. In addition, we determined the levels ofendogenous epoxy GAs in wild type and the eui2 mutant by LC-MS/MS analysis.
Experimental methods: Epoxy GAs in rice plants were analyzed by LC-MS/MS after
derivatization as ethyl esters. Biological activity of epoxy GAs was determined by a micro-drop
method using GA-deficient rice seedlings. The physical interaction between the GA receptor
GID1 and epoxy GAs was analyzed by isothermal titration calorimetry (ITC).
Experimental results: To confirm the results obtained last year, we analyzed endogenous epoxy
GAs in another genetic background of WT and eui2 mutant rice plants. Consistent with theprevious data, the eui2 mutant accumulated epoxy GAs at much higher levels than does WT. We
chemically synthesized epoxy GA4 and found that it is weakly, but significantly active inpromoting leaf elongation in rice. In addition, our data also showed that the biological activityof the hydrolyzed product (dihydroxy GA4) was significantly weaker. This finding suggests that
EUI2 plays a role in further deactivating epoxy GAs. ITC was used to examine the physicalinteraction of epoxy GA4 with the GA receptor GID1. The results demonstrated that epoxy GA4
is able to weakly interact with GID1 in vitro, supporting the notion that epoxy GA4 was weakly
bioactive. ITC analysis also showed that the interaction of dihydroxy GA4 with GID1 is weaker
than that of epoxy GA4.
Publications: In preparation.

－84－2021-85（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 many
processes of plant growth and development. They are also secreted from plant roots and function
as allelochemicals for symbiosis with arbuscular mycorrhizal fungi and stimulating seedgermination 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 not been 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 arephenotypically very similar to those well-characterized SL biosynthesis mutants and signaling
mutants. The physiological and biochemical roles of the identified transporters need to beexperimentally 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).
• 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 established the method to purify and analyzeboth the endogenous SLs (4-deoxyorobanchol and orobanchol) and their biosynthetic
intermediates (carlactone, carlactonoic acid, methyl carlactonoate) from the same plant sample
by using several solid-phase extraction（SPE）cartridges and LC-MS/MS, respectively. We aregoing to analyze the endogenous amounts of SLs and their biosynthetic intermediates using theknockout mutants of the transporters.
Publications: No publications from the collaboration in FY2021.

－85－

2021-86（国際）
1,3-Dipolar Cycloaddition Reactions of Cycloparaphenylenes with
Azomethine Ylide
Shingo Ito Nanyang Technological University
Objective
In this research, we aim to develop the synthesis of novel nitrogen-containing carbon
nanotubes and their application to novel organic electronic devices. Since Prof.
Yamago is a pioneer of cycloparaphenlyne (CPP) chemistry1 and Prof. Ito has aneffective -extension method using azomethine ylides (AMY),2 we offer novel
synthetic methods for breakthrough tube-shaped molecules throughout thiscollaborative research.
Results and Discussion
First, DFT calculations were performed to confirm whether the 1,3-dipolar
cycloaddition reaction of CPP and AMY is feasible. The results indicated that thereaction with neutral CPP may not proceed, but the reaction with cationic CPP could
proceed. Therefore, a cationic CPP was prepared by oxidation and used for a
cycloaddition reaction with azomethine ylide. However, no compound corresponding
to the cycloadduct was detected by MALDI and NMR analyses.

Scheme 1
Reference
1) Yamago, S.; Kayahara, E. J. Synth. Org. Chem. Jpn. 2019, 77, 1147–1158.
2) S. Ito, Tokimaru, K. Nozaki, Angew Chem. Int. Ed. 2015, 54, 7256–7260.

－86－2021-87（国際）Dendritic Amphiphilic Block Copolymers as Additive for
Polyvinylidenedifluoride Based Membranes
Mona Semsarilar

University of Montpellier

This project is a collaboration between Dr. Mona Semsarilar from University of Montpellier(France), Prof. Shigeru Yamago and A/Prof. Yangtian Lu from University of Kyoto (Japan).
Objectives:
The aim of this project is to prepare porous polyvinylidene difluoride (PVDF) membranes withhydrophilic character for water filtration. PVDF is hydrophobic and incompatible (immiscible)
with all other polymers apart from polymethyl methacrylate (PMMA). PVDF is normallyblended with hydrophilic polymers in order to confer hydrophilicity to the prepared membranes.
However, due to the immiscibility of PVDF with other polymers this method would result inmembranes with inhomogeneous and short-lived hydrophilic character. To solve this major
problem we propose to synthesize an amphiphilic block copolymer where one block is a linearhydrophobic PMMA and the other block is a dendritic hydrophilic polymer. The linear PMMA
block will fully blend with the high molecular weight PVDF and allow the homogeneous
dispersion of the hydrophilic polymer segments within the PVDF matrix.
Experimental methods and results: As per the original design of the project, Prof. Yamago’s
team has synthesied amphiphilic dendritic block copolymers via TERP controlled
polymerization. A library of twelve polymers have been prepared. The French team has studied
the blending properties of the synthesized block copolymers with the high molecular weight
PVDF and the membrane fabrication. Via solvent/ non-solvent phase inversion method (SNIPS).
The prepared membranes were fully characterized (SEM, AFM, FTIR and water contact angle).
The performance of the resulting membranes were verified via a dead-end filtration set-up. Flux
and permeability values at different pressure points were collected and evaluated.
Publications: This collaborative project started in March 2021. As all the countries are still
under restrictions imposed by COVID19 pandemic, none of the planned visits could take place.
As the proposed tasks in the project could not be carried as planned due to border closures, thetwo partners have rework the plan and deploy some exiting funds to carry on the work. The
Yamago team, prepared some block copolymers (sent to France by air post) and the French teamworked on the preparation and characterization of the membranes. An article based on the dataacquired is under preparation.

Regardless of the unfortunate circumstances, both partners are

enthusiastic to carry on with this collaboration.

－87－2021-88（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 also updating the theoreticalinterface to obtain the exclusion domain on the coupling parameter between a new particle stateand photons.
As the present status, we have succeeded to publish a paper on the search result to a journal. On
this paper we have called a press conference in Hiroshima University and the article has been
published in MyNavi. In addition, we have published a paper on a perspective of our approach
including GHz-band photon sources in addition to the laser sources. We summarize the publishedpapers, two relevant invited talks and the press release during FY2021 as follows.
Published papers:[1] Search for sub-eV axion-like resonance states via stimulated quasi-parallel laser collisions with the parameterization including fully
asymmetric collisional geometry, Kensuke Homma*, Yuri Kirita, Masaki Hashida, Yusuke Hirahara, Shunsuke Inoue, Fumiya Ishibashi, Yoshihide
Nakamiya, Liviu Neagu, Akihide Nobuhiro, Takaya Ozaki, Madalin-Mihai Rosu, Shuji Sakabe and Ovidiu Tesileanu (The SAPPHIRES
collaboration), Journal of High Energy Physics volume 2021, Article number: 108 (2021). (acknowledge the support by ICR)
[2] Perspective of Direct Search for Dark Components in the Universe with Multi-Wavelengths Stimulated Resonant Photon-Photon Colliders
high-quality vacuum system”, Kensuke Homma*, Yuri Kirita, Fumiya Ishibashi, Universe 7 (2021) 12, 479. (acknowledge the support by ICR)

Invited talk:[1]

Perspective of direct search for dark components in the Universe with multi-wavelengths photons
Kensuke Homma, Nuclear Photonics 2020 (2021.6.9)[2]

Search for Sub-eV Axion-Like Resonance States via Stimulated Quasi-Parallel Laser Collisions with the Parameterization Including Fully
Asymmetric Collisional Geometry
Kensuke Homma, 29th ANNUAL INTERNATIONAL LASER PHYSICS WORKSHOP (2021.7.22)

Press release:[1] https://www.hiroshima-u.ac.jp/research/news/68458－88－2021-89（国際）Development of Perovskite and Perovskite-like Emitters andTheir Applications
Hao-Wu Lin National Tsing Hua University
Developing high-performance halide perovskite light-emitting materials has also become apopular research topic. The research topics of this study are the syntheses, properties, andapplications of 0 ~ 2 dimensional perovskite and perovskite-like halide materials.
We developed an antisolvent reprecipitation
method to synthesize lead-free halide double
perovskite materials Cs2(Na,Ag)(In,Bi)Cl6. Afterthe optimization of process parameters andcompositions, yellowish-white light-emitting
materials with ultra-broad photoluminescence
spectrum from visible to near-infrared (see Figure1) and a decent photoluminescence quantum yield(PLQY) of 50% were obtained.
We also investigated the ball-millingmechanosynthesis procedure, which has attracted
much attention recently. A variety of emitting Fig. 1. Emission spectra of Cs2(Na,Ag)(In,Bi)Cl6.
materials were synthesized through ball-milling,including CsPbBr3, lead-free halide double
perovskites, and 0-dimensional copper(I)-based
halide materials such as Cs3Cu2I5, CsCu2I3, and(MA)4Cu2Br6. The convenience and universalityof the ball-milling procedure were verified throughthese attempts.
These materials were utilized as X-ray
scintillators for X-ray image applications. Fig. 2
shows the detected photon counts versus X-ray
dose rate curve. The scintillator exhibited Fig. 2. X-ray response of light emitting
promising linear response characteristics and very Cs2(Na,Ag)(In,Bi)Cl6.
low detection limit of 15 nGy/s, indicating a great
potential of using these lead-free Cs2(Na,Ag)(In,Bi)Cl6 perovskite for X-ray detectors targeting
to the medical and industrial inspection applications.
[1] Po-Ting Lai, Hao-Cheng Lin, Yung-Tang Chuang, Chien-Yu Chen, Wei-Kai Cheng, GuangHsun Tan, Bo-Wei Hsu, Lin Yang, Shiu-Cheng Lou, Li-Jen Chien, Hau-Wei Wang, and HaoWu Lin, ACS Appl. Mater. Interfaces 2022, 14, 19795.
[2] Shu-Wen Dai, Ying-Lin Lai, Lin Yang, Yung-Tang Chuang, Guang-Hsun Tan, Shin-Wei Shen,
Yu-Sheng Huang, Yuan-Chih Lo, Tzu-Hung Yeh, Chih-I Wu, Lih-Juann Chen, Ming-Yen Lu,
Ken-Tsung Wong, Shun-Wei Liu, Hao-Wu Lin, ACS Appl. Mater. Interfaces 2021, 21, 25202.

－89－2021-90
モデルポリアルキルスチレン類を用いた分子構造と粘弾性パラメータの相関解析
高野敦志 名古屋大学【緒言】高分子物性の中には高分子を構成するモノマーの分子構造には依存しない性質（例えば、ゼ
ロずり粘度の分子量依存性など）がある一方で、個々の分子構造に依存する性質（例えば、ガラス転、絡み合い点間分子量（Me）、など）もある。後者の研究例として、モノマーユニットに移温度（Tg）
対して炭素数、線状－分岐状、および結合位置などの異なるアルキル側鎖が導入された一連の高分子を利用したものがあり、例えばポリ（n-アルキルメタクリレート）系などで Tg などのアルキル側鎖依存性が調べられている。しかし、分子量分布が狭く、かつ高分子量に及ぶ広い分子量範囲で試料調製を行い、分子構造を系統的に変化させた一連のモデル高分子を用いて粘弾性評価がなされた例は少ない。本研究では一連のポリアルキルスチレン類（Figure 1）を精密合成し、分子構造と粘弾性パラ
メータの相関関係を調査、検討した。
【実験】側鎖の直鎖アルキル基の炭素数（m）が異なる n-アルキルスチレン（m = 1, 2, 3, 4, 6, および
8）、ならびに分岐アルキル基（イソプロピル、tert-ブチル、sec-ブチル）を有するアルキルスチレンをモノマーとしてリビングアニオン重合により、狭い分子量分布を持ち、かつ広い分子量範囲でポリマーを合成した。ポリマー試料の分子量および分子量分布は多角度光散乱（MALS）およびサイズ排除クロマトグラフィー（SEC）により評価した。Tg は示差走査熱量（DSC）測定により求めた。動的粘弾性（TA instruments 社製 ARES-G2 使用）は、8mm パラレルプレート、N2 雰囲気下、 歪み 1～
5%（線形領域）の条件下で測定した。
【結果と考察】ポリアルキルスチレン試料の Tg の分子量依存性を調べたところ、両者の関係は Fox-Flory の経験式により概ね記述できることが示された。ポリ（n-アルキルスチレン）試料のアルキル炭素数と Tg の関係を

Figure 1. The molecular structure of the polymers
used in this study.

調べてみると、ポリスチレンの Tg（＝100℃）を基準とするとき、メチル基の導入により一旦 Tg は増加するが、その後炭素数の増加に伴い、Tg は単調に低下していくことが分かった。一方、分岐アルキル基の導入は Tg の増加をもたらすことが確認された。分子構造と Tg の関係を考察してみると、まずポリ（4-メチルスチレン）では、メチル基は回転に伴う分子鎖まわりの自由体積の変化はほとんどないことから、主鎖に対してはフェニル基より大きな側鎖官能基が連結しているとみなすことができる。大きな官能基は主鎖の運動性を低下させるため、Tg の上昇につながると予想される。一方、ポリ（4-エチルスチレン）になると、エチル基の C-C-C 結合が 109.28 度で連結しているため、側鎖の回転運動に伴い、分子鎖まわりに自由体積の変化が起こる。これが主鎖の運動性を高め、Tg を低下させると予想される。従ってエチル基→オクチル基への炭素数の増加に従い、Tg は低下していくと考えられる。一方、ポリ分岐アルキルスチレン類の場合、側鎖官能基が嵩高く、側鎖官能基の回転に伴う分子鎖まわりの自由体積の変化は少ない。そのため上述のメチル基同様、大きな側鎖官能基が連結されているとみなすことができる。
【成果報告】以上の成果は、レオロジー討論会（オンライン）にて口頭発表した。
－90－2021-91
Study on the Regulatory Network of Plant Epidermal Cell Differentiation
Rumi Tominaga

Hiroshima University

Objectives: The cell differentiation and its deposition pattern are crucial determinants of plantstructures and functions. Among multiple types of plant cells, the root epidermis of
Arabidopsis thaliana has served as an excellent model system for studying plant celldifferentiation and pattern formation. In Arabidopsis, the root epidermis is composed of the
non-hair (N) and hair (H) cell files, and only cells in the H cell files develop root hairs. For root
hair development, numerous transcription factor genes constitute a regulatory network, and
GLABRA2 (GL2) is located at the bottleneck between the cell pattern formation and subsequentcell differentiation. We have identified several Arabidopsis bHLH transcription factor genes,
including ROOT HAIR DEFECTIVE6 (RHD6), ROOT HAIR DEFECTIVE6-LIKE1 (RSL1),
RSL2, Lotus japonicus ROOTHAIRLESS1-LIKE1 (LRL1), and LRL2, as direct targets of GL2.
These genes are suppressed by GL2 in N cell files and are expressed in various developmental
stages of root hair cells. Among transcription factors encoded by them, only LRL1 and LRL2
conferred root hairs in N cell files when ectopically expressed. To understand thetranscriptional network and cell biological events downstream LRL1 and LRL2, we performed
genetic analysis in combination with a glucocorticoid (GR) induction system.
Experimental Methods: Transgenic Arabidopsis lines with the transgene LRL1g-GR, which
expressed the fusion protein LRL1-GR by the LRL1 promoter, were established under the lrl1
mutant background. Root hair phenotypes of the transgenic lines and the lrl1 mutant wereobserved under normal conditions or induction conditions with glucocorticoid treatment. The
transgenic lines were crossed with the lrl2 mutant line to establish the transgenic line with thelrl1lrl2 background.
Results and Discussion: Seedlings of the lrl1 mutant exhibited significantly shorter root hairs
than the wild type. The phenotype was completely rescued by the LRL1g-GR transgene underglucocorticoid treatment conditions, but not under normal conditions, indicating that the fusion
protein LRL1-GR is conditionally functional depending on glucocorticoid. After crossing thetransgenic rescue lines with the lrl2 mutant line, we first selected LRL1g-GR transgenic plants
with the genetic background of lrl1lrl2/+ (lrl1-homozygous and lrl2-heterozygous) among theF2 plants. When the selected plants were grown under normal growth conditions, their progeny
didn't include transgenic plants with the lrl1lrl2 background (LRL1g-GR/lrl1lrl2). However,
LRL1g-GR/lrl1lrl2 plants were obtained by continuously treating their parental plants withglucocorticoid. The LRL1g-GR/lrl1lrl2 plants exhibited a no-root-hair phenotype, which was
rescued by glucocorticoid treatment. These indicate that the LRL1 and LRL2 genes redundantly
function in essential processes for both root hair development and male gametophyte fertility.
－91－

2021-92
免疫賦活化するナノ集合体
山崎晶

大阪大学

ワクチンは感染症を予防するための最も良い医学的介入の一つである。安全なワクチンとして、病原体の抗原となる部分だけをとりだしたサブユニットワクチンが開発され、臨床的に広く用いられている。しかしながら、サブユニットワクチンは十分な免疫原性を有しておらず、十分な免疫応答を誘導するためにはアジュバントと呼ばれる抗原性補強剤との併用が必要である。これまでにアラムや水中油型エマルションなどが開発されているが、数が限られている。新興ウイルスに対応して効果的なワクチンを準備しなけ
ればならず、また、今後実用化されるであろう癌ワクチンにもアジュバントが必要とされる。アジュバントのレパートリーを増やすことが急務である。一般に、免疫応答とアジュバント活性には、分子の大きさが関与している。本研究では、自発的に集合して巨大化する「自己集合」という材料化学の概念、ケミカルバイオロジー、免疫学の手法を組み合わせて、アジュバント材料を発見・理解することを試みた。
2021 年度は、コリカマイドと抗原ペプチドとの併用による抗腫瘍活性を検討した。しかし、骨髄由来樹状細胞(BMDC)においてコリカマイドは細胞毒性を示したため、コリカマイドの構造を最適化して低毒性化することにした。アジュバントの安全性は実用化にとって極めて重要である。12 種類の新しい誘導体を評価した結果、C7 が発見され、BMDC においてコリカマイドの 3 倍以上の免疫賦活効果を示すことがわかった。重要なことに、C7 は 80μM まで BMDC にほとんど細胞毒性を示さなかった。C7 の毒性をマウ
スでも評価した。500 µg 投与しても、肝毒性の指標である ALT、AST、ALP および腎毒性の指標である UREA、CREA の上昇は認められなかった。C7 を新たな候補として研究をすすめた。
C7 は免疫賦活作用が強く、毒性も低いことから、癌ワクチンのアジュバントとしての可能性を検討した。マウスにメラノーマを移植し、癌体積、生存率、体重減少を評価した。対照群および C7 のみを投与した群では、癌体積が増加し、15 日以内にすべてのマウスが死亡したが、抗原ペプチドと C7 を投与した群では、癌体積の増加が著しく抑制
され、21 日生存率は 80%に達した。一方、抗原ペプチドのみを投与した群では、癌体積の増加はわずかに抑制されたものの、21 日生存率は 20％にとどまった。C7 の細胞毒性が低い理由はまだ不明である。動的光散乱実験から、C7 の集合体は、コリカマイドの集合体よりも熱力学的に安定であることが示唆された。この C7 集合体の安定度が、癌ワ
クチンアジュバントとしての優れた特性の一端を担っているのかもしれない。

－92－2021-93
自己集合性分子による心筋細胞移植の効率化
柴祐司

信州大学

現在の内科的、外科的治療法は心不全患者の症状の緩和と、病気の進行抑制に有効であるが、病気を治癒させることは出来ない。重症心不全に対する唯一根本的な治療は心臓移植であるが、ドナー不足は深刻である。近年、多能性幹細胞から心筋細胞を作製する
プロトコールが複数報告され、大量の心筋細胞を作製することが可能となっている。
本研究では、京都大学化学研究所の上杉グループと共に、心筋細胞分化を誘導する化合物 KY02111 のメカニズムを解明した。本化合物は上杉グループと中辻グループによって発見された化合物であり、強力な心筋分化能力をもつ。現在、心筋分化の大量調整に利用されている。しかし、そのメカニズムは解明されていなかった。共同研究研究により、KY02111 の標的タンパク質として酵素 SQS を同定した。面白いことに、KY02111 は
SQS の酵素活性には影響せず、SQS と TMEM43 とのタンパク―タンパク相互作用を阻害していた。
TMEM43 は核膜の維持に重要とされているがその役 割は明確にされていない。
TMEM43 の変異は主に心臓疾患に見られる。最も侵攻性の高い不整脈原性心筋症/ARVC
サブタイプは ARVC5 型（ARVC5）で、TMEM43 の S358L 変異が原因である。S358L 変
異が SQS との相互作用に及ぼす影響を調べたところ、変異した TMEM43 は SQS と会合しなかった。TMEM43 と SQS の相互作用の阻害が ARVC の表現型と関係している可能性が示唆された。
柴グループでは、心筋形成において、KY02111 によって SQS-TMEM43 の相互作用が阻害され続けることが、ARVC の表現型につながるのではないかと推測した。この仮説を検証するために、ヒト iPS 細胞の 18 日間の心筋形成プロトコルの間、KY02111 を培養液に添加した。この確立されたプロトコルは、高い TNNT2 発現レベルを有する 80％の
cTNT 陽性細胞を生成する。これら 2 つの心筋細胞マーカーの発現レベルは、KY02111 による連続処理によって有意に減少した。KY02111 処理細胞は、前脂肪細胞マーカー（DLK1 および PPARG）のレベル上昇を示した。これらのデータを総合すると、SQSTMEM43 相互作用の破壊が ARVC 表現型に寄与し、KY02111 は疾患を模倣するツールとして機能することが示唆された。これらの上杉グループとの共同研究は 2021 年に Angew.
Cheｍ. Int. Ed.に発表した。
Y. Takemoto, S. Kadota, I. Minami, S. Otsuka, S. Okuda, M. Abo, L. L. Punzalan, Y. Shen, Y. Shiba,
M. Uesugi, Chemical Genetics Reveals a Role of Squalene Synthase in TGFβ Signaling andCardiomyogenesis, Angew. Chem. Int. Ed. 2021, 60, 21824.

－93－

2021-94
共役系ポリマーの開発と非フラーレン型太陽電池の高効率化
尾坂格

広島大学

【研究背景と目的】
有機薄膜太陽電池（OPV）は、次世代の太陽電池として注目されている。OPV の課題はエネル
ギー変換効率（PCE）の向上であり、これに向けて高性能な発電材料の開発が求められている。一方、発電材料の結晶状態は OPV 特性に大きな影響を与えるため、これを制御することが高効率化に向けて重要である。我々は以前、ドナー材料に高い結晶性を有するチアゾロチアゾール系ポリマ
ーPTzBT（Figure 1）、アクセプター材料にフラーレン誘導体 PCBM を用いた OPV 素子が、良好なPCE を与えることを報告した。一方、PTzBT は非フラーレン系アクセプター材料を組み合わせると、変換効率が低下することを報告した。これは、非フラーレンと組み合わせることで、PTzBT の結晶性が著しく低下したためである。そこで本研究では、PTzBT におけるアルキル基をエステル基に置換した PTzBTE（Figure 1）を合成した。PTzBTE は、エステル基内の酸素と主鎖内の硫黄との分子
内非結合性相互作用により、結晶性の向上が期待できる。
【実験結果と考察】
PTzBTE は PTzBT とほぼ同様の吸収スペクトルを示したが、HOMO および LUMO 準位は PTzBT よりも深いことが分かった。これは、エステル基の電子求引効果に起因する。
また、ポリマー単独膜の X 線回折測定を行ったところ、
PTzBTE は PTzBT に比べて、結晶性がやや高く、電荷輸送性に有利な Face-on 配向性が強くなっていることが明らかとなった。
次に、PCBM を用いた OPV 素子を作製したところ、PTzBT

Figure 1. Chemical structure of PTzBT and
PTzBTE.

は約 7%の PCE を与えたが、PTzBTE は主に VOC が向上し、8%を超える高い PCE を示した 3)。一方、非フラーレンアク
セプター材料である IT-4F や Y6 を用いた OPV 素子では、PTzBT の PCE は 6〜8%程度であったが、PTzBTE の PCE は
12〜13%と顕著に高い値を示した。しかし興味深いことに、Y6 と類似の非フラーレンアクセプターである Y12 を用いた素子では、PTzBT は最大 13.8%、PTzBTE は最大 14.8%と高い PCE を示した。これは、ポリマーとアクセプターの組み合わせにより、それぞれの結晶状態が変化したことと相関す

Figure 2. Current-voltage curves of theOPV cells based on PTzBT and PTzBTE.

ることが分かった。
【成果報告】＜論文＞ (1) K. Yamanaka, M. Saito, T. Mikie, I. Osaka, Bull. Chem. Soc. Chem., 2021, 94, 2019-2027.
＜学会発表＞ (1) 山中 滉大, 三木江 翼, 斎藤 慎彦, キム ヒョンド, 大北 英生, 尾坂 格「分子内非結合性相互作用によるチアゾロチアゾール系ポリマーの高結晶化と有機太陽電池の高効率化」，第 70 回 高分子討論会（オンライン）－94－

2021-95
Demonstration of topological phase control in chalcogenide superlattice
Misako Morota AIST
Purpose: The aim of this research is to create topological properties from materials used in the phasechange memory devices and to demonstrate new functions of these materials. Topological materials
have a characteristic surface electronic state caused by strong spin-orbit coupling, and are expected
to be the next generation of highly efficient spin current sources to replace transition metals. On theother hand, the superlattice type phase-change memory, which is currently being developed, iscomposed of germanium telluride (GeTe) and antimony telluride (Sb2Te3), which are normal insulator(NI) and topological insulator (TI), respectively. This superlattice is expected theoretically to bepossible to produce various topological phases by controlling the degree of hybridization of wave
functions on the TI surface. In this study, the goal is to investigate the correlation between the spin
generation efficiency of GeTe and Sb2Te3 multilayers and the stacking order by Spin Torque
Ferromagnetic Resonance (ST-FMR) measurements. So firstly, we confirmed the fabrication process
and the measurement system for a single layer of topological insulator Sb2Te3.
Experimental: ST-FMR measurement samples were first deposited at AIST using RF sputtering of
Sb2Te3 5nm/CoFeB 5nm/SiO2 3nm, and then the device and electrode fabrication and ST-FMR
measurement were performed at Institute for Chemical Research, Kyoto University. In order to checkthe fabrication process and to compare with topological insulators, the sample was also prepared byreplacing the Sb2Te3 layer with transition metal platinum (Pt).
Results and Discussion: The figure shows therelationship between the external magnetic
field and the voltage at different frequencies in
the Sb2Te3 and Pt layers with 5-nm thickness.
Comparing the Sb2Te3 and Pt samples, thevoltage spectra are asymmetric in the Pt
samples, while apparently symmetric in the
Sb2Te3 samples. This means that the spin
torque generated by the spin current from
Sb2Te3 is larger than the torque induced by themagnetic field caused by the current flowing
in the Sb2Te3 layer. this result suggests that thehighlyefficientcharge-spincurrent

conversion property of Sb2Te3, which isworthy of further investigation in the future.

Figure. ST-FMR signals as a function of external
field for (a) Sb2Te3 and (b) Pt with varied
frequencies. The inset shows the direction of theapplied external magnetic field for a sample.

－95－2021-96
Study of spin dynamics in garnet nanocrystal thin films preparedby co-precipitation method
Keisuke Yamada

Gifu University【Introduction】 Thermoelectric conversion elements utilizing the spin Seebeck effect (SSE)

enabled in such a simple structure have recently attracted much attention owing to their uniqueproperties and demands for future practical use. Synthetic YIG, including bismuth-doped YIG(Bi-YIG), is also attractive as materials gain large SSE voltages. Since Bi is characterized bystrong polarizability, the effective spin-orbit coupling (SOC) is induced in Bi-YIG, therefore, theSOC might affect the spin–thermoelectric phenomena for SSE. In this report, we report on thelongitudinal SSE (LSSE) voltage in Bi-YIG films prepared on a Si substrate via a sol-gel solution
using a spin-coating process to investigate the effect of Bi composition on the LSSE voltage.
【Experimental Method】BixY3-xFe5O12 (0 ≤ x ≤ 1.2) film samples were made on a Si substrateby sol-gel, spin-coating, and annealing at Ta = 973-1073 K for 2 hours in air. Their structure andmagnetic properties were characterized by X-ray diffractometry (XRD), scanning electron
microscopy (SEM), ferromagnetic resonance (FMR) measurements and LSSE measurements.
FMR measurements were performed at ICR of Kyoto Univ.
【Results and Discussion】According to the X-ray diffraction spectra of the samples, diffraction

peaks associated with the garnet phase are readily observed. Figure 1(a) shows surface and crosssectional SEM images of the Bi-YIG film at x = 0.8 annealed at 973 K. The thickness of the film
formed by the agglomeration of nanoparticles was approximately 50 nm. Figure 1(b) shows that
the LSSE constant (S) and thermoelectric performance (TP) of the Bi-YIG/Pt (5 nm) films tends
to increase with increasing Bi composition (0 ≤ x ≤ 0.8), and the value of the TP at x = 0.8 is 1.7
times larger than that at x = 0. This result indicates that the increasing tendency of the TP occurs
because of the efficient spin current conversion from Bi-YIG to the Pt layer due to Bi substitution.

Figure 1: (a) Surface and cross-sectional SEM images of Bi-YIG at x = 0.8 annealed at 973 K.
(b) Bi composition x dependence on S (left axis) and TP (right axis) at various Ta.
【Achievement reports】(1) M. Yamamoto, et al. under Review. (2) K. Yamada, et al. Journal of Magnetismand Magnetic Materials 535, 168093 (2021).
－96－2021-97
Study on electronic and magnetic behavior of perpendicularly magnetizedcobalt ferrite films
Masaaki Tanaka

Nagoya Institute of Technology

The tunneling electron through ferromagnetic insulator films is spin-polarized becauseof the barrier height difference depending on spin. Ferrimagnetic insulator CoxFe3-xO4+δ (CFO,
0<x<1) films with in-plane elongational strain, which have large perpendicular magnetic
anisotropy (PMA), can be applied for spin injection source of PMA spintronics devices. In thisstudy, the tunnel magnetoresistance (TMR) effect using perpendicularly magnetized CFO films
was investigated.
CFO (x=0.6, t = 0.8 nm, 1.5 nm, and 3.0 nm)/MgO (2.0 nm)/Co (1.5 nm)/{Tb/Co}n (13nm)/Co(2.0 nm) films were grown on conductive Co0.2Fe2.8O4+δ’ films of 20 nm thickness. The
conductive Co0.2Fe2.8O4+δ’ films, which have conductivity due to electron hopping between
Fe2+ and Fe3+ and have PMA, are used for the bottom electrodes of magnetic tunnel junctions(MTJs). The CFO films grown on the Co0.2Fe2.8O4+δ’ films can be expected to decrease
antiphase boundary because both CFO and Co0.2Fe2.8O4+δ’ are inverse spinel structures. The
out-of-plane hysteresis loops of these films show two magnetization switching steps. The MTJs
with a junction diameter of 15 μm were fabricated using photolithography and dry etching by
an ion-milling method. This microfabrication was carried out at ICR, Kyoto University. The
current-voltage and magnetoresistance measurements of the MTJs were performed using afour-probe method at various temperatures.
The current-voltage measurements indicated that the CFO/MgO layer shows goodtunneling properties. The resistance increased dramatically with decreasing temperature, whichindicates that the conductivity of the junction
is governed by the tunneling current. Figure
1 shows the magnetoresistance of the MTJ(t= 3.0 nm) at 300 K at the bias voltage of
200 mV. The TMR effect caused by themagnetization

switching

of

CFO

and

CoFe/{Tb/Co}n layers was observed. The
TMR ratio at 100 K and 300 K were －18%
and －2.7 %, respectively. It was also foundthat the TMR ratio decreased with thedecrease of CFO thickness.

Fig. 1 Magnetoresistance of the MTJ (t= 3.0nm) at 300 K at the bias voltage of 200 mV.

－97－

2021-98
Electronic and spintronic properties of multilayer system including NiCo2O4
and Fe3O4
Taro Nagahama Hokkaido University
Introduction: Recently, spinel oxides have attracted considerable attention because of their potential in
spintronics research. The inverse spinel oxide NiCo2O4 (NCO) is a promising magnetic oxide with potential
applications in spintronics devices due to its metallic conductivity and ferrimagnetism. In particular, NCO wastheoretically predicted to have electronic states corresponding to a half-metal with perfect negative
polarization of −100% at the Fermi level, indicating that it provides a highly spin-polarized current. Morerecently, large TMR ratios in excess of 200% were experimentally observed for NCO/MAO/NCO
perpendicular MTJs, demonstrating that NCO has a large spin polarization. However, the sign of spinpolarization remains unclear. In this study, direct evidence of negative spin polarization, namely the inverse
TMR effect, was observed in NCO/MgO/Fe MTJs.
Experiment: Multilayers were prepared on MgO(100) substrates by reactive molecular beam epitaxy method.
The layer structure of the MTJs was MgO(100) substrate/MgO buffer (20 nm)/NiO (5 nm)/NCO (24 nm)/MgO(2.2 nm)/Fe (10 nm)/Au (30 nm). The MTJ structures with a junction area of 10 × 10 m2 were patterned bya conventional microfabrication process involving photolithography and Ar ion milling.
Results and discussions: We confirmed the epitaxial growth of films by RHEED. The RHEED patterns of
NCO film changed from rock salt-type crystal structure to spinel-type by annealing under an oxygen
atmosphere. Figure 1 shows the TMR curve of MTJ with NCO at 14 K at 10mV with the in-plane magnetic
field. An inverse TMR effect was observed, which is the direct evidence of negative spin polarization of NCO.
As the bias voltage increased, the absolute value of the TMR ratio decreased monotonically. With regarding
to the temperature dependence of the TMR ratio, the TMR ratio was -25% at 10 K, and the absolute value of
the TMR ratio decreased with increasing temperature and was less than -1.0% at 100 K. The behavior could
be attributed to the temperature dependence ofmagnetization of NCO.
Publication and Conference: 1. Hara et al.,"Inverse Tunnel Magnetoresistance of Magnetic
Tunnel Junctions with a NiCo2O4 Electrode"submitted to Appl. Phys. Lett. 2. Nagahama et al.,"Tunnelmagnetoresistanceeffectof

NiCo2O4/MgO/Fe magnetic tunnel junctions"2022 Joint MMM-Intermag Conference, online.

Fig.1 The inverse TMR curve of NCO/MgO/Fe MTJ.
Inset is the enlarged plot of low magnetic field region.

－98－2021-99
ナノ秒オーダーの逆項間交差を示す熱活性化遅延蛍光材料の開発
相澤直矢

大阪大学

本研究は、化学研究所 環境物質化学研究系 分子材料化学領域の梶 弘典教授と共同で、三重項励起状態から一重項励起状態への遷移である逆項間交差 (RISC) をナノ秒オーダーで引き起こす熱活性化遅延蛍光 (TADF) 材料を創出することを目的とする。
本年度は、その候補分子として、大きなスピン–軌道相互作用が期待できる Se を含む
MOCz-SXT (Fig 1a) を設計し、その RISC の速度定数 (kRISC) を理論的に予測した。
【実験】時間依存密度汎関数 (TDDFT) 法を用いて、MOCz-SXT の励起一重項および三重項状態とそれらの間の最低エネルギー交差シームの構造最適化計算を行った。汎関数には長距離補正を含む LC-BLYP を用い、その距離補正パラメーターを Janak の定理に基いて非経験的に最適化した。基底関数には 6-31G(d)を用いた。スピン–軌道相互作用の計算には一電子近似 Breit-Pauli ハミルトニアンを用いた。各励起状態のエネル
ギーとスピン–軌道相互作用を用いて、マーカス型の非断熱遷移モデル（式 1）より、
kRISC を算出した。
(1)
ここで、HSO は一重項および三重項励起状態間のスピン–軌道相互作用、λ は再配列エ
ネルギー、EA は活性化エネルギー（交差シームと三重項励起状態の平衡構造とのエネ
ルギー差）、ћ はディラック定数、kB はボルツマン定数、T は温度である。
【結果】MOCz-SXT の最低エネルギー交差シームは、第一励起一重項 (S1) と第二励起三重項 (T2) の間で発見された (Fig 1b)。その構造における HSO は 29.7 cm–1 と有機分子として大きな値が計算された。この大きな HSO に由来して、kRISC は 3.6 × 109 s–1 とナノ秒オーダーに達することが予測された。

Fig 1 (a) MOCz-SXT の分子構造 (b) 励起状態のポテンシャルエネルギープロファイル－99－2021-100
時間分解分光計測による熱活性化遅延蛍光における逆項間交差の機構解明
山方啓

豊田工業大学目的 熱活性化遅延蛍光(TADF)は有機発光素子の高効率化に有用であることから盛んに研究が行われている．京都大学化学研究所の梶教授らによって近年開発された MATA[1-3]は塗布成膜可能な青色 TADF 材料として注目されているが，その励起ダイナミ
クスはまだに十分明らかにされていない．そこで本研究ではこの理解を深めるため，
フェムト秒時間分解分光装置を用いて MA-TA の光励起過程を詳しく調べた．
実験方法 MA-TA は本課題の共同研究者である梶教授より提供を受けた．過渡吸収分
光計測におけるポンプ光には波長 355 nm，パルスエネルギー1 μJ，パルス幅 90 fs(ピコ秒領域用)または 800 ps(ナノ秒領域用)のレーザーパルスを使用した．プローブ光には1250 nm のフェムト秒パルスを BaF2 板に集光して発生させた白色光パルスを用いた．
実験結果と考察 MA-TA のトルエン溶液を Ar ガスでバブリングした後に過渡吸収を測定すると，ピコ秒領域では図 1a のように，500~1000 nm にかけてブロードな吸収が観測されるが，時間の経過と共に 850 nm 付近の吸収が減少し 600 nm 付近の吸収が増加することが分かった．これは MA-TA のドナー(D)部位で励起された電子がアクセプ
タ(A)部位に移動する過程に対応し，その時定数は 7.8 ps と求められた．次にナノ秒領域を測定すると，図 1b のように 600 nm 付近の吸収は減少し，逆に 800~1000 nm のブ
ロードな吸収が増加した．この吸収は O2 バブリングで減衰が加速されることから(図1c)，三重項励起子に帰属され，項間交差が 17ns の時定数で進行することが確認できた．なお，TADF を誘起する MA-TA の逆項間交差の速度は D-A 連結接合部位のねじれ角によって変化するという興味深い性質が報告されており[2]，今後，赤外パルスによる振動励起や発光測定を組み合わせてこの過程を詳細に調べる予定である．
参考文献[1] Y. Wada, S. Kubo, and H. Kaji, Adv. Mater. 30, 170564 (2018).
[2] Y. Wada, Y. Wakisaka, and H. Kaji, ChemPhysChem 22, 625 (2021).
[3] Y. Wada, K. Shizu, and H. Kaji, J. Phys. Chem. A 125, 4534 (2021).
成果報告

0.5

850 nmCSmdb1016MTAr355n1u__d600_20n
CSmdb1016MTAr355n1u__d850_20n

0.0
0

5
Time / ps

10

0.0

1.0x10-2

1-2 ns10-12
50-55
300-390
1200-1350
2700-3000

0.5

3.0x10

1.0

Smdb6372MTArR_sp50_55_1
Smdb6372MTArR_sp100_110_1
Smdb6271MTArRe355n1u_d600_20n

600 nm

Smdb6271MTArRe355n1u_d850_20n

0.0

0

50
Time / ns

100

0.0
500

600

700
800
Wavelength / nm

900

1000

-3

2.5

850 nm

Smdb6271MTArR_sp11_12_1
Smdb6271MTArR_sp20_22_1

Smdb6271MTArR_sp60_65_1
0.5
Smdb6372MTArR_sp20_23_1

AbsorbanceAbsorbance

CSmdb1016MTAr_sp45_47_1
CSmdb1016MTAr_sp55_57_1
CSmdb1016MTAr_sp140_145_1
CSmdb1119MTAr_sp20_21_1
CSmdb1119MTAr_sp105_110_1

0.5(b)ns, Ar

600 nm1.0

Norm. Absorbance-2

1.0x100-0.2 ps
1 -1.210-10.5
100-110950-1000

Absorbance(a)ps, Ar

Norm. Absorbance[1] 学術変革領域 A・動的エキシトン，第 4 回領域会議.
(c)

Arバブリング後

Smdb5361MTO355n1u_1n_d850_20
Smdb6271MTArRe355n1u_d850_20

2.0
1.5

O2バブリング後

1.0
0.5
0.0

500

600

700
800
Wavelength / nm

900

1000

0

20

40 60
Time / ns

80100

図 1 MA-TA トルエン溶液の過渡吸収スペクトル。内挿図はそれぞれの 600 nm および 850 nm の時間変化．
(a)ピコ秒領域，Ar バブリング後．(b) ナノ秒領域，Ar バブリング後．(c) 850 nm の減衰曲線の比較．
－100－

2021-101
Functional characterization of extracellular vesicles produced byintestinal bacteria and development of their applications
Shino Yamasaki

Kansai University

Introduction:
The human gastrointestinal tract is inhabited by a wide variety of intestinal bacteria whose
metabolites affect host physiology. Furthermore, it has been found that the extracellular vesicles(EVs) released by intestinal bacteria play important roles in the interaction between bacteria andthe host, such as the regulation of biological functions and colonization of the host. In this study,
we analyzed the production and secretion mechanisms of EVs by intestinal bacteria andinvestigated the biological responses elicited by EVs. Based on the findings, we developed novel
systems for the secretion and production of heterologous proteins using EVs.
Results:
1. Immunomodulatory effects of EVs produced by intestinal bacteria
To prevent inflammatory bowel disease, EVs produced by intestinal bacteria with
anti-inflammatory effects were screened. EVs derived from Lactiplantibacillus plantarum
suppressed the inflammation induced by lipopolysaccharide in human colonic epithelial HT29
cells. This anti-inflammatory effect was found to be unique to these EVs, suggesting that theeffect was induced by the uptake of nano-sized EVs by HT29 cells.
With regard to the immunostimulatory effect, it was elucidated that EVs produced by
Lactobacillus sp. induced IL-6 production from macrophage-like RAW264 cells and enhanced
IgA secretion by murine Peyer's patch cells. GAPDH was identified as a specific protein in theEVs by MALDI-MS analysis. Recombinant GAPDH also induced IL-6 production fromRAW264 and monocyte THP-1 cells, suggesting that GAPDH in the EVs activates immune cells.
2. Improvement of EV production by breaking outer membrane-peptidoglycan linkage
Shewanella vesiculosa HM13, a Gram-negative bacterium isolated from intestinal contents ofhorse mackerel (Trachurus japonicus), abundantly produces EVs and is considered useful as ahost for production of heterologous proteins as cargoes of EVs. In this study, we aimed toenhance the EV productivity of this bacterium. For this purpose, the linkage between the outermembrane (OM) and the peptidoglycan (PG) was weakened by deleting the genes coding for
Braun’s lipoprotein (Lpp), which connects OM to PG, and L,D-transpeptidase, which catalyzes
the formation of a covalent crosslink between Lpp and PG. Both gene deletions resulted in about
2.5-fold increase in EV productivity. Thus, this approach will contribute to the development of
the EV-based protein production system by using S. vesiculosa HM13 as the host.
－101－2021-102
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. and Komagataeibacter spp. can produce acetic acid from ethanol and possess
exceptional resistance to acetic acid, which is not found in other bacteria. It is thought that
there is a close relationship between the cell membrane of AAB and their resistance to acetic
acid, but the molecular analysis of membrane function has not been progressed.
AAB produce phosphatidylcholine (PC) as a membrane phospholipid (PL) constituting thecell membrane. Although previous studies suggested that PC is involved in acetic acidtolerance, the physiological functions of PC in detail are still unclear. In this study, weconstructed the PC-deficient mutant of Acetobacter pasteurianus SKU1108, isolated fromThailand, and investigated the phenotypes of the mutant under various growth conditions.
[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. The
membrane PL composition of ΔpmtA was analyzed by thin-layer chromatography andcompared with the parental strain. As a result, it was confirmed that PC was not produced, but
PE was accumulated in ∆pmtA. 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 acidthan the 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
is important for the growth of this strain both in the presence of acetic acid and in low pH
environments. Interestingly, the colony-forming ability of ΔpmtA was restored to the parental
level when the medium containing acetic acid was neutralized with potassium hydroxide but
not when neutralized with sodium hydroxide. These results suggested that PC is also involvedin the tolerance of this strain to sodium acetate under neutral pH conditions.

－102－2021-103
擬秩序ガラスの熱伝導
増野敦信 弘前大学

目的：ガラスとは一般に，SiO2 等の網目形成酸化物によって形成される，隙間の多い三次元不規則
ネットワーク構造を有する非晶質材料であると認識されている．それに対して我々は，原料を空中に浮かせたまま溶融，凝固させる無容器法を用いて，ネットワークを形成していないガラスの合成に成功している．これまでの構造解析の結果から，この特異なガラス中の構成成分は，結晶に準じたある程度の秩序をもって密に詰まっていることがわかってきた．我々がよく知るガラスとは全く異なる，「擬秩序ガラス」とも呼ぶべき新しいカテゴリーの物質である．酸化物ガラスの熱は主にフォノンによって伝播することを考えると，特異な構造を有する擬秩序ガラスの熱伝導特性は，従来型のネットワーク系ガラスとは異なる振る舞いを示す可能性がある．そこで本研究ではまず，
CaO-Al2O3 系ガラスについて，熱伝導特性の組成依存性を調べることとした．
実験：CaO-Al2O3 二元系は，通常の溶融急冷法では共晶点近傍組成でのみしかガラス化しないが，無容器法によってガラス化範囲は大幅に広がる．ガス浮遊炉を用いて，xCaO-(100−x)Al2O3 (x = 50,
55, 60, 65, 70)を合成した．浮遊には O2 ガスを用いた．ガラス転移温度（Tg）は，TG-DTA により決定した．物性計測や構造解析には，Tg 近傍でアニール後，徐冷することでガラス内部のひずみを取り除いた試料を用いた．密度はピクノメータによって計測し，充填密度を算出した．室温での熱拡
散率は温度波法によって，また室温から低温までの比熱は京都大学化学研究所島川研究室の PPMS
によって測定した．ラマン散乱分光，27Al MAS NMR によってガラスの構造解析を行った．

結果：合成したガラスはいずれも透明であった.
xCaO-(100−x)Al2O3 ガラスの充填密度は，CaO 含有量増加に対して大きな変化はなかったが，x =70 でやや増加していた．27Al MAS NMR からは，
Al のほぼ全ては 4 配位となっていることがわ
かった．NMR のケミカルシフトにおける組成依
存性は小さかったが，Raman 散乱スペクトルでは，x の増加とともに非架橋酸素の割合が増加する傾向が確認された．熱拡散率は，CaO 含有量増加に伴って減少する傾向が見られた（Figure1）．比熱のデータについては，今年度は x = 70

Figure 1. xCaO-(100−x)Al2O3 ガラスの熱拡散率．

のガラスで室温近傍のみ取得することができた．得られた密度，熱拡散率，比熱の値から算出した
熱伝導率は，1.5 (W/m·K)であった．一般的なネットワーク系ガラスと比較して，1.5～3 倍程度の値である．今後は，熱伝導率の組成依存性とガラス構造との相関を，構造モデルをもとに明らかにすることが求められる．
－103－

2021-104
異常高原子価イオンを含む機能性酸化物合成とその構造物性研究齊藤高志

高エネルギー加速器研究機構

鉄イオンは通常+2 価や+3 価の状態が安定であるが、強い酸化雰囲気を利用して+4 価、+5 価、+6 価といった異常高原子価と呼ばれる価数を持つ場合がある。このような異常高原子価 Fe イオンを含む化合物では Fe-3d 軌道と O-2p 軌道が強く混成した特徴的な電子状態を持つ。Fe4+イオンは低温で 2Fe4+ → Fe3+ + Fe5+で表される電価不均化反応を起こし、これに伴って金属絶縁体転移や負の熱膨張等の興味深い性質がしばしば発現する。CaFeO3 や CaCu3Fe4O12 等、酸素に八面体配位された
B サイトに Fe4+のみを含むペロブスカイト型化合物にける電荷不均化では、価数が低くイオン半径が大きな Fe3+と価数が高くイオン半径が小さな Fe5+がランダムに配置するより交互に並んだ方が系全体のエネルギーが低くなるため、電価不均化状態では Fe3+/Fe5+が交互に並んだ構造をとる。このように Fe3+/Fe5+が交互に並んだ構造は、Fe4+を含む高温相におけるフォノンのブリージングモー
ドが凍結した状態と見ることができる。一方、CaFeO3 における B サイトの Fe4+の半分を Mn4+で置換して得られる Ca(Fe0.5Mn0.5)O3 では、B サイトにおいて Fe4+と Mn4+がランダムに配置していることから Fe3+/Fe5+が交互に並ぶことはできないが、低温で Fe4+が電価不均化を起こすことが知られている。したがって Ca(Fe0.5Mn0.5)O3 における電価不均化状態では、フォノンのブリージングモード
凍結とは異なる形で Fe3+と Fe5+の電荷不均化が起こっている可能性がある。Ca(Fe0.5Mn0.5)O3 における電価不均化状態を明らかにするためには Fe3+/Fe5+の配列情報を含む詳細な結晶構造解析を行う必要があるが、一般に電荷不均化による構造変化は酸素の原子座標の微細なズレによるものである
ことから、これを検出するためには酸素原子座標をきわめて精密に求める必要がある。
Ca(Fe0.5Mn0.5)O3 において軽元素である酸素の原子座標を高精度で求めるためには統計精度の高い
中性子回折データが不可欠であることから、Ca(Fe0.5Mn0.5)O3 の中性子回折実験を行った。
試料合成には化学研究所・島川研究室の高圧合成装置を利用した。炭酸塩、酸化物原料から作製した前駆体 Ca(Fe0.5Mn0.5)O2.5 を KClO4（酸化剤）と共に 3GPa、1000℃で処理することにより、Ca(Fe0.5Mn0.5)O3 多結晶試料を得た。また J-PARC/MLF の BL09 に設置された高強度・高分解能 TOF
中性子回折装置 SPICA を用い、300 K～20 K における粉末中性子回折実験を行った。室温では Fe/Mnの長距離秩序/短距離秩序の痕跡は観測されず、Fe/Mn がランダムに配列した Ca(Fe0.5Mn0.5)O3 が得られたことが確認された。低温の電荷不均化相における詳細な結晶構造解析を現在進めている。

－104－2021-105
界面活性剤を抽出剤として利用した固相抽出による Eu 分離法の開発
倉橋健介

１．

大阪府立大学工業高等専門学校

目的

工業分野における需要の高まりから，希土類元素のリサイクルが期待されている．
希土類元素の主要な分離法である溶媒抽出法は，揮発性有機溶媒の使用が問題視されており，揮発性有機溶媒の少ない固相抽出法が注目されている．先行研究では，陰イ
オン界面活性剤のみを用いて溶媒含浸樹脂（SIR）を調製し，Eu の固相抽出を行った
場合でも，界面活性剤の濃度上昇に伴い抽出率が向上するが，疎水基が同じ陽イオン
界面活性剤の場合は低下することを見出した．界面活性剤は安価で多様な種類の試薬が市販されており，界面活性剤単独で希土類金属を抽出できれば，高価な抽出剤の使用を削減し，分離コストを大きく下げることができる．そこで本研究では，親水部が同じで疎水基の長さが異なる界面活性剤を使い，疎水基の長さが与える抽出率への影
響を観察するとともに，物性の近いその他の希土類元素との選択性について検討した．
２．

実験方法

含浸する界面活性剤は親水基が陰イオン性である Sodium Dodecylsulfate (SDS)とSodium Hexadecylsulfate (SHS)を使用した．エタノールで洗浄後、乾燥した Amberlite
XAD-7HP 1.0 g に対して任意の濃度の界面活性剤を含むエタノール溶液を加え，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．
0.1 mM の La, Eu, Lu 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 2.5mL を HCl と NaOH で任意の pH に調整した．この水相に SIR を 0.1 g 加え，2 時間振とうした．振とう後，水相を分取し pH を測定した．分取した水相は Ni を内標準として，誘導結合プラズマ発光分光分析装置(ICP-OES)を用いて金属濃度を測定した．
３．

結果と考察

界面活性剤 SHS は溶解度が低いことから，先行研究で用いた調製法では，含浸溶媒
中に溶けずに粉状で残ることがわかった．そこで，SDS を含浸させる際の溶媒量を増やしたところ，含浸する SDS の物質量が同じなら，溶媒の量を変えた場合でも抽出率はほとんど変化せず，溶媒量を増やすことで SHS の低溶解度を回避し，SHS を含浸した SIR を調整できることがわかった．調製した SIR を用いて，界面活性剤疎水基の影
響を比較ところ，疎水基の短い SDS で調製した SIR がより高い抽出を示した．また，希土類金属同士の分離選択性の検討では，La > Eu > Lu の順で抽出率がわずかに下がっているがその差は小さく，元素間の分離は難しいことがわかった．
４．

成果報告

1) 小笠原拓海ら，第 23 回化学工学会学生発表会，オンライン開催，2022.3.

－105－2021-106
Fine synthesis of polymer brush on nano-platelet for functional photonic LC
Yoshiaki Uchida

Osaka University

The rapid spread of automated systems in factories and vehicles has required visible light
communication systems using optical fibers made of inexpensive polymers. As thecommunication accelerates, the number of nodes incorporated in the systems increases. Thesesystems have potential problems: interference between cables, complicated wiring, and bending
flexibility limits. Fiber-free visible light communication systems are promising to solve theproblems.
We have focused on switchable photonic structures of liquid crystalline (LC) phases.
Cholesteric LC (CLC) materials and hyperswollen lamellar (HL) materials with flexible onedimensional periodic structures [1,2], nematic LC (NLC) materials showing strong lightscattering as random laser resonators [3], and whispering gallery mode (WGM) in an LC
microsphere [4] are promising. Light is trapped inside the LC materials. Magnetic fields are
expected to be useful for the remote control of optical transmission devices. We have alreadyfabricated magnetically switchable photonic systems with LC materials. The random laser action
in NLC materials doped with ferromagnetic nano-platelet is magnetically controllable [3].
We focus on the stable dispersion of the ferromagnetic nano-platelet in the photonic LC phases
to obtain ferromagnetic photonic materials for the magnetic switching of light emission. We haveinvestigated the dispersion of ferromagnetic particles with polymer brushes into various liquid
crystals. To disperse the nano-platelet in photonic LC materials, we have been optimizing thepolymer brush structure in this project. This year, we have tried to disperse the nano-platelet in
HL phases to prepare magnetically controllable photonic LC materials. We successfully prepared
ferromagnetic LC mixtures using previously reported methods to disperse nanosheets and nanoplatelet in the HL phases [5]. Now we are preparing the paper on the ferromagnetic LC mixtures.
References
1. Y. Iwai, R. Iijima, K. Yamamoto, T. Akita, Y. Uchida, N. Nishiyama, Adv. Opt. Mater., 8,1901363 (2020).
2. Y. Uchida, T. Nishizawa, T. Omiya, Y. Hirota, N. Nishiyama, J. Am. Chem. Soc., 138, 1103–
1105 (2016).
3. T. Naruta, T. Akita, Y. Uchida, D. Lisjak, A. Mertelj, N. Nishiyama, Opt. Express, 27, 24426–
24433 (2019).
4. Y. Uchida, Y. Takanishi, J. Yamamoto, Adv. Mater., 25, 3234–3237 (2013).
5. K. Sasaki, T. Okue, T. Nakai, Y. Uchida, N. Nishiyama, Langmuir, 37, 5872–5877 (2021).

－106－2021-107
高分子ブラシ層内の水の構造および凍結挙動の解析
源明誠

[目的]

富山大学

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

glycolmonomethoxy

ether

methacrylate)（P(PEGMA)，Fig. 1）ブラシ内部の水構造を評価した。
[実験]

自作の ATR セルを使用し，種々濃度の P(PEGMA)

水溶液および種々膜厚（70, 218, 1130 nm）の P(PEGMA) ブラ 図 1 P(PEGMA) の構造
シ中の水の ATR near/mid-IR スペクトルを得た。水の OH 伸縮
振動1+3 領域（7800－5860 cm1）の解析は，二次微分スペク
トルから決定したピーク位置をもとにした成分分離により行った。
[結果および考察]

Fig. 2 に，純水，ブラシ中および遊離高分子水溶液（32.1 wt%）中の水の OH 伸縮振動1+3 領域（左図 2 膨潤 P(PEGMA) ブラシ中の水図）および基準振動領域（右図）の ATR near/mid-IR スペクト の ATR near/mid-IR スペクトルルを示す。ブラシ膜厚が薄くなるにつれてスペクトル形状は 実線：P(PEGMA)ブラシ

純水（点線）に近くなり，それは基準振動領域で特に顕著で

白抜き点線：P(PEGMA) 水溶液
点線：純水

あった。これはもぐり込み深さの波数依存性により，膜厚の薄いものではブラシ外の水まで観測していることに由来する。種々濃度の P(PEGMA) 水溶液とブラシ中の水の吸収強度の比較から膨潤ブラシの含水率は～29 wt% と推測した。また，1+3 領域の成分分離結果から，P(PEGMA)ブラシでは，
水の回転運動に由来する成分（1+3+R）の吸収が，ブラシの含水率に最も近い P(PEGMA)水溶液よりも小さくなっている

図 3 ブラシおよび遊離高分子水溶ことがわかった（Fig. 3）。このことは高分子鎖の片末端が固定 液の OH 伸縮振動1+3 領域の ATR
near-IR スペクトル化されたブラシは，遊離高分子鎖と比較し，高分子鎖の運動
実線：P(PEGMA)ブラシ（1130 nm）性が抑制されており，その結果，水の回転運動が制限されて 点線：P(PEGMA)水溶液
いることを示唆する。

－107－2021-108
Study on water freezing with lignocellulose nanofibers and their surface
modification toward functional materials
Keita Sakakibara

National Institute of Advanced Industrial Science and Technology

Objective. Cellulose nanofiber (CNF) has attracted much attention in material sciences, since itis thin (3 to sub-microns in diameter), renewable, biocompatible, low cost, and exhibits
remarkable mechanical properties such as high Young’s modulus. CNF can be obtained fromwood pulp fibers through chemical and/or mechanical disintegration methods. When applying
wood flour to the mechanical disintegration, lignocellulose nanofiber (LCNF) can be obtained,
in which macromolecular lignin and hemicellulose are tightly adhered to CNF as the same
composition ratio of the raw materials. LCNF provides a variety of applications to reinforce andstrengthen plastics, rubbers, coatings and paintings, and others. Furthermore, surface properties
of LCNF can be regulated by polymer grafting, forming polymer brush as a shell around LCNF
as a core. Especially, concentrated polymer brush (CPB), which is highly dense assemblies ofgrafted polymers, have successfully been synthesized through surface-initiated (SI) reversibledeactivation radical polymerization [1]. Recently, with the collaboration of Prof. Yoshinobu
Tsujii (ICR, Kyoto University), it has been revealed that CNF (not having lignin andhemicellulose) surface-modified with CPB, so called CNF-CPB, has exhibited synergistic
properties including high mechanical strength, ultralow friction, and bioinertness [2]. Hence,
LCNF (having lignin and hemicellulose) could also be upgrading by the CPB modification,
generating LCNF-CPB. One of the promising properties of CPB is to form anti-icing layer on
top surfaces. Thus, we, with the collaboration of Prof. Tsujii, attempted to study the preparation
Results. To begin with, LCNF was prepared by ball-milling. Oven(w/v)

ofwater,

N,N-dimethylacetamide(DMAc),

N,N-

dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and Nmethylpyrrolidone (NMP) was subjected to a ball-milling for 4 h at 450
rpm (repeated milling and pausing of 10 min each). The solvent of

SSA (m2 g-1)

dried wood flour (particle size < 0.2 mm, Japanese cypress) with 7.5%

80

100
60

40

50

20

0

Dielectric constantof LCNF-CPB toward novel functional materials

0

Water DMAc DMF DMSO NMP

Fig. SSA of LCNFs.

LCNF slurry was substituted to tert-butanol, and then lyophilized. The specific surface areas(SSA) of the LCNFs were determined by the BET plots from their nitrogen adsorptiondesorption isotherms (Fig).The thin LCNFs with SSA of more than 100 m2 g-1 was only obtainedusing water. The CPB modification was carried out following our previously reported procedure[2]. The characterization for LCNF-CPBs is underway.
References. 1) Y. Tsujii, et al., Adv. Polym. Sci., 2006, 197, 1–45. 2) K. Sakakibara, et al., ACS
Appl. Nano Mater., 2021, 4, 1503–1511.
－108－2021-109
Giant Magnetic Resistance on Single-Electron Transistor
Yutaka Majima

Tokyo Institute of Technology

The purpose of this study is to observe the giant magnetic resistance on single-electrontransistor. Spin-dependent single-electron tunneling, which is based on interplay between
single-electron changing effect and tunnel magnetoresistance (TMR) effect, has attracted muchattention owing to its unique phenomena such as the enhancement and the oscillation of TMR.
These phenomena have been observed in ferromagnetic tunnel junctions and ferromagnetic granularstructures.
Recently, we have reported a chemically-assembled single-electron transistor (SET) using
Pt-based nanogap electrodes and an Au nanoparticle, which showed clear and ideal Coulomb
diamonds. To realize the chemically-assembled SET, robust Pt-based nanogap electrodes with a
10-nm-scale ultrafine linewidth were fabricated by electron-beam lithography (EBL) andelectron-beam (EB) evaporation, and an alkanethiol-protected Au nanoparticle was chemisorbed
between the gap using alkanedithiol self-assembled monolayer (SAM).
In this project, we studied external magnetic field dependent current in achemically-assembled SET based on Pd nanogap electrodes and an Au nanoparticle. Pd was used asa paramagnetic material for nanogap electrodes. Pd nanogap electrodes with a gap separation of 7.5
nm were fabricated on Si substrates by a combination of EBL and EB evaporation. An Au
nanoparticle with a core diameter of 5.8 nm was synthesized at Prof. Teranishi laboratory and thenintroduced between the gap using alkanedithiol SAM.
Finally, an SET structure consisting of Pd source/tunnel
barrier/Au island/tunnel barrier/Pd drain (Pd/Au/Pd) withgate was realized.
The electrical characteristics of the fabricated SET
were measured at 9 K with and without an external
magnetic field. In the absence of a magnetic field, clear
Coulomb blockade was observed, indicating thatsingle-electron charging effect (Figure 1). When amagnetic field was applied to the SET, an increase anddecrease in current compared to the one without magnetic
field were observed in accordance with applied drain
voltage, which could be attributed to spin-dependent
single-electron tunneling in the Pd/Au/Pd SET structure.
The manuscript related to the above results is inpreparation.

－109－

Figure 1: Stability diagram of theSET based on Pd nanogap
electrodes and an Au nanoparticle
at 9 K.

2021-110
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：研究代表者は、カルボニル基をもつ化合物（ステロイド等）を誘導体化し、化学研究所の FTICR MS 装置を⽤いることにより、極めて⾼分解能（質量分解能 100 万）かつ⾼感度な質量分析
検出、及び、イメージング解析を⾏なう系を構築している。⼜、スギ⽊幹部の光学顕微鏡切⽚の組織切⽚上で化学反応を⾏い、反応⾏程の前後変化を、光学/蛍光顕微鏡、及び、電⼦顕微鏡（無蒸着 SEM 観察）レベルで追跡する実験系を構築した。⼜、顕微 FT-IR イメージングを⽤いて、⽊材の主要成分である Lignin, Cellulose 等のイメージング検出を⾏ない、晩材部において早材部よりも Lignin 及び Cellulose 量が多い結果を得た。本年度は、薄い⽊材切⽚を⽤いて、簡便で効率的な⽊材分解条件を探索する実験系の構築を⾏ない、化学研究所・中村研究室が⾏っている再⽣
可能バイオマス資源であるスギ等の⼈⼯森林⽊材から有⽤化合物⽣産を⾏う研究に適⽤することを⽬的として⾏った。
実験方法、実験結果、考察：
本年度は、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、40 μl の 30 %、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 24 時間後、20 % H2O2 液中では 48 時間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、触媒の添加なしでも効率的に仮道管細胞壁の分解が起こると考えられた。⼜、0 % H2O2 中では、切⽚の形状は１週間経過後も保たれていた。この実験系
は、薄い切⽚を 60 ℃の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、反応液（40 μl）を⽤いて、効率的にスギの化学分解条件を探索できる利点を持つ。今後、化学研究所・中村研究室で⾏われている鉄錯体触媒、イオン液体触媒、有機酸触媒等の効率的な⽊材化学分解の濃度、温度、時間等の条件を探索する実験系に応⽤していきたい。
⼜、分解過程の組織形態変化を解析する⽬的で、スギ切⽚の Lignin, Cellulose の同時検出を⾏っている。Cellulose を Calcofluor White（UV-A 励起、⻘⾊）で、Lignin を Basic Fuchsin（G 励起、⾚⾊）で染⾊したところ、Cellulose は仮道管の細胞壁に、Lignin は隣り合う仮道管の細胞間層に強く染⾊が認められた。
今後、中村研究室の共同研究者、研究協⼒者らが⾏っている触媒を⽤いたスギ等の⽊質バイオマスから有⽤化学物質を⽣産するための⽊質分解過程の解析に、これらの実験系（触媒のスクリーニング法や、Lignin, Cellulose の同時検出法）を適⽤していくと共に、超解像光学顕微鏡（解像度：数 10nm）、SEM による⽴体観察、顕微 FT-IR イメージング法、MS Imaging 法等と組み合わせて、⽊材分解過程の組織形態イメージング解析を⾏っていきたい。
成果報告：
Hayazaki M, Hatano O, Shimabayashi S, Akiyama T, Takemori H, Hamamoto A.
Zebrafish as a new model for rhododendrol-induced leukoderma.
Pigment Cell Melanoma Res. 2021 Nov;34(6):1029-1038. doi: 10.1111/pcmr.13005.

－110－2021-111
新規細胞内取込誘導タンパク質の同定
桑田啓子

名古屋大学

細胞膜透過ペプチド (CPP)は、細胞内移行性を示す数残基から 20 残基程度のペプチドで、タン
パク質や核酸等の生理活性物質の細胞内導入キャリアーとして利用されている[1]。オリゴアルギニ
ンは代表的な CPP の一つであるが、このうち D 体のオクタアルギニン (r8)、ドデカアルギニン (r12)が腫瘍組織集積性を示すことが化学研究所の二木教授らによって報告され[2]、医薬品等の送達への応用も期待される。CPP と血清タンパク質との相互作用が知られており[3]、CPP−血清タンパク質複合体が、Enhanced Permeation and Retention (EPR)効果によって腫瘍組織に集積する機構が考えられる。しかし、CPP がいずれの血清タンパク質と相互作用するかに関しては詳細には調べられていない。本研究では、オリゴアルギニン、特に r8 と相互作用する血清タンパク質の同定を目指した。
オリゴアルギニンとして、高い腫瘍集積性を示した r8、r12 とともに、顕著な集積性を示さない
D 体のテトラアルギニン (r4)をコントロールに用いた。これらのペプチドの蛍光標識体を Fmoc 固相合成法により調製し、質量比で血清タンパク質の大部分を占めるアルブミンとの相互作用に関して検討した。r4、r8、r12 それぞれについて、アルブミンと混合した後に限外濾過を行い、フィル
ター上に残った CPP と透過した CPP の割合を算出した。その結果、いずれの CPP も、アルブミンと混合することでフィルター上に残存する割合が高まったことから、アルブミンの相互作用が示唆された。さらに、等温滴定型カロリメトリー (ITC)を用いてこれらの相互作用を確認したところ、算出された解離定数はいずれも数十 µM オーダーであった。以上より、r4、r8、r12 はいずれもアルブミンと相互作用するがその相互作用は比較的弱いものであると示唆された。
これらの結果から、血清中にはアルブミンの他に、オリゴアルギニンと相互作用する血清タンパ
ク質が存在しているのではないかと考え、その探索を行った。上記 3 種のオリゴアルギニンの中で最も高い腫瘍集積性を示す r8 と血清との混合液を Native PAGE で展開し、蛍光の検出されたバン
ドを切り出してトリプシン消化した。得られたペプチド断片を質量分析により解析しデータベースと照合することで、バンド中に含まれていたタンパク質の候補が得られた。これら候補タンパク質と r8 との相互作用を、蛍光相関分光法 (FCS)を用いて個別に評価した。その結果、r8 と特に強く相互作用するタンパク質が明らかになった。また、r12、D-Rev、D-FHV などの CPP においても同様の傾向が見られた。現在、上記で見出されたタンパク質の CPP の細胞内移行における寄与に関して精査しているところである。

【参考文献】[1] Futaki, S., Biopolymers, (2006) 84, 241-249[2] Nakase, I. et al. J. Control. Release, (2012) 159, 181-188[3] Kosuge, M. et al. Bioconjugate Chem., (2008) 19, 656-664－111－

2021-112
マクロピノサイトーシスによる細胞内取込様式
前川大志

慶應義塾大学

目的：マクロピノサイトーシスは、細胞骨格(アクチン)の再構築と細胞膜の隆起・融合を伴い、広い範囲の細胞外液および細胞膜を細胞内に取込む。外的刺激により誘導される普遍的な液相エンドサイトーシス(細胞の生理的養分取込機構)であると共に、
近年では、がん細胞への養分取りこみにおける外的誘導を特に伴わない定常レベルのマクロピノサイトーシスの重要性が指摘されている。最近、マクロピノサイトーシスに注目が集まっている一方で、その分子基盤や細胞膜形態変化の詳細については不明な点が多く残されている。そこで本研究では、ペプチドによるマクロピノサイトーシ
スの誘導様式ならびに、細胞外微粒子の取り込みにおけるマクロピノサイトーシスの寄与とその分子機序解明に焦点を当て、理解を深めることを目的とする
実験方法：共同研究者である京都大学化学研究所の二木、広瀬らが開発したマクロピ
ノサイトーシス誘導活性が報告されているペプチドを HeLa cells に処理し、細胞膜形
態変化を走査型電子顕微鏡で観察した。また、マクロピノサイトーシス様の経路で取り込まれる事が示唆されている蛍光ビーズについても、二木、広瀬から提供してもらい、HeLa cells に添加し、細胞膜形態変化を走査型電子顕微鏡で観察した。更に、ア
クチン重合やカルシウムシグナリング等の既知の各種エンドサイトーシス阻害剤を
HeLa cells に処理し、細胞膜形態変化を走査型電子顕微鏡で観察した。
実験結果：HeLa cells にマクロピノサイトーシス誘導ペプチドを処理しても、顕著な細胞膜の形態変化は認められなかった。一方で、蛍光ビーズが HeLa cells に取り込まれる際に、特殊な細胞膜の形態変化が観察された。更に、この蛍光ビーズが取り込まれる際に生じていると考えられる細胞膜形態変化を阻害する阻害剤を複数同定するに至った。
考察：本研究を通して、HeLa cells は一般的なマクロピノサイトーシスとは異なる経路でマクロピノサイトーシス様の細胞外微粒子取り込み活性を有する事が示唆された。
今後は、本研究で同定した阻害剤を足掛かりにその分子機構の解明を継続する。
成果報告：該当なし。今後、データを更に集めて論文発表を計画している。

－112－

2021-113
原子レベル平坦表面ダイヤモンドを用いた量子情報科学研究徳田規夫 金沢大学【緒言】
ダイヤモンド中の単一窒素‐空孔複合体（NV）中心は優れたスピン特性及び光学特性を有する。他材料と比べ特筆すべき点は、NV 中心では単一スピンを室温において光検出・操作できる点である。その単一スピンをプローブとし、単一 NV 中心を用いた磁気センサ、電場センサ、
温度センサに関して、近年、優れた実証研究がなされてきた。
NV 中心のセンサ応用において、NV 中心は感度向上のため
数ナノレベルの浅い領域に存在していることが望ましい。しかし、ナノレベルでの表面付近では、センサとして使える電荷状態が－1 価に荷電した NV－の電荷状態が不安定になる
ことや、スピンコヒーレンス時間の短時間化によりセンサ感度が著しく低下するなど、重要な克服すべき課題がある。

図 重水素合成を用いた原子レベルで平坦化された表面における AFM 像[発表
文献 1]

【実験と結果】
ダイヤモンドにおいて、ある CVD 合成条件を満たすと、図に示したように数十 m 四方の面積において、原子レベルでフラットな表面を持つ試料を作成することができる。成膜プロセスの提案や合成条件における窒素濃度の制御の条件出しを、共焦点レーザ顕微鏡によって行った。課題として、新たな表面処理等を施して更なる安定化を行い、それらの測定を目指している。
また、共同研究成果として、京大化学研究所の我々の研究室で立ち上げた化学気相堆積（CVD）法によるダイヤモンド合成装置により、ダイヤモンドを合成し、n 型半導体ダイヤモンドの合成に成功した。
単一 NV 中心の T2 をスピンエコー法により確かめ、ミリ秒以上に十分に長くなることも実証した[2]。
また、共同研究成果として、我々はドレスト状態生成によるスピンコヒーレンス時間の桁違いの長時間化を実現し、それを用いて温度感度向上の実証研究を行った[3]。ダイヤモンド中の NV 中心は、細胞内部の温度分布の不均一性や局所的な温度変化によって引き起こされる細胞の生理機能の研究における高感度量子温度センサとしての応用が期待されている。
【参考文献】[1] N. Mizuochi, N. Tokuda, M. Ogura, S. Yamasaki, Jpn. J. Appl. Phys., 51, 090106 (2012).
【成果報告】[2] 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", 審
査中．
[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", 審査中．

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2021-114
量子センサの高感度化に向けたダイヤモンド合成と量子技術開発研究牧野俊晴 産業技術総合研究所【緒言】ダイヤモンド中の複合欠陥である窒素‐空孔複合体（NV）中心は、量子科学技術分野において研究が精力的に行われ、優れた特性が明らかにされてきた。特に、NV 中心は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（T2）を持つことにより高い感度が実現し、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。
【実験と結果】
これまで産総研グループが合成した n 型ダイヤモンド中のNV 中心を用いて、単一 NV ダイヤモンド量子センサで世界最長の T2 と室温での最高磁場感度を実現していたが [1]、今回、図 1 に示した京大化学研究所の我々の研究室で立ち上げた化学気相堆積（CVD）法によるダイヤモンド合成装置によ
図１り、ダイヤモンドを合成し、特性を評価した。
以前の合成条件とは異なり、今回、より毒性の低いター

京大化学研究所で立ち上げた

CVD 法によるダイヤモンド合成装置

シャルブチルフォスフィンガス（TBP）を用いてリンドープを行った。ホール測定の結果、n 型半導体ダイヤモンドが合成できたことが確かめられた。ダイヤモンドにおいて、n 型
半導体は天然に存在せず、不純物制御等の難しさから、合成できたグループは世界でも 4 つのみであったが、今回、不純物制御の最適条件を丹念に調べ、n 型半導体ダイヤモンドが合成できた。
単一 NV 中心の T2 をスピンエコー法により確かめ、ミリ
秒以上に十分に長くなることも実証した[2]。今回の成功は、将来の量子センサ高感度化や、半導体特性を生かしたデバ

図２

合成したダイヤモンド試料中のイス作製、及び集積化にとって重要な一歩である。

単一 NV 中心におけるスピンエコー測定結果．十分に長いスピンコヒーレン【参考文献】[1] E. D. Herbschleb, H. Kato, Y. Maruyama, T. Danjo, T. Makino,

ス時間が得られた。

S. Yamasaki, I. Ohki, K. Hayashi, H. Morishita, M. Fujiwara, N. Mizuochi, Nature Communications, 10, 3766(2019).
【成果報告】[2] 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",
審査中．

－114－

2021-115
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

A

AXILLARY

B

Me

C

O

A

GROWTH1 (CYP711A). We previously identified methyl esterified

4-deoxyorobanchol(4DO)

derivative of CLA, methylcarlactonoate (MeCLA) in Arabidopsis,and found that MeCLA can interact with the Arabidopsis SL receptor

O

O

D

O

D

O

methylcarlactonoate（MeCLA）

canonical-SL＝ABCD 4-ringprotein, 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,aO

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 convert 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 possesses only 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 thiscollaborating project with Prof. Shinjiro Yamaguchi in ICR, Kyoto University, we planned to clarify the
biological role of non-canonical SL by chemical and genetic approach.
【Results】Using an important crop, tomato, we have successfully identified a CLAMT candidate by abiochemical analysis. Now we are preparing the tomato clamt knockout mutants using CRISPR-CAS9
technology. In parallel with the genetic analysis, we decided to explore chemical inhibitors for CLAMT. We
aimed to prepare some structural analogs of the CLAMT substrate, CLA, and we have synthesized two analogs(Fig. 2). One of these two analogs (CLA analog2) lacks the methyl group in the butanolide D-ring, which wasdemonstrated to be an important part for the SL activity. We found that CLAMT could accept this analog as a
substrate. We expect that the methylation product of

HO

O

HO

O

this analog does not have the SL activity. Thus,O

although this analog is not a simple inhibitor for
CLA

CLAMT, this analog may function as a functional
inhibitor when applied to plant.

O

O

O

CLA analog1

OO

CLA analog2

Fig. 2, Chemical structures of CLA and its synthetic analogs.

－115－2021-116
光励起に伴うシクロパラフェニレン酸化体の芳香族性・反芳香族性のスイッチング
藤塚守 大阪大学

ベンゼン環オリゴマーであるパラフェニレンが環状構造になっているシクロパラフ
ェニレン(CPP)は、高い歪みと環状に整列した p 軌道に由来する物性が関心を集めており、その機能評価が近年進められている。われわれは、化学研究所の山子教授のグループと CPP 類の励起状態およびラジカルイオン状態などに関する共同研究を展開し、種々の知見を報告してきた。近年、山子グループは CPP 内にエチニル基を導入した化合物(Fig.)の合成に成功し、諸物性ならびに酸化挙動を報告している。1) 本研究では種々の時間分解分光法を適用し、当該化合物の励起状態物性の検討を行った。
本化合物の蛍光物性を Table に示す。エチニル基が 1 個 2 個のいずれの場合においても蛍光量子収率(f)がベンゼン環とともに増加する傾向はエチニル基を含まない CPPと同様であるが、エチニル基を 2 個含む場合には 1 個のものよりf が小さくなることが示されている。蛍光寿命
も短寿命化が確認されたが、輻射速度(kr)にはエチ
ニル基の数により顕著な差がみられなかったこと
より、項間交差および内部
転換速度がエチニル基の数により依存することが示唆された。これらに関し
過渡吸収測定により検討を進める予定である。

Fig. Molecular structures of CPPs in this study.

Table. Fluorescence quantum yield (f), lifetime (f) and radiative rate (kr) of CPPs.
em / nm a,b
f a,bf / 10-9 s
kr / 108 s-1 b
in THFin CH2Cl2(ene)[6]CPP
520
1.44
2.14
(ene)[8]CPP
483
0.59
2.01
2.72
2.17
(ene)[10]CPP
462
0.84
2.46
2.35
3.57
(ene)2[4]CPP
1.10
0.93
(ene)2[6]CPP
409, 424
0.25
0.89
0.79
3.16
(ene)2[8]CPP
419, 434
0.36
1.11
0.90
4.00
a
b
From ref. 1. in CH2Cl2【文献】(1) T. Terabayashi, E. Kayahara, Y. Mizuhata, N. Tokitoh, T. Nishinaga, T. Kato, S.
Yamago ChemRxiv DOI: 10.26434/chemrxiv.14547384.v1－116－2021-117
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 µm 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を生成するとともに、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。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、上述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上述の仮説を検証することを目的とする。
【得られた成果】(1)高アスペクト比のロッドターゲットの作製：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用いて、京大ナノハブ拠点において、厚さ 500 m のシリコンウエハ（基板）上に、直径がサブm で間隔がm オーダの円柱状ケイ素が多数配列したターゲット（ロッドターゲット）を作製した。京大化研
T6 レーザーを用いた照射実験(2019 年 11 月実施)では、ロッドの高さが 5 m 程度と T6 レーザーのレイリー
長 20 m と比較して小さく、レーザーと基板との相互作用が支配的である可能性があった。そこで本年度は、エッチングパラメータを調整することで、高アスペクト比(高さ/半径~50-100)のロッドの作製に成功した(図 1)。
2021 年 9 月には作製したロッドを用いた照射実験を実施し、電子エネルギーに関するデータを取得した。
(2)アライメントのための新奇ターゲットの開発：ロッドに対する正確な照射実験を実施するため、図 1 に示すようなターゲットを開発した。
具体的には、T6 レーザー集光時のスポット径(3-4 m 程度)を正確に同定するため、ロッド周辺に数m オーダの様々なサイズの円柱と角柱を設置した。また、照射位置を厳密に決定するため、ロッド集合体
から正確な距離に鋭利なくさび型の構造物を設計・配置した。加えて、高性能のデジタルカメラと、従来のレンズと比較して収差の少ない顕微鏡用高倍率対物レンズを導入し、無限遠光学系によるロッド
集合体の観察手法を確立した。
(3)実験システムの構築：ロッドターゲットは、質量を保った場合に半径を変化させることで表面積が自在に調節可能であり、レーザーとの相互作

図 1 レーザー照射実験におけるアライメントへの利用を想定した
ターゲット（SEM 画像）。

用において元の形状を保持したまま「バルク」としてのプラズマが生成することを粒子シミュレーションにより見いだしている。我々は、プラズマの２方向（ロッド軸方向／ロッド側面方向）からの電子温度の同時測定を目的として、拠点予算の援助を得て、京大化研の電子スペクトルメータ(ESM)と同一の性能を有する ESM を製作した。また、プラズマの干渉計測と磁場計測を目的として、チャンバー内において光学機器、観察用モニ
ターの配置の検討を行っている。2021 年度で構築した実験体制を踏まえ、2022 年度ではレーザー照射実験を実施し、プラズマの２方向電子温度および電子密度を測定し、３次元粒子シミュレーション結果との比
較・検証を行う予定である。
参考文献：松井隆太郎, 上田永樹，太田雅人，福田祐仁, 坂和洋一，岸本泰明、「高強度レーザーと波長オーダの構造性ターゲットとの非線形相互作用特性」、日本物理学会 2021 年秋季大会、
2021.9.20、online－117－2021-118
Coupling of concentration fluctuation and orientation fluctuationin mixture of nematic liquid crystal and solvent
Ryoko ShimadaJapan Women’s University

In a mixture of a liquid-crystalline (LC)-forming material and an ordinary (non-LC) material, thevolume fraction  and the orientational order parameter Q of the LC molecules serve as the orderparameters that may couple with each other to affect the static (thermodynamic) and dynamic(rheological) properties of the mixture. Utilizing 4-cyano-4’-pentylbiphenyl (5CB) and dimethyl
phthalate (DMP) as the LC and ordinary materials, this study examined the dielectric relaxation andviscosity of a DMP/5CB mixture in an isotropic one-phase state. The phase diagram reflecting thethermodynamics in the mixtures of various DMP content wDMP was well described by a simple model offree energy contributed from the Flory-Huggins type mixing entropy (no enthalpic contribution) and theLandau-de Gennes type nematic interaction.
For the mixture with wDMP = 3.1 wt% in a high-T asymptote (T > TIN+10C with TIN 27.0C being theisotropic-to-nematic transition temperature of the mixture), the dielectric relaxation time was close tothat of pure 5CB, as noted in Fig.1(a); compare red and green symbols at high T. This result suggests no
significant effect of the above coupling on the 5CB dynamics in the mixture at such high T. Nevertheless,in a significantly wide pre-transition zone of T between TIN and TIN+10C,  of the isotropic one-phasemixture increased on cooling much more significantly compared to  in that high-T asymptote. The
kinematic viscosity  of the mixture exhibited aqualitatively similar but quantitatively weaker increase inthat pre-transition zone, as noted in Fig.1(b).
This difference between the dielectric  and therheological  can be attributed to coupling of the orientationand the composition fluctuations mentioned above. Namely,
the composition fluctuation governs , and also enhances
the orientation fluctuation in the mixture thereby providing (reflecting the orientation fluctuation) with an extra
increase. Pure 5CB exhibited similar increases of  and ,
being stronger for the former, but only in a close vicinity of
its TIN (within 2-3C), because pure 5CB exhibits nocomposition fluctuation and the orientation fluctuation iscoupled only with the density fluctuation. This behavior ofpure 5CB in turn suggests an importance of the coupling of
the orientation and composition fluctuations in the
DMP/5CB mixture.
Publication: R. Shimada, O. Urakawa, T. Inoue andH. Watanabe, Soft Matter, 17, 6259-6272 (2021).

－118－

Fig. 1 Temperature dependence of (a) dielectricrelaxation time and (b) kinematic viscosity of
5CB and DMP/5CB mixture (wDMP = 3.1 wt%).

2021-119（国際）Determine the three-dimensional structure of 13C labeled α-synuclein(61-95)
in the Langmuir-Blodgett film and supported phospholipids bilayers by
p-MAIRS FT-IR
Chengshan 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－119－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 amethod for membrane proteins in monolayer structure with residue resolution by pMAIRS, which
will be a supplement to X-ray crystallography and NMR.
E. Publication.
All the results in Figure 1 have been presented in conference SciX 2021. In addition, one paper
about Figure 1 is in preparation for the submission to Chemistry A European Journal.
－120－

2021-120（国際）Modulation of in-cell protein-protein interactions using mid-sized peptides
Yoshio Hayashi Tokyo University of Pharmacy and Life Sciences
Protein-protein interactions (PPIs) are difficult targets for typical small molecule ligands.
Mimicking folded domains of proteins, we can modulate the function of a particular protein withmetabolically stable synthetic molecules. Therefore, strategies for developing structured midsized peptides that display protein-like functionality are highly demanded in drug discovery. This
project aims to invite three world-wildly prominent professors in chemical biology and medicinal
chemistry to discuss the scope and limitation of current strategies in development of structured
mid-sized peptides targeting PPIs. The applicant was the organizer of The 58th Japanese Peptide
Symposium (JPS), which was originally scheduled to be held in Hachioji on Oct 20-22, 2021
(Figure 1). Although it is a domestic meeting, all the presentations are made in English every
year to facilitate the participationfrom abroad. The world-wide
prominent professors in thisresearchfield,

includingprofessors Paramjit S. Arora(New York University), Ronald T.
Raines (Massachusetts Instituteof Technology),

MichaelD.

Burkart (University of California,
San Diego) were nominated as
the Invited speakers at the 58th
JPS (Figure 2). Supported by theinternational

Joint

Usage/Research Center (iJURC),
Institute for Chemical Research(ICR), Kyoto University, these
professors were also supposed tomake lectures at Institute for
ChemicalResearch,

Kyoto

University. However, due to theprevalence of COVID-19, we had
to give up on inviting these

Figure 1. The poster of The 58th Japanese Peptide Symposium－121－speakers to the symposium and to
Kyoto as well and to hold the meeting
via internet (Figure 3). We were
happy to know that Professors Arora
and Burkart agreed to make invited
talk at the 58th JPS (unfortunately,schedule of Professor Rains did not
permit his participation), under thetitles of “A Sos proteomimetic as a
Pan-Ras inhibitor” and “Directing
biosynthesis

in

type

II

NRPS

Figure 2. Invited lectures from abroad.

pathways”, respectively. The threeday

symposium

was

held

as

scheduled. Even though held as a
web-based meeting, we had 51 oralpresentations including 7 invited
talks from abroad and 4 award talks
together

with

125

posterpresentations. Total numbers ofparticipants were 395 which included
23 participants from abroad and 152
students. The applicant finally thanks
to iJURC-ICR to give an opportunity
to invite these professors to TUPLS,
and ICR Kyoto University although

Figure 3. The website of The 58th JPS.

we were not able to make it due to the COVID-19 affairs. The applicant wish to have anotherchance to invite the above professors to TUPLS and ICR Kyoto University, Japan to have faceto-face discussion.

－122－2021-121（国際）Rheology symposium at ICR
Instead of the 16th International Workshop for East Asian Young Rheologists
Tadashi Inoue

Osaka University【Purpose of project】The ICR budget was initially proposed to organize the 16 International
Workshop on Young Rheologists in East Asia (IWEAYR-16, Thailand). Unfortunately,
COVID-19 prevents having the workshop on site. This workshop aims to promoteinternational exchange among young faculty and graduate students in cooperation withresearchers from various countries in East Asia in several research fields such as polymer
science and materials science. The workshop has contributed to deepen our research activity
and formed the basis for future cooperation. Prof. Watanabe (ICR, Kyoto University)
launched this workshop as a core member. Considering his retirement in 2022, we decided tohave an alternative symposium at ICR to share the new research results and discuss the future
plane of IWEAYR with COVID-19. The symposium was organized by Japanese members of
IWEAYR.
【Place and schedule of workshop】We had a special rheology symposium with seven invited
speakers. The symposium was held from Dec 17, 2021, including the business meeting after
the symposium.
【Purpose of the symposium】The purpose of IWEAYR is to promote international exchange
and collaboration among young faculties and graduate students who will be the main
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.
The alternative symposium was designed to provide an opportunity for participants to share
the new research results and exchange research ideas in an amiable atmosphere.
【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 (January2011), Beijing (February 2012), Phuket (January-February 2013), Seoul (February 2014),
Fukuoka (February 2015), Shenzhen (January 2016), Pattaya (February 2017), Jeju Island(January 2018), Nagoya (January 2019) (in a circulating order of Korea, Japan, China, andThailand).
【Participants】The number of participants in this rheology symposium was over 40. The
main participants were:Hiroshi Watanabe, Professor,
Kyoto University
Japan
Yumi Matsumiya, Asso. Professor,
Kyoto University
Japan
Takeshi Sato, Assi. Professor,
Kyoto University
Japan
Mikihito Takenaka, Professor,
Kyoto University
Japan
Yoshinobu Tsujii, Professor,
Kyoto University
Japan
Takashi Taniguchi, Asso. Professor,
Kyoto University
Japan
Kenji Urayama, Professor,
Kyoto Institute of Technology
Japan

－123－

Shinichi Sakurai, Professor,
Yuichi Masubuchi, Professor,
Takashi Uneyama Asso. Professor,
Junichi Takimoto, Professor,
Satish K. Sukumaran, Asso. Professor,
Takamasa Sakai, Professor,
Naoyuki Sakumichi, Project Lecturer,
Takuya Katashima, Project Lecturer,
Osamu Urakawa, Asso. Professor,
Tadashi Inoue, Professor,

Kyoto Institute of Technology
Nagoya University
Nagoya University
Yamagata University
Yamagata University
University of Tokyo
University of Tokyo
University of Tokyo
Osaka University
Osaka University

Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan

Snap shots of the symposium.

【Overview of the symposium】After welcome address by Professor Watanabe, the author
provided a topic concerning on “Relationship between molecular structure and entanglement.”
Professor Urakawa presented his recent results on “Dynamics of polymer systems with specificinteractions.” After a short break, Professor Uneyama introduced his study on “Static andDynamic Shielding Effects of Interaction in Interacting Dumbbell Systems.” Professor
Takimoto presented his results on “Simulation study of the high-speed flow of entanglementfree polymers.”
Young Professors Katashima and Sakumichi respectively talked about “Dynamic oftransient networks” and “Negative energetic elasticity of hydrogels.” Professor Masubuchi
showed “Relationship between Strength of Tetra-PEG Gel and Molecular Weight Distributionof Prepolymer Studied by Simulation.” Finally, Professor Urayama presented his study on“Crack characterization of elastomers in biaxial elongation field.”【Summary】 Throughout the symposium, the discussion was very active. The professors
gave all presentations, and the scientific level of each presentation was quite high and exciting.
This symposium gave us a new trend in rheology and polymer science. The high-density
collaboration among researchers is essential for the policy and direction of IWEAYR in the
coming years. We appreciate the financial support from ICR. I would like to finish thisreport hoping to have IWEAYR-16 on-site in Udon Thani, Thailand in next year.

－124－

12/17 (Fir) Rheology symposium@Uji Obaku Plaza, Seminar rooms 1＆2

12:50-13:30
13:30-14:00(Uji Campus, Kyoto University)

Chair: Hiroshi Watanabe (Kyoto Univ.)
Relationship between molecular structure and entanglement.
Tadashi Inoue (Osaka Univ.)
Dynamics of polymer systems with specific interactions.
Osamu Urakawa (Osaka Univ.)

Break

14:20-14:50

14:50-15:20

Chair: Takuya Katashima (Tokyo Univ.)
Static and Dynamic Shielding Effects of Interaction in Interacting Dumbbell
Systems.
Takashi Uneyama (Nagoya Univ.)
Simulation study of the high-speed flow of entanglement-free polymers.
Junich Takimoto(Yamagata Univ.)

Break

15:40-16:10
16:10-16:40

16:40-17:10

Chair: Sathish Sukumaran (Yamagata Univ.)
Understanding the science of dilute polymer networks
Takamasa Sakai (Univ. Tokyo)
Relationship between Strength of Tetra-PEG Gel and Molecular Weight
Distribution of Prepolymer Studied by Simulation.
Yuichi Masubuchi (Nagoya Univ.)
Crack characterization of elastomers in biaxial elongation field.
Kenji Urayama (Kyoto Institute of Technology)－125－2021-122（国際）Micro- and Nano-structural Characterization by Advanced Transmission Electron
Microscopy of Novel Functional Materials for Battery Development
Torranin Chairuangsri Chiang Mai University
Our research group in Thailand has been collaborating with researchers at the ICR including Hiroki KURATA and Mitsutaka
HARUTA in micro- and nano-structural characterization by advanced transmission electron microscopy of novel functional
materials for battery development. The results can be summarized as follows:
I. Novel Composites as Anode in LIBs
Online experiment has been conducted on examining the novelcomposites as anode in LIBs. Ge/NrGO and SiO2-rGO were
examined using the JEM-200FC microscope for determining
distribution and characteristics of the nanocomposites. EDS
mapping of Ge/NrGO and SiO2-rGO was performed using the
JEM-ARM200F microscope including Ge, N, C, O, and Si.
Individual Ge particle sizes were in the range 5–20 nm. It wasnoticed that the good dispersion of Ge particles was observed on
the NrGO sheet because NrGO obstructed the agglomerated
matrix of nanoparticles, resulting in an increased dispersion
ability of nanoparticles. Both the separated nanostructure andFig. 1 (a) HAADF-STEM image and EDS mapping images of element
cluster morphology of GeNPs were presented in the pre-pared
distribution
corresponded to (b) C, (c) N, (d) Ge, and (e) O signals.
composites. The existence of Ge has been confirmed, which was
unableto reveal by
XRD. Polyaniline-SiO2/rGO
nanocomposites has been also examined. Polyaniline deposition on the surface of SiO2/rGO composites has been confirmed.
It is anticipated that its distinct structure will improve the electrochemical performance of Polyaniline-SiO2/rGO composites
as LIBs anodes.

Fig. 2 Power density versus loaded current density of
Zn-Mg anodes from the single-cell test.

II. Novel Zn-Mg Alloys as Anode in Metal-Air Batteries
Experiment in Thailand has been conducted and TEM/STEM experiment
at ICR is on arranging. Zn-Mg alloys containing Mg up to 5.0 wt.% havebeen prepared. SEM revealed that the microstructure of hypoeutectic
compositions (0.1, 0.5 and 1.0 wt.%Mg) contained Zn-rich primary phase.
The composition close to the eutectic point (3.0 wt.% Mg) has almost fully
eutectic structure consisting of Mg2Zn11 and Zn-rich phase. The
hypereutectic composition (5.0 wt.%Mg) had a primary phase of
Mg2Zn11/MgZn2. Potentiodynamic polarization testing in 6 M KOH has
been conduced and the single-cell test using MnO2 as the air catalyst has
been performed. The assembly had an open circuit voltage of 1.4 V andthe alloys with small Mg content up to 1.0 wt.% showed better
electrochemical performance as anode as compared to pure Zn.

III. Novel Manganese-containing Phosphate Glasses as Cathode in LIBs
Experiment in Thailand has been conducted and TEM/STEM experiment at ICR is on arranging. Structural and local chemical
analyses of manganese-lithium-phosphate glasses containing MnO 10-30 mol.% were studied. XRD pattern of the samples
showed the containing of some crystalline phase(s). The highest amount of crystalline phase(s) was found in sample withhighest MnO containing. It seems likely that Mn ions play an important role on the structural changing, oxidation states of
Mn itself and electrochemical property. FTIR, shows the changes in bonding between P-O in the samples as MnO containing
increases. Moreover, EXAFS also shows the different in Mn environment as MnO containing changes as two environments
was detected. Sample with highest MnO (30 mol%) possess highest specific capacitance.
One paper has been published [Autthawong, T.; Promanan, T.; Chayasombat, B.; Yu, A.-S.; Uosaki, K.; Yamaguchi, A.; Kurata, H.; Chairuangsri,

T.; Sarakonsri, T. Facile Synthesis Sandwich-Structured Ge/NrGO Nanocomposite as Anodes for High-Performance Lithium-Ion Batteries. Crystals. 2021.
https://doi.org/10.3390/cryst11121582] and other two manuscripts are being prepared.

－126－2021-123（国際）－127－2021-124（国際）High-pressure synthesis of potential multiferroic oxides
Kunlang Ji University of Edinburgh
Objectives: High pressure-high temperature (HPHT) synthesis is used to stabilise unusual
oxidation states and coordination environments in transition metal oxides, resulting in interesting
physical properties. In collaboration with Professor Shimakawa in ICR at Kyoto University, aunique high-pressure multianvil apparatus which reaches up to 20 GPa and 2273 K is available touse. This equipment provides a good opportunity for synthesize the double corundum/perovskite
with small tolerance factor and develop their potential multiferroics.
Experimental methods: Due to the Covid-19 special circumstance, we developed ourcollaboration by communicating e-mails. We focus on writing paper of the new double corundum
Co2InSbO6 synthesized at Kyoto University during early 2020, while Professor Shimakawa
providing very useful scientific guidance for the paper through emails.
Experimental results: 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 theordered-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 initialordered-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. Amano Patino, Y. Shimakawa and J. Paul Attfield, A
new cation-ordered structure type with multiple thermal redistributions in Co2InSbO6, in
preparation.

－128－2021-125（国際）Synthesis and Characterization of Novel Group 16 Element Compouds
Mao Minoura Rikkyo University
In the field of organoselenium and organotellurium compounds, their synthesis,
structural analysis, and reactivity have recently attracted a great deal of research interest not
only in chemistry but also in biological applications.1) It is generally known that P=P and
Sb=Sb double bond compounds are highly reactive species and such double bond compounds
can easily dimerize. The use of bulky protecting groups enables the synthesis and isolation ofsuch double bond compounds, Tokitoh et al. reported the synthesis of those P=P and Sb=Sb
double bond compounds with a large aromatic Tbt group. However, in the case ofalkyl-substituted species, stable Sb=Sb double bond compounds have not been reported due tothe difficulty of ligand design. In recent years, our group has designed and synthesized novel
triptycene (Trp)-based aliphatic bulky groups, i.e., Trp* with bulky fused-ring-type substituentsaround the periphery of the Trp skeleton. In this study, we have synthesized thermally stable
Trp*2P2 and Trp*2Sb2 and investigated the reactivity of these double bonded compounds withselenium and tellurium.
The Trp*2P2 and Trp*2Sb2 were synthesized by the reductive coupling reaction of thecorresponding dichlorides, Trp*PCl2 and Trp*SbCl2, with alkali metal, respectively. The
isolated Trp*2P2 and Trp*2Sb2 are thermally very stable and moisture sensitive, the molecular
structures were determined by X-ray crystallographic analysis.2)
We thank Professors Norihiro Tokitoh, Yoshiyuki Mizuhata, Mariko Yukimoto (ICR,
Kyoto University) and Professor David G. Churchill (KAIST, Korea) for their helpful discussions.

1) David G. Churchill et al. Molecules, 2021, 26, 692. doi:10.3390/molecules26030692
2) Mao Minoura et al. Bull. Chem. Soc. Jpn., 2021, 94, 2919. doi:10.1246/bcsj.20210350－129－2021-126
固体 NMR を駆使した有機結晶および有機薄膜の分析
家裕隆 大阪大学

π共役系有機分子を有機半導体材料に用いた、有機 EL,有機太陽電池等の有機エレクトロニクス研究が盛んに行われている。これらのデバイスでは、有機半導体材料の薄膜を活性層がその特性に大きな影響を与えることから、原子間力顕微鏡による表面
モルフォロジー、粉末 X 線構造解析による分子配列評価を中心とする薄膜解析が行われている。しかし、有機薄膜では、分子の固体状態で様々な集合状態、すなわち、結晶、非晶、結晶―非晶混合状態をとるため、これらの解析手法では、分子レベルの情報を得ることが困難である。一方、固体 NMR を用いた薄膜分析は、有機非晶性膜の局所構造、ダイナミクス解析が可能であることから、有機エレクトロニクス素子開発において、極めて重要な測定技術である。しかし、現状では研究例は極めて少ない状況である。NMR 測定において 19F 核は天然存在比が高く、高感度な核種であることか
ら、含フッ素材料を用いることで 19F 核をプローブとした高感度分析の実現が期待できる。そこで、本研究では我々が見出した含フッ素キノイド構造のアクセプター分子（FTQ2）とドナー性分子（TIPS-p）を混合して得られる結晶あるいは非晶性膜を作製し、固体 19F NMR 測定を行うことで、分子レベルの相分離構造、分子コンフォメーシ
ョン、分子運動性を解明し、有機太陽電池の高効率化に繋がる学術的知見を得ることを目的とした研究を行った。
これまでに FTQ2 と TIPS-p の 2:1 混合比のクロロホルム溶液からドロップキャスト法で薄膜作製すると結晶性薄膜が得られることを見出している。そこで、薄膜作製条
件の違いによる結晶構造の調節を目的として、より TIPS-p と親和性の高いトルエン溶
媒で薄膜作製を行った。XRD 測定の結果、クロロホルム溶媒の時とは異なる結晶系となることが明らかとなった。さらに、ドロップ
キャストの温度を 65度まで上昇させること
で、結晶性が変化することも明らかとなった。京都大学化学研究
所の梶・鈴木グループ
でこれら薄膜の固体
19

F NMR 測定の測定・解析を進めている。

－130－2021-127
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

核融合炉発電の実現には，高性能プラズマの安定維持に加え，それを取り囲む材料との相互作用を正確に把握する必要がある．特に，プラズマ対向材料中の水素同位体およびヘリウムの挙動の理解は，プラズマ制御および材料の健全性に関わる極めて重要な課題である．本研究では，昨年度に引き続き，国際熱核融合実験炉(ITER)のプラズマ対向材料に利用が予定されているベリリウムを対象として，バブル内のヘリウムの定量化を試み，さらにその形状や温度依存性について評価した．
図には，室温で 3keV-He+を 1x1021 /m2 照射後，673 K で焼鈍したベリリウム試料内部に観察された(a)ヘリウムバブルの高角度散乱円環暗視野(HAADF)像，(b)ベリリウムの母相と形状の異なる 2 つのバブルの中心部から得られた EELS スペクトルを示した．図(b)に見られるように，バブル中心から得られた EELS スペクトルには，22 eV 付近にヘリウム原子のK-edge に起因する電子線エネルギー損失ピークが観察され，バブル内にヘリウムが存在していることが確認できる．さらに，サイズが同程度(d~40 nm)で，形状の異なるバブルから得られたエネルギー損失ピークの強度は，真円度が高いほど大きい傾向が見られた．図(c)には，EELS 面分析から得られたピーク強度分布からヘリウム密度分布を算出した
結果を示しているが，真円度(R)が高いバ
ブル(R~0.93)では，晶癖面を有するバブル(R~0.63)と比較して 2 倍程度の圧力差があることが明らかになった．さらに，同様の試料を 1073 K 程度まで TEM 内で加熱し，その場観察したところ，バブルの移動度に大きな違いがみられ，球状に近い高圧なバブルほど高い移動度を有する
ことが定量的に示された．バブルの移動
度は，照射材料において問題となるボイ
ドスウェリング(体積膨張)に影響を与える一因となることから，本研究で得られた成果は，プラズマ対向材料の寿命評価
や使用条件の提案においても有意義な知図 ヘリウムイオン照射したベリリウム試料の(a)HAADF 像，(b)ベリリウムの母相と形状の異なる 2 つのバブルの中心部から得られた EELS ス
ペクトル，および(c)ヘリウム密度分布像．

見となる．
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），杉本有隆，原一智（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，2021 年
10 月に開催された核融合炉材料国際会議 ICFRM-20 にて 2 件の報告を行った．
－131－

2021-128
希土類共ドープナノ粒子の寿命制御
斉藤光 九州大学

希土類イオンを発光中心とした酸化物蛍光体は熱的・化学的安定性が高いことから照明器具や蛍光センサ、検出器など多くの分野で応用されている。このタイプの蛍光体の高輝度化には、固溶限内で希土類イオンの添加量を増やしつつも、母体中に均一に分散させることが重要であることが報告されている[G. Dosoviskiy et al., J. Lumin.,236, (2021), 118140.]。本研究では、優れた特性を示す酸化物蛍光体の一つである、セリ
ウムを発光中心としたイットリウム・アルミニウム・ガーネット（Ce:YAG）の発光効率向上を目的とし、Ce を高濃度かつ均一に分散させる合成条件について検討した。
純水とエタノールの混合液中に AlCl3・6H2O、YCl3・6H2O、CeCl3・7H2O、およびポ
リビニルピロリドンを添加して攪拌した。次いで、酸化プロピレンを加えて 2 分攪拌
した後、30 分静置した。このゾル溶液をアルミナボートに移し、ホットプレート上で80 ℃、200 ℃、300 ℃の各温度で 30 分ずつ段階的に加熱し、電気炉内において 1150 ℃
で 2 時間焼成することで成生物を得た。また、ゾル溶液調製の際、Ce 添加量を Y に対して① 2.0 mol%、② 4.0 mol%、③ 8.0 mol%と変調した。成生物の Ce 含有量・分布を走査透過電子顕微鏡-エネルギー分散型 X 線分光（STEM-EDS）により評価するとともにフォトルミネセンス（PL）測定により、それぞれの試料の蛍光特性を評価した。
STEM 観察により、得られた生成物はどれも数 10 nm の大きさの YAG の結晶である
ことがわかった。また、Fig. 1 に示すように、どの試料からも Ce:YAG 由来の 575 nmを中心とした幅広い PL ピークが確認された。YAG 中の Ce 量と分布を STEM-EDS で評価したところ、①、②では YAG 中に Ce が均一に分布しており、③では Ce の偏析が確認された（Fig.2）。Fig.2 の視野全体における、Y に対する Ce 含有量はそれぞれ① 2.3
mol%、② 4.2 mol%、③ 9.4 mol%であり、③において Ce 偏析が確認されない Area 1 の領域では 3.9%であった。したがって、YAG 中に固溶できる Y に対する Ce の最大濃度は、4 mol%程度であることが示唆され、Ce を高濃度かつ均質に分散させるという観点から当該条件が Ce:YAG の発光効率を最大化すると考えられる。

Fig. 1 Normalized PL spectra of
Ce:YAG nanoparticles.

Fig. 2 EDS maps of Ce:YAG nanoparticles superimposed to their HAADFSTEM images.

－132－2021-129
単結晶 X 線構造解析を用いた、含フッ素共役分子の結晶構造におけるフルオラス相互作用の解明
吾郷友宏

茨城大学

フッ素置換基は化合物の電子受容能の向上や凝集状態での分子配列制御に寄与するが、フッ素置換基の構造と分子間相互作用の関係に未解明の点が多く、有機材料の凝集構造制御にフルオラス相互作用を積極的に活用するまでに至っていない。例えば、
平面π共役分子は有機半導体の重要な構造モチーフであるが、単結晶 X 線構造解析が困難であることが多く、含フッ素共役分子におけるフルオラス相互作用の実験的知見はほとんど無い。本研究では、化学研究所の極微小結晶用 X 線単結晶 X 線構造解析装置である VariMax を用いて、フッ素置換基を導入したπ共役分子の凝集構造制御に有効なフッ素置換基の構造を明確化する。また、昨年度から環境適合の含フッ素有機材料の開発に着手しており、VariMax を用いたミクロ構造解析も実施している。
本年度の研究では、COP9 で廃絶対象物質に追加された長鎖フッ素置換基に代わる、環境負荷が低い新規フッ素置換基の開発を検討した。具体的には、ペルフルオロアル
キレンユニットがビニレンユニットで架橋された構造のフッ素置換基であり、COP9で指定された長鎖ペルフルオロアルキル基と異なりペルフルオロオクタン酸（PFOA）
等の生物濃縮性物質は生じない一方、長鎖フッ素置換基に期待される撥水・撥油性や耐熱性などの物性は維持できると考えられる。昨年度の検討では、本フッ素置換基を側鎖としたポリ(メタ)アクリレート樹脂を合成し、既存の長鎖フッ素置換基を持つ類縁樹脂と同等の耐熱性、撥水・撥油性を持つことを明らかにしている。今年度は本フッ素置換基のさらなる応用として、本フッ素置換基を導入したホスホン酸型表面処理剤
を合成し、ガラス及び SUS 基盤の表面処理機能を検討した。開発した表面処理剤は、
PFOA 発生源となる長鎖ペルフルオロアルキル基を持つ既存のホスホン酸型表面処理剤と同等の撥水・撥油性、耐熱性を持つだけでなく、SUS 基盤の表面処理速度が飛躍的に向上していることも見出した。今後は、本フッ素置換基を導入した含フッ素共役分子を合成し、単結晶 X 線構造解析によるフルオラス相互作用評価を実施する。

【成果報告】Shirai, T.; Yamauchi, S.; Kikuchi, H.; Fukumoto, H.; Tsukada, H.;
Agou, T. Applied Surface Science 2022, 577, 151959.
－133－

2021-130
Synthesis and Structural Characterization of Halostannylenes
Tsukasa Matsuo

Kindai University

In this collaborative research, we examined the synthesis and structures of aseries of halogen-substituted divalent tin compounds, halostannylenes, (Rind)XSn:,
by virtue of the steric effects of the fused-ring bulky Rind group (Rind =1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl).
As shown in Scheme 1, the bulkier MPind-based bromostannylene,(MPind)BrSn: (1), was obtained by the reaction of SnBr2ꞏdioxane with anequimolar amount of (MPind)Li in THF, similar to the synthesis of the bulky
Eind-based bromostannylene, (Eind)BrSn: (2). In contrast, the less bulky
EMind-based halostannylenes, (EMind)BrSn: (3), and (EMind)ClSn: (4), wereobtained by the ligand redistribution between the diarylstannylene, (EMind)2Sn: (5),and SnX2ꞏdioxane (X = Br and Cl) in toluene.
A series of arylhalostannylenes 1–4 were isolated asthermally stable orange crystals. and their structures wereconfirmed by X-ray crystallography. While the monomeric
structure was found for the bulkier MPind-based 1, the lessbulky EMind-based 4 exhibits a unique one-dimensional
polymer with alternating Sn and Cl atoms.

Scheme 1. Synthesis of 1 and 4.

－134－

2021-131
Theoretical design of planar silicene nanoribbons
and search for new operating principles
Masae Takahashi Tohoku University【Objectives】The emergence of flat one- and two-dimensional materials, such as graphene andits nanoribbons, has promoted the rapid advance of the current nanotechnology. Silicene, asilicon analogue of graphene, has the great advantage of its compatibility with the present
industrial processes based on silicon nanotechnology. The most significant issue for silicene isinstability in the air due to the nonplanar puckered (buckled) structure. Another criticalproblem is that silicene is usually synthesized by epitaxial growth on a substrate, whichstrongly affects the  conjugated system of silicene. The fabrication of free-standing silicene
with a planar configuration has long been pursued. Here, we report the strategy and design torealize the flat zigzag silicene nanoribbon.
【 Structure of Theory 】 We theoretically investigated the stability of various silicene
nanoribbons with substituents at the zigzag edges.
【Results and Discussion】We found that zigzag silicene nanoribbons with beryllium (Be)bridges (Be-bridged 2-chain ZSiNR) are very stable in a planar configuration. The obtained
zigzag silicene nanoribbon has an indirect negative band gap (Fig. 1) and is nonmagnetic
unlike the magnetic buckled silicene nanoribbons with zigzag edges. The linearly dispersive
behavior of the  andbands associated withthe out-of-plane 3psi and
2pBe orbitals is clearlyobserved, showing theexistence of a Dirac point
slightly above the Fermi
level. We also observedthat spin−orbit coupling
induces a gap opening at
the Dirac point.

Fig. 1 Electronic band structures of the band gap region of (a)Be-bridged 2-chain ZSiNR and (b) buckled silicene. The solid and【Publications】

dashed lines are the results with and without spin−orbit coupling,[1] M. Takahashi, ACS

respectively. The inset in (a) is magnification around the Dirac

Omega, 2021, 6, 12099.

point.

[2] M. Takahashi, M. Kowada, H. Matsui, et al., Appl. Phys. Lett. 2022, 120, 051104.

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2021-132
Synthesis and structures of cationic aromatics
bearing thiopyrylium units
Noriyoshi Nagahora Fukuoka University
Introduction
Thiopyrylium salts exhibit a unique electronic structure, which renders these compounds interesting
potential building blocks for sulfur-containing aromatic molecules. Recently, thiopyrylium-containing
molecules have received substantial attention due to their fascinating structures, optoelectronic andphysicochemical properties. In this work, we present studies on the synthesis of linearly fused thiopyrylium
compounds via Lewis- or Brønsted-acid-promoted intramolecular cyclization of thioethers.

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 reaction still proceeded when the pi-expanded 1-pyrenyl thioether
1b was treated with TfOH at room temperature for 2 h. This reaction afforded pyrene-fused thiopyrylium salt
2b as the sole product. These reactions demonstrate that this transformation could be used to form moleculeswith extensive pi-systems as well as molecules that contain sulfur or nitrogen heterocycles, such as 2c/2d.
Consequently, we have established the Lewis/Brønsted-acid-induced cyclization of thioethers that contain aformyl group at the 2´-position as an extremely versatile reaction that allows constructing a variety of
thiopyrylium frameworks.

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.
－136－2021-133
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
布施泰朗 京都工芸繊維大学【目的】

FT-ICR-MS は，その高い質量分解能と質量確度により，溶存有機物（Dissolved Organic

Matter：DOM）の分子組成解析においてもっとも優れた機器のひとつである．我々は，化学研究所
保有の FT-ICR-MS を用いて，琵琶湖をはじめとする自然環境下での水域や土壌における溶存有機物の分子構造の推定を行うとともに，鉄イオンなどの金属イオンと錯体形成したときの化学形態を評価する手法について検討を行い，物質循環における金属元素移送への腐植物質の役割を明らかにすることを目指している．本年度は，FT-ICR-MS による DOM の測定条件の最適化をまずおこない，将来的な高頻度分析の土台固めをすることを目的とした．
【実験】 国際腐植学会頒布の標準フルボ酸（Pony Lake Fulvic Acid：PLFA）を超純水とメタノー
ルを等量混合した溶媒に溶解させた溶液を用いて条件検討をおこなった．検討事項は以下の通り．
1 回目検討事項
TOF：0.575～0.45 秒，accumulation: 0.25～1.25 秒, 濃度：3～100mgC/L．（積算回数 100）
2 回目検討事項．
Q1 mass：150，545，TD：1～4M（試料濃度 3mgC/L，TOF0.5 秒，accumu. 0.75 秒，積算回数 200）
Accumulation：0.2～0.75（試料 3 mgC/L），0.2～0.8（試料 10 mgC/L），0.2～0.8（試料 20 mgC/L：一部 SRNOM を使用）全て TOF 0.5 秒，TD 2M，Q1 mass 150 により検討した．
【結果と考察】・第 1 回目の検討では，TOF：0.5 秒，accumulation：0.75 秒で良好なスペクトルが得られた．濃度については，6 mgC/L の時に最大ピーク強度を示し，12.5 mgC/L 以上では高 m/z 側にピークのスプ
リッティングが確認され，accumulation 0.75 秒では試料濃度が高すぎると考えられた．
・第 2 回目の検討より，Q1 mass は適正

A）accum.: 0.3sec

値の 150（観測幅の最小値）に変更した．
TD１M では分解能が足りず，4M では測
定時間がかかりすぎるため，2M とした．
accumulation：TD 2M 条件では，試料濃度 10 mgC/L までは十分な強度が得られず ． 試 料 濃 度 20 mgC/L 時 に はB）accum.: 0.5sec

accumulation 0.5 秒以上時に m/z 300 以上
でピークのスプリッティングが観測された．以上より，試料濃度 20 mgC/L，accumulation 0.2 もしくは 0.3 秒が最適であると考えられた．

Fig. FT-ICR-MS spectrum of SRNOM（left: range150-1500m/z, right: range 365.12-365.20m/z）－137－－138－

2．国際会議、シンポジウム・研究会報告

6th International TADF Workshop 実施報告書
主催：九州大学最先端有機光エレクトロニクス研究センター

共催：京都大学化学研究所

国際共同利用・共同研究拠点、公益財団法人九州先端科学技術研究所（福岡市）、公益財団法人福岡県産業・科学技術振興財団、沖縄県科学技術大学院
大学、大阪府立大学（現・大阪市立大学）、仏・ソルボンヌ大学、英・セント・アンドリュース大学、豪・クイーンズランド大学、独立行政法人日本学術振興会
日時：2021 年 12 月 9 日（木）～12 月 10 日（金）場

所：オンライン開催（実施本部、九州大学最先端有機光エレクトロニクス研究センター）
2021 年 12 月 9 日（木）～12 月 10 日（金）の 2 日間にわたり、6th International TADF

Workshop (学会ホームページ https://www.tadf.jp/)をオンライン開催した。TADF Workshop
は熱活性化遅延蛍光（TADF）及びそれに関連する有機エレクトロニクスの最新の研究成果を議論する場として、第 1 回（2013 年）が開催されて以来、2017 年より継続的に開催してきた。第６回目となる今回は、九州大学最先端有機光エレクトロニクス研究センター・安達千波矢センター長がチェアを務め、京都大学化学研究所国際共同利用・共同研究拠点、公益財団法人九州先端科学技術研究所（福岡市）、公益財団法人福岡県産業・科学技術振興財団、
沖縄県科学技術大学院大学、大阪府立大学（現・大阪市立大学）、仏・ソルボンヌ大学、英・セント・アンドリュース大学、豪・クイーンズランド大学の協力、並びに独立行政法人日本学術振興会・研究拠点形成事業（Core to Core Program））の支援を受けている。
未曾有のコロナ渦に始まったオンライン開催は昨年度に引き続き 2 回目であったが、、昨年度開催を上回る 21 カ国から総勢 250 名の参加者があった。参加国は従来の日本、アジア
周辺国に加え、ポーランドやリトアニアなど東欧からの参加が目立った。
今回は、「The cutting-edge science and technologies of TADF」、「related topics basedon charge-transfer complexes」、「new application based on organic electronics」を小テーマとして設け、幅広い研究分野をカバーした。また、「Future Organic Electronics」という題目にて有機エレクトロニクス分野をリードする 11 名の研究者による特別パネルディスカッションを行ったほか、若手研究者・大学院生交流と育成を目的としたショートプレ
ゼンテーションの場を設けた。世界の各国からのライブ参加を促進するために、日本時間の午後 15 時開始としたことにより、海外参加者のライブ参加が促進されたと考えられる。秘密保持上の問題から、各講演の録画は行わずリアルタイムの講演とし、視聴者との質疑応答に専念した。
今回の TADF Workshop では、今回の TADF Workshop では、 最先端 TADF の材料技術、また、それを用いた OLED の高性能化に関する議論が進んだ。さらに、有機 CT 状態の学理と次世代研究の方向性に関する端緒を掴むことができた。
最後に、本ワークショップ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：安達

－139－

千波矢

10th Aquatic Virus Workshop (AVW10) 実施報告書
主催：日本微生物生態学会

共催：京都大学化学研究所

協

賛：ゴードン・アンド・ベティ・ムーア財団

国際共同利用・共同研究拠点

サイモンズ財団
京都大学教育研究振興財団
日時：2021 年 6 月 27 日（日）～7 月 1 日（木）場

所：オンライン開催（実施本部、京都大学化学研究所）
2021 年 6 月 27 日（日）～7 月 1 日（木）の 4 日間にわたり、10th Aquatic Virus Workshop(AVW10, ホームページ https://www.avw10.jp/)をオンライン開催した。AVW は水圏ウイル
スに関する最新の研究成果を議論する場として、ノルウェーで第 1 回（1998 年）が開催されて以来、2～3 年毎に継続的に世界各国で開催されてきた。記念すべき第 10 回にあたる
AVW10 は、日本微生物生態学会主催、京都大学化学研究所国際共同利用・共同研究拠点共催のもと、京都大学化学研究所 緒方博之教授 を実行委員長として、京都大学、高知大学、海洋研究開発機構、筑波大学、東京工業大学、水産研究・教育機構所属の実行委員と海外の国際委員（表１）の協力を得て開催された。また、ゴードン・アンド・ベティ・ムーア財団、
サイモンズ財団、京都大学教育研究振興財団からの支援を受けた。
AVW10 では、招待講演（Featured Talk）13 題、一般公演（Live Talk）37 題、オンデマ
ンドプレゼンテーション 46 題の研究発表があった（要旨集を添付する）。演題は「Virushost interaction」、「Isolation, genome, structure」、「Infection cycle, molecularbasis」、「Ecogenomics」、「Microbial food web & biogeochemical cycle」、「Modelling」、「Evolution」の 7 つのテーマにわたり、幅広い水圏ウイルス研究分野をカバーした。また、
21 カ国から総勢 200 名の参加者を得た（表２）。従来の対面開催では 100 名程度以下の参加人数であったところ、オンライン開催により広く参加者を募ることができ、参加者からも好評であった。
今回のオンライン開催では下記の三点を含む工夫を行った。第一に、時差対応である。世界の各国からのライブ参加を促進するために、午前（9 時～12 時）、午後（3 時～6 時）、夜間（10 時～11 時）の 3 つのセッションを設けた。これにより、海外参加者のライブ参加が促進された。第二に、全てのセッションを録画配信し、時差により参加できなかったセッシ
ョンの発表を後日視聴できる仕組みを設け、参加者の利便性を図った。第三に、従来のポス
ターセッションに代わり「オンデマンドプレゼンテーション」を設けた。録画済のプレゼン
テーションを会議前から視聴できるようにし、当日の発表の場では、繰り返しの説明を行わずに、質疑応答に専念できる形式である。その他、参加ルールの説明等の文書配布を丁寧に行った。参加者からは「今までに見たことのない最高のオンライン会議であった」など、好－140－評をいただいた。
今回の AVW10 では、世界各地で得られた水圏ウイルスを巡る最新の研究成果を踏まえた議論ができた。そして、環境中でのウイルスの挙動や微生物との関係性を理解することが、生態系を根底から理解する上で必要不可欠であるとの認識が高まった。また、総会にて次回
AVW11 はカナダ主催で実施することに決定された。
最後に、本ワークショップ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たい。
文責：緒方博之

－141－

表１

AVW10 実行委員会構成員

国内
京都大学・化学研究所

緒方

博之

京都大学・化学研究所

遠藤寿

京都大学・化学研究所

岡崎友輔

産業技術総合研究所

鎌形

洋一

北海道大学

岡部

聡

京都大学・農学研究科

吉田

天士

高知大学

長崎

慶三

高知大学

高橋

廸子

海洋研究開発機構

布浦拓郎

東京工業大学

望月

智弘

筑波大学

浦山

俊一

国立研究開発法人水産研究・教育機構

外丸

裕司

海外
University of Bergen, Norway

Gunnar Bratbak

Royal Netherlands Institute for Sea

Corina Brussaard

Research/University of Amsterdam, The
Netherlands
University of Nebraska-Lincoln, US

David Dunigan

Max Planck Institute, Germany

Matthias Fischer

Technion-Israel Institute of

Debbie Lindell

Technology, Israel
University of Toronto, Canada

Steven Short

University of British Columbia, Canada

Curtis Suttle

Georgia Institute of Technology, US

Joshua S. Weitz

－142－

表２

AVW10 参加国

国

参加者数

日本

56

米国

54

イスラエル

15

カナダ

13

ドイツ

10

ノルウェー

9

フランス

9

オランダ

6

中国

6

メキシコ

5

スウェーデン

4

英国

2

スペイン

2

ブラジル

2

シンガポール

1

パナマ

1

インド

1

フィンランド

1

エジプト

1

デンマーク

1

オーストラリア1－143－

付録１ 国際共同利用・共同研究拠点からの支出
項目

金額（円）

ミーティングポータル作成費

396,900

Zoom オンライン開催サポート

482,218

合計

878,218

付録２ オンライン会議風景－144－

第 5 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：2021 年 11 月 19 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，

分子配向制御の先駆者に敬意を表して

日本分光学会・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 5－（久保野 敦史・静岡大）
2.

回を，京大化研の国際共共拠点を支援により，対面とオンラインのハイブリッド方式で実有機半導体の塗布変換成膜における分子配向制御（鈴木 充朗・阪大）

3.

キラルな低分子量ゲル化剤の分子配向施した．昨年は，コロナ禍の行く末がまったの研究：フィブリール形成におけるパー

く見えず，あえなく中止としたが，今回は状フルオロ基の特異性（佐藤 久子・愛媛

況の改善が見込めたため，講師の方々の交流

大）にとって重要な対面式を含む方式とした．一4.

有機薄膜の分子配向形成に関わるエネ方，コロナ終息後もオンライン参加のメリッルギー障壁（永井さえ・ソニーグループ

トは残ることを考え，今後ハイブリッド方式(株) R&D センター）

がスタンダードになる可能性を視野に入れ

5.

テトラピリジルポルフィリンの超分子て，試しに運用してみることにした．その結構造を利用した分子配向制御（冨田 和果，対面に 24 名，オンラインで 47 名で合計

孝・京都大 D3）

71 名の参加者を得た．学生の参加者が 22 名

6.

Ph-BTBT-Cn の製膜温度を利用した分子配向制御（吉田 茉莉子・京都大 M2）と，若手の参加者も多かった．
今年は日本化学会，日本分析化学会，分7.

子科学会，応用物理学会の 4 学協会の協賛を

MAIRS2 による極低温の真空蒸着薄膜のその場構造解析（羽馬 哲也・東大）

得て実施し，これら協賛学会からの参加者は分光学会員と同額の参加費とした．また，コロナ禍での出費の厳しさも勘案して例年より低価格に設定し，学生は例年通り無料とした．
ハイブリッド開催をスムーズに実現するため，専門業者にマイクなどの設定を任せた
ことが功を奏し，非常に順調なハイブリッド
はじめに，基調講演枠で久保野先生によ開催が実現した．
5 回目の今回は“第 5 回 MAIRS ワークシる分子配向制御の重要性について，その歴史

ョップ｜MAIRS で進める薄膜工学”としてを含む専門家ならではの視点でお話しいた開催した。対面式の会場は京大化研で，プロ

だいた．Langmuir-Blodgett（LB）法のようなグラムは次のとおりである。

湿式法が全盛の 1980 年頃に，蒸着法による

1.

分子配向の制御を始められた上田裕清先生

有機薄膜における高次構造形成機構－－145－（神戸大）らの研究を紹介され，そこから熱最後の東大の羽馬哲也先生による講演は，力学的考察を経て配向制御に向かった道の宇宙の原子が分子になる過程を，宇宙に浮かりを示されて圧巻だった．本ワークショップ

ぶ塵に吸着した原子の反応として理解する

は，配向マニアが集まる場であることを意識話題である．実験室で超高真空中で疑似宇宙した，素晴らしい導入講義であった．

空間を作り，ここに MAIRS2 を組み込んで氷阪大の鈴木充朗先生は，塗布熱変換法と表面のダングリング OH 結合を定量的に解析呼ばれる，湿式で前駆体化合物を製膜した後することで，赤外線の吸光係数（吸収断面積）に，加熱により目的の薄膜を得る手法につい決定という長年の課題を初めて解決したとて，詳しく説明された．合成化学の立場から

いう革新的な内容であった．

のお話しながら，MAIRS2 および pMAIRS を

このように，今年の講演会は，MAIRS が使った配向解析の取り組みについて紹介さユーザーの手によって自由に羽ばたき，想像れ，定量解析でなければ見逃してしまうよう以上の広がりを示し始めていることを実感

な配向変化をたよりに，研究を進めている実できる内容となった．

際を熱く語っておられた．

会のスムーズな運営を可能にしてくれた，

愛媛大の佐藤久子先生は，信州大の英先生らが始められたゲル化剤に，パーフルオロ

国際共共拠点にこの場をお借りして，厚く御礼を申し上げる．

アルキル（Rf）基を導入すると，炭化水素のときとは大きく異なるゲル化の特性が現れることについてお話しされた．炭化水素では鎖長とともにゲル化能が増すのに対し，Rf基を導入すると，その鎖長の偶奇がゲル化能に反映される興味深いものである．こうした
Rf 鎖の特性を，水面上の単分子膜を用いて解析する試みも紹介され，そこで LB 膜のpMAIRS スペクトルが登場し，階層双極子アレー（SDA）理論との一致について述べられた．
ソニーグループ（旧 SONY）の永井さえ氏は，有機薄膜の成長過程を基板上分子の運動性により解明する，開拓的な取り組みを示された．ここでは，分子 1 個の動くに注目するのではなく，クラスターが水平および垂直配向のパターンに大別できると仮定し，その間のエネルギー障壁を MAIRS スペクトルから定量的に決められるというもので，物理化学的にも極めて面白い内容であった．実際，
この話題は優れた質疑が続き，大変に会場を盛り上げた．
続く 2 題は化研・長谷川グループの学生によるもので，pMAIRS を用いた実際の分子配向制御の話題が提供された．

－146－

長谷川健（分子環境解析化学研究領域）

第 42 回生体膜と薬物の相互作用シンポジウム
二木史朗 京都大学化学研究所

第 42 回生体膜と薬物の相互作用シンポジウムを、本年（2021 年）10 月 28 日（木）、29 日（金）、オンラインで開催しました（主催：日本薬学会物理系薬学部会；実行委員長：二木 史朗）。
生体膜と薬物の相互作用シンポジウムは、1976 年に第１回が開催された日本薬学会が主催する
多くのシンポジウムの中で最も長い歴史を持つシンポジウムです。細胞生物学・分子生物学に加え、薬剤学・薬物動態学の観点も交えつつ、本シンポジウムは、生体膜に関わる生命現象の解明・創薬の基礎から臨床までをカバーする学際的でユニークな成果発表・情報交換の場として発展しています。
今回のシンポジウムでは、特別講演に、アミノ酸トランスポーターとアミノ酸シグナルの生理機能や病態との関連において世界を先導する研究を展開しておられる大阪大学大学院医学系研究科の金井好克先生をお招きしました。また、シンポジウム初日には「生体膜研究の新視点」を、二日目には「膜タンパク質研究の分子的視点」の二つのミニシンポジウムを企画しました。前者では、
オートファジー、エクソソームの形態制御機構や、膜タンパク質の光操作など、生体膜に関連する最先端の研究対象や手法に関して、また、後者では、構造生物学から明らかになってきた膜タンパ
ク質・トランスポーターの姿や機能に関して、計 10 名の第一線の研究者の方から研究内容をご紹介頂きました。また、口頭発表 33 題、ポスター発表 8 題の計 41 題の一般講演も行われました。
当初は、京都大学化学研究所での実地開催を計画しておりましたが、新型コロナウイルスの蔓延状況からオンライン開催となりました。しかし、オンラインにかかわらず、124 名（うち、学生 58名）もの方に参加いただき、活発な討論が繰り広げられました。
本シンポジウム開催にあたり、生体膜に関わる分子相互作用を学際的な視点から密に討論する
シンポジウムの趣旨は、京都大学化学研究所の「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」における共同研究の輪を一層拡げるものとして、後援を頂きました。お陰様で、本シンポジウムを、盛会の裡に終了する
ことが出来ました。この場を借りて厚く御礼申し
上げます。

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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 Nat. Commun., 12, 306 (2021)

ARTICLEhttps://doi.org/10.1038/s41467-020-20561-x

OPEN

Ultra-high dynamic range quantum measurement
retaining its sensitivity

1234567890():,;

E. D. Herbschleb

1 ✉, H. Kato

2, T. Makino2, S. Yamasaki2,3 & N. Mizuochi

1✉

Quantum sensors are highly sensitive since they capitalise on fragile quantum properties
such as coherence, while enabling ultra-high spatial resolution. For sensing, the crux is tominimise the measurement uncertainty in a chosen range within a given time. However, basic
quantum sensing protocols cannot simultaneously achieve both a high sensitivity and a large
range. Here, we demonstrate a non-adaptive algorithm for increasing this range, in principle
without limit, for alternating-current ﬁeld sensing, while being able to get arbitrarily close to
the best possible sensitivity. Therefore, it outperforms the standard measurement concept inboth sensitivity and range. Also, we explore this algorithm thoroughly by simulation, anddiscuss the T−2 scaling that this algorithm approaches in the coherent regime, as opposed to
the T−1/2 of the standard measurement. The same algorithm can be applied to any modulolimited sensor.

1 Institute for Chemical Research, Kyoto University, Gokasho, Uji-city, Kyoto 611-0011, Japan. 2 National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Ibaraki 305-8568, Japan. 3Present address: Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan.
✉email: herbschleb@dia.kuicr.kyoto-u.ac.jp; mizuochi@scl.kyoto-u.ac.jp

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upreme sensitivities are realisable by exploiting the coherence of quantum sensors1. For quantum-sensing applications, nitrogen-vacancy (NV) centres in diamond haveattracted considerable attention due to their exceptional quantummechanical properties1,2, including long spin-coherence times3,4,
and due to their great potential for far-ﬁeld optical nanoscopy5–8.
Furthermore, an increase in sensitivity can be gained for alternating current (AC) ﬁeld sensing by prolonging the NV spin
coherence with dynamical decoupling of the centre’s spin from its
environment2,3,9–12. Therefore, AC ﬁeld sensing is applied invarious areas of physics, chemistry and biology: to detect single
spins13–15, for nuclear magnetic-resonance of tiny samplevolumes16–20, for nanoscale magnetic-resonance imaging13,21–23
and to search for new particles beyond the standard model24,25. In
these applications, both a wide range of the AC ﬁeld amplitude
and a high sensitivity are very important, because the magnitudeof the AC ﬁeld strongly depends on the distance r from the NV
spin (r−3 in case of a magnetic dipole ﬁeld). This outlines the most
relevant variable for this ﬁeld of research: the dynamic range,
which is the ratio of the range to the sensitivity, the latter being ameasure for the smallest measurable ﬁeld amplitude.
In previous research, NV centres were utilised for sensitive
high-dynamic range direct current (DC) magnetic ﬁeld measurements. A theory paper26 discussed the application of a moregeneral phase-estimation method27 to a single NV nuclear spin indiamond, read out with single-shot measurements. They combined Ramsey interferometry on the nuclear spin with different
delays to improve the sensitivity via Bayes’ theorem applied tobinary data, which precision, given full visibility, scaled as T �1meas(with Tmeas the measurement time), dubbed Heisenberg-likescaling28. Adaptive27 and non-adaptive28,29 approaches werediscussed, but they found to their surprise that under more realistic circumstances, only the non-adaptive method could stillshow sub-T �0:5
meas scaling, by applying different amounts of iterations in a linear way29. The range itself remained the same as withthe standard measurement, but they improved the sensitivity forthis range, hence improving the dynamic range. This theory wasapplied to the electron spin30 and the nuclear spin31 of the NV
centres via the non-adaptive method. Indeed, they found that the�0:77 3031), while they
uncertainty scaled sub-T �0:5
and T �0:85
meas (T meas
meas
improved the dynamic range by 8.530 and 7.431. More recently, inan experiment at low temperature the adaptive method showed
improved results, with scaling close to T �1meas and a claimed
improvement (compared to refs. 30,31) of the dynamic range by
two orders of magnitude32.
A similar method for AC magnetic ﬁeld sensing applied different order dynamic-decoupling sequences33. Their improvement of the dynamic range compared to a sequence with 16
π-pulses was about 26, and they explored the effect of the phase of
the measured ﬁeld in depth. Besides, one of the advantages of thepreviously reported dynamical sensitivity control11 was theincrease in the range by 4000 times, up to a theoretical maximumof 5000 times. Their uncertainty for a single measurement was
about double that of a similar standard measurement, while therequired multi-measurement for the large range worsened
pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ thesensitivity
further(whichistheuncertainty
times
T meas ) by
pﬃﬃﬃﬃﬃﬃ
N ϕ with Nϕ the number of phases applied in their method (themore phases, the larger the range, but each phase requires anadditional measurement).
As to see why dynamic-range increasing algorithms are
required, we look at the standard measurement. In the standard
method to measure the AC magnetic ﬁeld with NV centres with asynchronised Hahn-echo measurement2,3,9,10 (Fig. 1b), after
initialisation into a superposition state with a laser pulse and theﬁrst microwave (MW) π/2-pulse, the AC magnetic ﬁeld isapplied. Hence, the spin rotates along the z-axis, thus its phase2changes. Halfway the period of the magnetic ﬁeld, a MW π-pulse
ﬂips the spin, such that the phase accumulated during thenegative half of the period doubles the acquired phase. The ﬁnal
phase is essentially converted into a population with a ﬁnal MW
π/2-pulse before read-out with a laser pulse. The larger theamplitude of the ﬁeld, the further the spin rotates, thus the ﬁnal
phase of the spin relates directly to this amplitude.
However, the phase of the spin can be determined only within
2π at best, thus the range of amplitudes is limited. If the sensor ismore sensitive, the spin accumulates more phase, thus it revolves
for 2π for a smaller AC ﬁeld amplitude already. Therefore, themore sensitive the system, the smaller the range is. Thus, tobeneﬁt from extremely sensitive sensors which utilise entanglement34–36 without the limitation of their minuscule range, it isimportant to increase this range, while retaining their high sensitivity (thus low uncertainty) as much as possible. Moreover,since the measurements of the electron spin of a single NV centre
consist of iterating a sequence many times to accumulate sufﬁcient signal (photons for NV centres), the uncertainty scales as37
T �0:5
meas .
In this work, we demonstrate and explore a non-adaptivealgorithm for quantum sensors to measure AC ﬁelds with a large
range for which the loss in sensitivity is negligible (thus maximising the dynamic range), both by measurement and extensive
simulation. This shows that our algorithm scales nearly
Heisenberg-like (here T �2
meas ) under realistic circumstances, thus
even with the reduced contrast in the spin read-out (normally
about 30% for NV centres); we explain why this happens, and its
importance. Finally, we establish with our algorithm how toincrease the range beyond the limit given by the best possible
standard measurement, which in principle allows to extend it
without bound. Throughout this paper, we use the electron spinof a single NV centre to measure magnetic ﬁelds with the phase of
the spin coherence. However, the insights of this paper remain
the same for similar quantum systems.
Results
Base algorithm. We start with explaining the base of our algorithm (illustrated in Fig. 1), and we clarify the terms referred tothroughout the paper and supplementary information. The
standard measurement for AC magnetic ﬁelds, applying theHahn-echo sequence, has a limited range Brange = Bperiod/2 due tothe sinusoidal shape (with period Bperiod) of the signal response tomagnetic
pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬁeld amplitudes (Fig. 1a). The sensitivity is deﬁned asσ B T meas with σB the uncertainty of the sensed quantity (heremagnetic ﬁeld amplitude) and Tmeas the measurement time. For
this standard measurement, σ B ¼ σ S =gradmax where σS is theuncertainty in the measured signal of a single measurement (inour case shot-noise limited), and gradmax the maximum gradientin the response3 (for example at the inﬂection point of thesinusoid in Fig. 1a). Therefore for these measurements, theshorter Bperiod (thus the smaller the range), the steeper the slope,thus the more sensitive, as mentioned earlier.
For the maximum sensitivity, a standard Hahn-echo sequenceis performed over the full period of the magnetic ﬁeld (Fig. 1b, forsingle NV centres this period should be shorter than about half
the coherence time3). Since the acquired phase of the spin is
proportional to the area under the magnetic ﬁeld curve (seeSupplementary Information of ref. 3), and hence Bperiod is
proportional to this area as well, by reducing the measured area
M times (Fig. 1b), the effective period increases by M (Fig. 1a, d).
The time delay between the π/2-pulses in the sequence follows
from integration to compute the probed area (Fig. 1c). Hereafter,
measuring an area A means applying a sequence with thiscalculated time delay, and A0 is the maximum area. Thus,

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Fig. 1 Algorithm base principle. a Since the measured signal (red dotted line) oscillates due to the rotating spin, the magnetic ﬁeld B can be determined up
to a certain range only. Example ranges are indicated by different colours, and the resulting magnetic ﬁeld for each range given the measured signal(horizontal black dashed line) with blue crosses. b The conventional and most sensitive way to measure an AC ﬁeld is given at the top left, with π/2-pulsesof a Hahn-echo sequence at the beginning and end of the period, and the π-pulse halfway at the inﬂection point. The measured area A0 can be reduced bymoving the π/2-pulses closer to the centre (top right A0/2, bottom left A0/4, bottom right A0/8). c The fraction of the maximum area A0 vs the fraction of
the longest time delay between the π/2-pulses for DC (green dotted line) and AC (cyan line) ﬁelds. For DC, this is linear, while for AC, this depends on thearea of a sinusoid, which resembles a line near the inﬂection point, thus the relation becomes quadratic for short time delays. The area and thus
uncertainty/range can be changed continuously by changing this delay. d For smaller measured areas, the probed ﬁeld decreases proportionally, as does
the effective frequency. In a, the signal for area A0 was shown, while here, the signals for areas A0/2 and A0/4 are drawn in similar fashion, which areoffset for clarity. Combining several measured areas reduces the potential ﬁelds (vertical grey dashed arrows), thus increasing the overall range. e Aftermeasuring the signal (horizontal green dotted line), with the known uncertainty of the signal (green line along the vertical axis), the probability distributionof the ﬁeld (magenta line along the horizontal axis) follows via the sinusoidal relationship (red dotted sine-shaped line for area A0/2). f The measurementwith the largest area A0 gives several similar peaks in the probability distribution (blue line). However, when combining measurements with different areas(magenta dashed line added A0/2, olive dotted line added A0/4 as well), the number of remaining peaks reduces, while the sharpness (thus uncertainty)
remains similar to that of the ﬁrst measurement.

performing a measurement with a sufﬁciently small area would be
the simplest approach for a large-range measurement. However,roughly comparing with the measurement over the maximum
area, using the same number of iterations of the sequence (thus σS
is similar) and the same measurement time (no optimisations),
the gradient for the reduced area gradmax;M ¼ gradmax;1 =M, hence
its sensitivity is M times worse.
To improve the sensitivity for a large range, initially, a numberof measurements with different areas are combined to uniquelydeﬁne the magnetic ﬁeld amplitude in a range limited by themeasurement with the smallest area (Fig. 1d). Consequently, only
part of the measurement time is spent on the largest area, which
has the best sensitivity (but a small range), while the remainder of
the time is spent on areas with a worse sensitivity. Therefore, thesensitivity of the combined measurement is strictly worse than
this best sensitivity. Using halved areas (hence requiring at leastlog 2 ðM Þ additional areas) and the same number of iterations
for each area and using no optimisations, for roughly thesame σB, the measurement time for the combined sequence
T meas;M ¼ d1 þ log 2 ðM ÞeT meas;1 . Thus, the sensitivity would
pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ
becomed1 þ log 2 ðM Þe times worse, which is already asigniﬁcant improvement compared to the straightforward casein the last paragraph.
The measurements resulting from different areas are combined
via Bayes’ theorem. For area An, the measurement gives signal Sn(for example the crosses/circles/triangles on the sinusoids in
Fig. 1a, d for three areas). The posterior probability distribution
for the magnetic ﬁeld B given measured signal Sn isPðSn jBÞPðBÞ
;PðSn Þ

ð1ÞPðSn jBÞ ¼ PðSn jSðBÞÞ;ð2ÞPðBjSn Þ ¼

with PðBÞ the prior distribution, PðSn Þ independent of B, andwith SðBÞ the relation between the signal S and the applied ﬁeld B(the sinusoids in Fig. 1a, d, e). Fig. 1e visualises these equations.
PðSn jSÞ is a Poisson distribution (counting photons), but it can beapproximated by a normal distribution (green line along y-axis in
Fig. 1e) when more than ~10 photons arrive (with continuity
correction). This is generally the case when the uncertainty is below
the maximum uncertainty, as described later. For the ﬁrst
measurement, the prior distribution is ﬂat since there is no initialknowledge about the ﬁeld, and for the remainder of themeasurements, the previous posterior is the new prior distribution.
This results in a combined distribution as demonstrated in Fig. 1f.
Uncertainty. Before performing measurements and simulating
the algorithm, a deﬁnition of merit is required that facilitates boththe sensitivity and the range. Therefore, we choose the uncertainty in magnetic ﬁeld σB, deﬁned as the standard deviation of

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the magnetic ﬁeld distribution centred around its maximum
value. For sufﬁciently long measurement times, this gives thesame result compared to applying the normal formula. However,the difference is visible for short measurement times, since ittakes the range into account: we know the magnetic ﬁeld is in thegiven range, which means that if the probability distribution
pﬃﬃﬃﬃﬃ isﬂat, the uncertainty is at its maximum σ B;max ¼ Brange = 12 (seepﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ
Supplementary Note 1). σB multiplied by T meas gives the sensitivity, but this is unsuitable as ﬁgure of merit at short measurement times, since its limit is 0 nT Hz−1/2 for Tmeas = 0 s
while approaching the asymptotic maximum uncertainty.
At ﬁrst, since the uncertainty in a range is limited by the worst
uncertainty in this range, we simulated the homogeneity of theuncertainty in the complete range. For a standard measurement,
the usually reported uncertainty (σ B ¼ σ S =gradmax ) is only true
for a single magnetic ﬁeld amplitude at inﬁnite measurement
time, but otherwise it is worse and inhomogeneous. By combining
two measurements with the same area but their response shiftedby a phase of π/2, the uncertainty becomes more homogeneous,and guarantees a lower uncertainty than the standard measurement across its range. Thus, such a measurement consists of twophases (see for example Supplementary Fig. 7a). The homogeneity is improved further by increasing the number of phases;
four phases are used throughout this paper. Supplementary
Note 2 describes the details of homogeneity for our algorithm,
and for previous ones it is explored in ref. 38. Since theuncertainty is nearly homogeneous, which ﬁeld is applied isirrelevant while determining this uncertainty. Without priorknowledge or feedback, the uncertainty is ultimately limited bythis combination of four phases for the largest area possible3.
Measurement compared with simulation. For our measurements, we use an n-type diamond sample. This was epitaxiallygrown onto a Ib-type (111)-oriented diamond substrate bymicrowave plasma-assisted chemical-vapour deposition withenriched 12C (99.998%) and with a phosphorus concentration of~6 × 1016 atoms cm−3 3,39. We address individual electron spins
residing in NV centres with a standard in-house built confocal
microscope. MW pulses are applied via a thin copper wire, whilemagnetic ﬁelds are induced with a coil around the sample. All
experiments are conducted at room temperature. We use single
NV centres with T2s of about 2 ms.
We measure and simulate σB for ﬁve sequences to show theconsistency between the measurements and simulations, and to
get an idea of the working of the base of our algorithm. Please
note that the only difference between our measurements andsimulations is that the simulations calculate the signal otherwise
measured using the known sequence, the set magnetic ﬁeld
amplitude, and the parameters of the measured NV centre. The
analysis applied otherwise is exactly the same, thus realistic
circumstances are simulated (small contrast, shot-noise as
described in Supplementary Note 2, decay due to coherence timeT2). The ﬁrst sequence measures the largest area (here a single
period of the ﬁeld); the second, third and fourth use half, aquarter and an eighth of the largest area; and the ﬁfth sequence
includes these four sequences equally in a separate measurement/
simulation. All include four phases as mentioned in the last
subsection. Initially, the objective is to investigate the details of
the algorithm itself, hence to nullify artefacts stemming fromoverhead times (which are implementation-dependent, and could
include laser pulses, MW pulses and waiting times), these are
ignored at ﬁrst and explored in the discussion.
The results are shown in Fig. 2a, which reveals a number ofimportant points. Firstly, the measurements closely match
simulations. Secondly, below a certain measurement time, no4knowledge about the ﬁeld is gained, and hence σB is at its
maximum. Thirdly, for longer measurement times, σB scales asT �0:5
meas . Fourthly, for the combined sequence there is a region in
Tmeas where σB scales more steeply (here referred to as the steep
region). Finally, as explained in the base-algorithm subsection,
the uncertainty of the combined sequence is always higher thanthe uncertainty of the largest-area sequence, since the former
spends measurement time on sequences other than this largestarea sequence which has the lowest uncertainty. Of course, theadvantage of the combined sequence over the largest-areasequence is its larger range (please remember that
Brange / σ B;max , see Supplementary Note 1).
Algorithm design. To design our eventual algorithm, its principle
is explored in more detail with additional simulations. Fig. 3ashows the result for changing the relative number of iterations foreach area, which reveals that there is a trade-off between thelowest uncertainty reached for measurement times at the steep
region and at long measurement times. In other words,
depending on Tmeas, a different relative number of iterations gives
the lowest uncertainty. When ﬁxing these (Figs. 2a and 3a), theuncertainty is not optimised, and thus it can display very steep
curves that can be tuned to even sub-Heisenberg-like scaling (forexample T �4:0
meas in Fig. 3a).
For our algorithm, we optimise the relative number of
iterations at each measurement time to minimise the uncertainty.
The result for this measurement-time-wise optimisation is plottedin Fig. 3b. This shows that the longer Tmeas, the closer thesensitivity gets to its ultimate limit, where the scaling approaches
�0:98
T �0:5
meas . At the steep region of this optimum, the scaling is T meas .
When we look at Fig. 3c, which depicts the relative number of
iterations, we can understand how our algorithm works. For very
short Tmeas, all measurement time is allotted to the smallest area,
since the larger areas are at their maximum uncertainty and hencecannot contribute. But for longer Tmeas, at some time the next area
becomes relevant and thus turns on, since it can receive sufﬁcientmeasurement time to lower σB below its maximum uncertainty.
This continues until the largest area turns on, which then keeps
increasing in relative importance, at which point the scaling of theuncertainty is about T �0:5
meas . Thus for longer Tmeas, the largest area
receives increasingly more relative measurement time, meaning
the uncertainty continuously approaches this ultimate uncertainty,
as plotted by the green dashed line in Fig. 3c.
If we would increase the number of areas in the sequence, theuncertainty becomes steeper during the turning-on region (whichis the steep region). Figure 3d plots the result for a large amountof areas, indicating that the uncertainty scales as T �2
meas up to
nearby the largest area. The scaling follows from the quadratic
dependence of the area on the subsequence length (see Fig. 1c).
Since closer to the largest area, this is not quadratic yet, it
becomes less steep (lowest yellow crosses in Fig. 3d). The decay incoherence due to the ﬁnite T2 negatively effects the uncertainty as
well in this region, further decreasing the steepness. Analogue for
DC measurements, the uncertainty scales as T �1meas in the steep
region. Supplementary Note 3 discusses scaling in more detailbeyond the indication given here. When taking any overhead
time into account, the effective measurement time decreases, thus
the curves would become even steeper.
So far in the examples with our algorithm, we used halved areas(An = A0/2n for integer n ≥ 0). Even though the uncertainty ismostly deﬁned by the largest area, and the range by the smallest, themiddle areas are important for reaching the lowest uncertainty (seeFig. 3c: they partake in the optimal combination). Adding moreareas at integer multiples of the smallest area decreases theuncertainty, though slightly (see Supplementary Note 4).

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Fig. 2 Measurement and simulation. a Example uncertainty σB vs measurement time Tmeas for AC sensing (1 kHz) comparing simulations (blue dashed line
for largest area A0; magenta, olive and grey dashed lines for A0/2, A0/4 and A0/8; green line for the equally combined sequence with these areas) withmeasurements (blue crosses, magenta circles, olive triangles, grey diamonds and green pluses, respectively; error bars indicate single standard deviations).
The simulations use the same parameters and analysis as the measurements, they are not ﬁts. b Optimised uncertainty vs measurement time for AC
sensing (2 kHz) around the steep region. Green pluses give the measurement results, the error bars are single standard deviations. Blue triangles are thesimulation results. Red circles display the estimation of the large-range limit. Cyan diamonds plot the Heisenberg limit for inﬁnite T2 (see Supplementary
1:6
Note 3 for details). The diagonal black dashed lines are guides to the eye for scaling T 2
meas and T meas . The overhead time is ignored in order to show theeffect of the algorithm only. c Sensitivity vs magnetic ﬁeld range (at 2 kHz). Blue dots with error bars (single standard deviations) give the sensitivity of ouralgorithm measured at each range excluding all overhead time. Grey circles plot the sensitivity including all overhead time assuming basic compact
sequence design (see Supplementary Note 8), while grey pentagons plot the sensitivity assuming each area requires a separate period. The green
diamonds plot the sensitivity for the standard measurement (excluding overhead time) extracted from the smallest area of our algorithm. Please note that
our algorithm goes beyond the range possible with the standard measurement (vertical green dashed line) by combining non-integer-multiple areas (seeSupplementary Note 6 for details). The horizontal magenta line indicates the sensitivity of the most sensitive standard measurement extracted from thelargest area of our algorithm, which thus has a single small range only (the leftmost: ~102 nT). The horizontal black dashed line (on top of the magenta line)
gives the ﬁtted sensitivity of our algorithm.

Algorithm measurement. In Fig. 2b, measurement results of ouralgorithm in the steep region are plotted (for details of the measurement see Supplementary Note 5), together with the Heisenberg
limit (which is only true for a small range and inﬁnite T2) and theapproximate large-range limit explained in Supplementary Note 3. As
mentioned before, and just like in Fig. 3d, the focus is on the scalingthat originates from the algorithm, hence all overhead time isignored. Our algorithm is very close to the limit, as could be expected
since at long measurement times most time is spent on the sequencewith the largest area. Moreover, our results scale approximately as
2
T 1:6
meas , which is less steep than the Heisenberg-like scaling of T meas ,since our algorithm keeps approaching this limit.
When merely halving areas in a measurement sequence, its
range is deﬁned by the smallest area. Therefore, it would only
improve the uncertainty with respect to the standard single-areameasurement, but not the range. In this way, given a limit on thetime delay between the π/2-pulses, for example owing to a
maximum time resolution or waiting time requirements, themaximum range is restricted. However, the range of ouralgorithm is the inverse of the greatest common divisor of thefrequencies in measured signal of all included areas (seeSupplementary Note 6). For halved areas, since all larger areas
are integer multiples of the smaller ones, this means that thegreatest common divisor is the lowest frequency, thus the one
related to the smallest area. To increase the range beyond thislimit, we combine areas that are not integer multiples of eachother. When purely looking at the range, combining two
sequences for slightly different areas increases the range far
beyond the standard measurement’s range. Thus in principle, therange can be extended unlimitedly. Adding the large areas as well,
it is still possible to get arbitrarily close to the ultimate uncertainty(for details see Supplementary Note 6).

The dynamic range of our algorithm is explored withmeasurements in Fig. 2c, which plots the sensitivity with respect
to the range of the measurement sequence. Initially, for eachincrease in the range, an additional subsequence of half thesmallest area is added. However, for the ﬁnal four ranges, a single
area is added at 1.5, 1.25, 1.1 or 1.05 times the smallest area. To
compare with shorter sequences and with other results fairly, thesensitivity is chosen instead of the uncertainty (to calculate thedynamic range) and the overhead time is still ignored. It is
computed by combining measurements from both the left sideand right side of the designed range (as explained before, given
the homogeneity of the uncertainty in our algorithm, the appliedmagnetic ﬁeld does not matter). The sensitivity for the standard
measurement with the same range is plotted as well (derived fromthe smallest area of our algorithm), and the sensitivity of the mostsensitive sequence (derived from the largest area of ouralgorithm), the latter having a small range only (~102 nT). Ouralgorithm is nearly as sensitive as the most sensitive sequence,and its range can go beyond that of a standard measurement. In
these measurements, the maximum range was limited by ourequipment only, and could be improved further.
Discussion
Given a ﬁxed sequence, a subsequence contributes only to theresult when the measurement time it receives is sufﬁciently longto lower the measured uncertainty below its maximum (seeFig. 3c). Therefore in our algorithm, the optimum sequence for agiven measurement time includes contributing subsequences
only. On the contrary, when combining subsequences in a ﬁxed
way with the least sensitive subsequence measured most often, forshort measurement times, the more sensitive subsequences do notcontribute, and hence their measurement time is wasted. This

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Fig. 3 Simulation analyses. a For different relative numbers of iterations of the subsequences (written directly left of each curve) of areas A, theuncertainty σB with respect to measurement time Tmeas changes. Depending on the measurement time, a different combination gives the lowest
uncertainty. b Minimised uncertainty for a large-range sequence by optimally combining the subsequences (red line). The dashed lines give the uncertainty
for single-area sequences (A0 blue, A0/2 magenta, A0/4 olive, A0/8 grey). See Supplementary Note 1 for maximum uncertainty ∝ range. c The relative
number of iterations for each area (A0 blue crosses, A0/2 magenta circles, A0/4 olive triangles, A0/8 grey diamonds kept at 100) for each measurement
time to minimise the uncertainty, which results in the red line in b. The vertical arrows indicate when a subsequence for its area turns on, since its relative
number of iterations becomes signiﬁcant. The green dashed line gives the relative difference between the most-sensitive small-range sequence (bluedashed line in b) compared to the optimally combined large-range sequence. This difference scales inversely with the measurement time. d When looking
at the turning-on points (yellow crosses, ﬁt with black dotted line) for many sequences with different areas (largest area blue line, smallest area red line), it
0:98
scales as T 2
meas for short measurement times. Please note that the optimally combined result in b scales as T meas , since it includes relatively large areas
only, equivalent to the lowest lines in this plot.

results in a steeper measurement time dependence in the same
way as overhead time does. This illustrates one conclusion of
Supplementary Note 3: a steeper dependence leads to a worsealgorithm, since when decreasing the measurement time, theuncertainty increases more quickly for a steeper curve.
For our algorithm, if it is possible to choose for which subsequence to increase the number of iterations while measuring,the uncertainty can be minimised for all measurement times (redline in Fig. 3b), since the absolute number of iterations for eachsubsequence is monotonically increasing over measurement time(see Supplementary Note 7). Please note that it is known
beforehand for which subsequence to increase the number of
iterations, it does not depend on the measurement results, thus it
is a non-adaptive method. Moreover, since our algorithm spends
most time on the largest area, any overhead time (which is
generally independent of the subsequence) is relatively as short as
possible. This is visualised in Fig. 2c, which plots the sensitivities
both with and without all potential overhead times, illustrating
the overhead is negligible indeed.
For measurement times in the steep region, since quantum
sensing is generally chosen for its high sensitivity, a sensor would
rather unlikely be used given the high uncertainty. Therefore, thisregion and its scaling are fairly irrelevant: if a short measurement
time is desired, less subsequences are required, which effectively
puts the sensor just at the inﬂection point (when scaling starts to
be T �0:5
meas ).
For measurement times beyond the steep region, σB and thus
sensitivity are very close to the limit for a homogeneous range.
6

pﬃﬃﬃ
This is still about 2 worse than the standard sensitivity for asingle ﬁeld at inﬁnite measurement time (Supplementary Fig. 2).
It is possible to improve towards this by applying feedback ofintermediate results during the measurement, and dropping all
but two phases in the process to focus on the two phases with theﬁeld to measure located at their maximum gradient, which gives
the smallest uncertainty. There is a trade-off between addedcomplexity of such an adaptive measurement32 (real-time processing of data, changing the sequence during the measurement
and/or set any phase in the measurement instead of just fourpwith
ﬃﬃﬃ
in-phase-quadrature modulation) and gained sensitivity ( 2 atbest for inﬁnite measurement time), even when ignoring theprocessing overhead. Moreover, even under these ideal circumstances, the dynamic range,prather
relevant for large-range meaﬃﬃﬃ
surements, is actually
2 worse for standard adaptive
measurements compared to non-adaptive measurements (seeSupplementary Note 2).
An important point ignored so far is how to implement thisalgorithm at all for AC ﬁelds, since its shape needs to be taken
into account. As opposed to DC measurements, where the area
can be reduced simply by shortening the time delay between theπ/2 pulses proportionally, for AC it is more complicated, as
illustrated in Fig. 1b, c. Moreover, it might seem that for each
iteration another period of the magnetic ﬁeld is required(resulting in the practical but non-optimal sensitivity plotted withpentagons in Fig. 2c), while for DC all measurements can be
strung together, the latter limiting the measurement time. However, something similar is possible for AC ﬁelds, since the DC

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part cancels, as explained in Supplementary Note 8. In our results,
we neglected the effect this stringing has on the total measurement time to focus on the working of the algorithm. However,since AC stringing is only slightly less effective than DC stringing,and since often most measurement time is dedicated to the largest
area (which has no stringing disadvantage), it justiﬁes the choice
to ignore the overhead time of these stringing effects. This is
explored in detail in Supplementary Note 8, which describes how
to design compact measurement sequences (resulting in thepractical closer-to-optimal sensitivity plotted with circles inFig. 2c). Measurements with these compact sequences illustratethat the practical sensitivity, compared to the overhead-ignored
sensitivity, would worsen with about 5% when all overhead timeis included using a basic sequence design (see Supplementary
Fig. 10).
Additionally, please note that the description of the algorithm
focussed on areas to easily translate it to any ﬁeld, such as DC
ﬁelds or square waves. Moreover, the frequency of the AC ﬁeld is
not relevant, since for lower frequencies the largest area will not
span a whole period, while for high frequencies additional
π-pulses are required to optimise the largest area. This deﬁnes thelowest uncertainty, which our algorithm approaches for every
situation. This uncertainty increases for lower frequencies, since asmaller area is measured within the coherence-limited time delay,
while for higher frequencies it decreases, due to the increase incoherence time by a dynamic-decoupling sequence (just for thelarger areas, the largest deﬁning the lowest uncertainty). Of
course, the shape of the area vs time-delay graph (Fig. 1c)
depends on the shape of the ﬁeld and the chosen pulse sequences.
For practical implementations of the algorithm, as in theexample with a single NV centre, the reader is advised that thelarger the range becomes, the more prominent the effects of offresonance MW pulses become. For DC, this is even more
important (see for example ref. 31), while for AC, the pulses areoften near low ﬁelds (for example for the sensitivity-deﬁning large
area they are at the inﬂection points). Thus, care should be taken
during the design depending on the chosen quantum system andthe available technology.
As a ﬁnal remark, applying the optimal number of iterations
for a long measurement time gives a small chance to conclude thewrong ﬁeld, since relatively little time is spent in the smaller
range-deﬁning areas (see Supplementary Note 9). However, theanalysis does not return a single measured ﬁeld amplitude, but aprobability distribution of the ﬁeld. As demonstrated in Supplementary Note 9, when the ﬁeld is within a few σB of the actual
ﬁeld, there is a single pronounced peak in this distribution.
Oppositely, there are multiple strong peaks if the expected ﬁeld of
the measurement is signiﬁcantly different. Thus, such a result
could easily be discarded (of course effectively slightly reducing
the sensitivity to redo the measurement for these cases).
To conclude, we have introduced an ultra-high dynamic-range
algorithm for measuring magnetic ﬁelds with a quantum sensor,
such as a single NV centre, for which the uncertainty, and hence
sensitivity, can be arbitrarily close to the ultimate uncertainty/
sensitivity by increasing the measurement time. The maximum
range depends on the smallest difference in areas attainable,
which results in a larger range than possible with a standard
measurement. As example, we demonstrated a dynamic range of~ 107, an improvement of two orders of magnitude compared toprevious algorithms32 (please note that a fair comparison between
algorithms corrects the results for the coherence time, the minimum/maximum time delays, the applied spin-measurement
method and the experimental equipment, as these change theresults independent of the applied algorithm). Moreover, we
explained the origin of Heisenberg-like scaling in algorithms andwhy steeper scaling indicates a worse algorithm. Our algorithm

and its implications are the same for other modulo-limited sensors, thus it paves the way to optimally beneﬁt from extremely
sensitive entanglement-based sensors for large-range applications.
Data availability
The data that support the ﬁndings of this study are available from the corresponding
author upon reasonable request.

Received: 6 December 2019; Accepted: 8 December 2020;

References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.

Degen, C. L., Reinhard, F. & Cappellaro, P. Quantum sensing. Rev. Mod. Phys.
89, 035002 (2017).
Rondin, L. et al. Magnetometry with nitrogen-vacancy defects in diamond.
Rep. Prog. Phys. 77, 056503 (2014).
Herbschleb, E. D. et al. Ultra-long coherence times amongst roomtemperature solid-state spins. Nat. Commun. 10, 3766 (2019).
Bar-Gill, N., Pham, L. M., Jarmola, A., Budker, D. & Walsworth, R. L. Solidstate electronic spin coherence time approaching one second. Nat. Commun.
4, 1743 (2013).
Rittweger, E., Han, K. Y., Irvine, S. E., Eggeling, C. & Hell, S. W. STED
microscopy reveals crystal colour centres with nanometric resolution. Nat.
Photonics 3, 144–147 (2009).
Maurer, P. C. et al. Far-ﬁeld optical imaging and manipulation of individual
spins with nanoscale resolution. Nat. Phys. 6, 912–918 (2010).
Jaskula, J.-C. et al. Superresolution optical magnetic imaging and spectroscopyusing individual electronic spins in diamond. Opt. Express 25, 11048–11064(2017).
Jin, D. et al. Nanoparticles for super-resolution microscopy and singlemolecule tracking. Nat. Methods 15, 415–423 (2018).
Taylor, J. M. et al. High-sensitivity diamond magnetometer with nanoscale
resolution. Nat. Phys. 4, 810–816 (2008).
Wolf, T. et al. Subpicotesla diamond magnetometry. Phys. Rev. X 5, 041001(2015).
Lazariev, A., Arroyo-Camejo, S., Rahane, G., Kavatamane, V. K. &Balasubramanian, G. Dynamical sensitivity control of a single-spin quantum
sensor. Sci. Rep. 7, 6586 (2017).
Knowles, H. S., Kara, D. M. & Atatüre, M. Observing bulk diamond spin
coherence in high-purity nanodiamonds. Nat. Mater. 13, 21–25(2013).
Grinolds, M. S. et al. Nanoscale magnetic imaging of a single electron spin
under ambient conditions. Nat. Phys. 9, 215–219 (2013).
Shi, F. et al. Single-protein spin resonance spectroscopy under ambientconditions. Science 347, 1135–1138 (2015).
Shi, F. et al. Single-DNA electron spin resonance spectroscopy in aqueous
solutions. Nat. Methods 15, 697–699 (2018).
Aslam, N. et al. Nanoscale nuclear magnetic resonance with chemical
resolution. Science 357, 67–71 (2017).
Mamin, H. J. et al. Nanoscale nuclear magnetic resonance with a nitrogenvacancy spin sensor. Science 339, 557–560 (2013).
Glenn, D. R. et al. High-resolution magnetic resonance spectroscopy using asolid-state spin sensor. Nature 555, 351–354 (2018).
Boss, J. M., Cujia, K. S., Zopes, J. & Degen, C. L. Quantum sensing with
arbitrary frequency resolution. Science 356, 837–840 (2017).
Schmitt, S. et al. Submillihertz magnetic spectroscopy performed with ananoscale quantum sensor. Science 356, 832–837 (2017).
Rugar, D. et al. Proton magnetic resonance imaging using a nitrogen-vacancy
spin sensor. Nat. Nanotechnol. 10, 120–124 (2014).
DeVience, S. J. et al. Nanoscale NMR spectroscopy and imaging of multiple
nuclear species. Nat. Nanotechnol. 10, 129–134 (2015).
Perunicic, V. S., Hill, C. D., Hall, L. T. & Hollenberg, L. C. L. A quantum spinprobe molecular microscope. Nat. Commun. 7, 12667 (2016).
Rong, X. et al. Searching for an exotic spin-dependent interaction with a single
electron-spin quantum sensor. Nat. Commun. 9, 739 (2018).
Budker, D., Graham, P. W., Ledbetter, M., Rajendran, S. & Sushkov, A. O.
Proposal for a cosmic axion spin precession experiment (CASPEr). Phys. Rev.
X 4, 021030 (2014).
Said, R. S., Berry, D. W. & Twamley, J. Nanoscale magnetometry using asingle-spin system in diamond. Phys. Rev. B 83, 125410 (2011).
Higgins, B. L., Berry, D. W., Bartlett, S. D., Wiseman, H. M. & Pryde, G. J.
Entanglement-free Heisenberg-limited phase estimation. Nature 450, 393–396(2007).
Berry, D. W. et al. How to perform the most accurate possible phasemeasurements. Phys. Rev. A 80, 052114 (2009).

NATURE COMMUNICATIONS | (2021)12:306 | https://doi.org/10.1038/s41467-020-20561-x | www.nature.com/naturecommunications

－155－

7

ARTICLE

NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20561-x

29. Higgins, B. L. et al. Demonstrating Heisenberg-limited unambiguous phaseestimation without adaptive measurements. N. J. Phys. 11, 073023 (2009).
30. Nusran, N. M., Momeen, M. U. & Dutt, M. V. G. High-dynamic-range
magnetometry with a single electronic spin in diamond. Nat. Nanotechnol. 7,
109–113 (2011).
31. Waldherr, G. et al. High-dynamic-range magnetometry with a single nuclear
spin in diamond. Nat. Nanotechnol. 7, 105–108 (2011).
32. Bonato, C. et al. Optimized quantum sensing with a single electron spin using
real-time adaptive measurements. Nat. Nanotechnol. 11, 247–252 (2015).
33. Nusran, N. M. & Dutt, M. V. G. Dual-channel lock-in magnetometer with asingle spin in diamond. Phys. Rev. B 88, 220410 (2013).
34. Leibfried, D. et al. Toward Heisenberg-limited spectroscopy with multiparticle
entangled states. Science 304, 1476–1478 (2004).
35. Nagata, T., Okamoto, R., O’Brien, J. L., Sasaki, K. & Takeuchi, S. Beating thestandard quantum limit with four-entangled photons. Science 316, 726–729(2007).
36. Jones, J. A. et al. Magnetic ﬁeld sensing beyond the standard quantum limit
using 10-spin NOON states. Science 324, 1166–1168 (2009).
37. Giovannetti, V., Lloyd, S. & Maccone, L. Advances in quantum metrology.
Nat. Photonics 5, 222–229 (2011).
38. Nusran, N. M. & Dutt, M. V. G. Optimizing phase-estimation algorithms fordiamond spin magnetometry. Phys. Rev. B 90, 024422 (2014).
39. Kato, H., Ogura, M., Makino, T., Takeuchi, D. & Yamasaki, S. N-type controlof single-crystal diamond ﬁlms by ultra-lightly phosphorus doping. Appl.
Phys. Lett. 109, 142102 (2016).

Acknowledgements
The authors acknowledge the ﬁnancial support from MEXT Q-LEAP (No.
JPMXS0118067395), KAKENHI (No. 15H05868, 16H06326) and the Collaborative
Research Program of ICR, Kyoto University (2019-103). They also thank Prof H. Kosaka
for helpful discussions.

Author contributions
E.D.H. designed the algorithm, performed the experiments/simulations/analyses andconceived the supplementary; H.K. grew the phosphorus-doped diamond, assisted by

8

T.M. and S.Y.; N.M. supervised the work; E.D.H. and N.M. wrote the manuscript, and all
authors discussed it.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/s41467020-20561-x.
Correspondence and requests for materials should be addressed to E.D.H. or N.M.
Peer review information Nature Communications thanks the anonymous reviewer(s) for
their contribution to the peer review of this work. Peer reviewer reports are available.
Reprints and permission information is available at http://www.nature.com/reprints
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Mixed lead–tin perovskite ﬁlms with >7 ms charge
carrier lifetimes realized by maltol post-treatment†
Shuaifeng Hu, a Minh Anh Truong, a Kento Otsuka, a Taketo Handa, a
Takumi Yamada, a Ryosuke Nishikubo, b Yasuko Iwasaki, a Akinori Saeki,
Richard Murdey, a Yoshihiko Kanemitsu a and Atsushi Wakamiya *ab

Mixed lead–tin (Pb–Sn) halide perovskites with optimum band gaps near 1.3 eV are promising candidates fornext-generation solar cells. However, the performance of solar cells fabricated with Pb–Sn perovskites isrestricted by the facile oxidation of Sn(II) to Sn(IV), which induces self-doping. Maltol, a naturally
occurring ﬂavor enhancer and strong metal binding agent, was found to eﬀectively suppress Sn(IV)Received 1st August 2021
Accepted 21st September 2021

formation and passivate defects in mixed Pb–Sn perovskite ﬁlms. When used in combination with Sn(IV)scavenging, the maltol surface treatment led to high-quality perovskite ﬁlms which showed enhanced

DOI: 10.1039/d1sc04221a

photoluminescence intensities and charge carrier lifetimes in excess of 7 ms. The scavenging and surface
treatments resulted in highly reproducible solar cell devices, with photoconversion eﬃciencies of up to

rsc.li/chemical-science

21.4% under AM1.5G illumination.

1. Introduction
Lead (Pb)-based perovskite solar cells (PSCs) have reacheda power conversion eﬃciency (PCE) of 25.6%.1,2 While suchdevices are highly optimized, the band gap of Pb-based perovskite materials (Eg > 1.45 eV)3 actually lies slightly outside therange of maximum performance for single-junction solar cells,
1.1–1.4 eV, as determined by Shockley and Queisser.4 The bandgaps of mixed lead–tin (Pb–Sn) perovskite absorbers, meanwhile, fall within the optimal range, being typically 1.2–1.4 eV.5,6
In the last few years, there has been remarkable progress in thedevelopment of Pb–Sn PSCs,7–11 with cell eﬃciencies now
reaching 21.7%.12,13 Despite the optimal band gap, however, thereported device eﬃciencies5,7,12–21 remain lower than those of
their Pb-based counterparts.1,2,22–24 One of the main impediments for any tin-containing perovskite is the facile oxidation of
Sn(II) to Sn(IV). Saidaminov et al.25 and Pascual et al.26 found thatthe starting material, SnI2, can be easily oxidized, even by thesolvent used for the lm fabrication (dimethyl sulfoxide,
DMSO). Oxygen levels as low as a few ppm can cause Sn(II) in theperovskite lms to oxidize, creating Sn(II) vacancies which leadto an increase in hole density.27–30 This p-doping eﬀect has a verystrong negative impact on device performance.31

aInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011,
Japan. E-mail: wakamiya@scl.kyoto-u.ac.jpbDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University,
2-1 Yamadaoka, Suita, Osaka 565-0871, Japan† Electronic supplementary information (ESI) available. CCDC 2080061, 2080062
and 2080063. For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/d1sc04221a

Various strategies for mitigating this issue have been
proposed.32 One eﬀective way to reduce the Sn(IV) content in theperovskite lms is to remove it from the precursor solution, by
modifying the perovskite precursor solution via various
methods. It was reported that the addition of Sn(0) powder into
the Sn-containing precursor solution not only improved thepurity of the precursor solution but also reduced Sn(II) vacancies
in the resulting perovskite lms due to extra Sn(II) generated by
the reaction of Sn(IV) with metallic Sn(0).8,9,33 Antioxidants or
reducing reagents, like formamidinesulnic acid,12 pyrazine,34hydroquinone sulfonic acid,35 and 8-hydroxyquinoline,36 havealso been found to reduce the Sn(IV) content in perovskite
precursor solution.
It is also important to reduce the Sn(IV) in the starting
materials used to prepare the precursor solution. To this end,
we have previously developed highly puried starting materials
for the fabrication of Sn-based PSCs.37–39 We have also recently
reported a Sn(IV) scavenging method based on the high chemical selectivity of an 8p electron system 1,4-bis(trimethylsilyl)2,3,5,6-tetramethyl-1,4-dihydropyrazine (TM-DHP) for SnF2
over SnI2.40 We found that when TM-DHP is added intoa FA0.75MA0.25SnI3 precursor solution in the presence of SnF2,
the Sn(II) from SnF2 is reduced to generate Sn(0) nanoparticles.
These Sn(0) nanoparticles eﬀectively scavenge Sn(IV) impurities
at the precursor preparation stage, giving Sn(IV)-free perovskites
in the bulk of the obtained lms.
Despite these notable improvements to the quality of the asfabricated materials, the perovskite lms remain vulnerable tooxidation aer fabrication, especially at the exposed surfaces.41
To address this, post-treatments for the perovskite lms havebeen developed to protect and passivate the perovskite

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surfaces.42 From a chemical point of view, a strong chelating
agent would be a good choice to stabilize the Sn(II) species.
Kamarudin et al. reported that amine groups in ethylenediamine bind to the undercoordinated Sn(II) species on the Sn
perovskite surface, resulting in improved stability towards
oxidation.43 Unfortunately, however, the high basicity of theethylenediamine resulted in damage to the Sn perovskite
lms.44,45 Milder, but eﬀective reagents are therefore desirable
for the post-treatment of the Sn-containing perovskite lms.
Among the candidates, the environmental-friendly molecule; 3hydroxy-2-methyl-4-pyrone (maltol), known as a ‘avor
enhancer’, is a promising candidate due to its noteworthy metalchelating ability.46
In this work, we extend the use of the Sn(IV) scavenging
method to mixed Pb–Sn perovskite system, and introduce anadditional post-treatment of the perovskite surface with maltol.
The maltol treatment was found to suppress Sn(II) oxidation andreduce the density of defects at the perovskite lm surface. The
photoluminescence (PL) lifetime increasing from 1.3 to 7.4 ms
accompanied with a vefold increase in PL intensity. The PCE of
the champion device fabricated with the combination of Sn(IV)scavenging and maltol post-treatment was 21.4%.

2.

Results and discussion

Maltol, C6H6O3, is a small a-hydroxy ketone known for having
an intense chemical activity towards hard metal ions. We foundthat the electron-rich oxygen atoms in the carbonyl and thehydroxyl groups of maltol simultaneously coordinate to the
Sn(II) in SnI2 to form SnI(maltol) complex (Fig. 1a and b).
Similar complexes were observed to form with SnF2 and SnBr2(Scheme S1 and Fig. S1–S7†). We therefore surmise that if
maltol binds to the undercoordinated Sn(II) sites (Fig. 1c) at thesurface of Pb–Sn perovskite lms, it should eﬀectively suppress
the formation of the defects, like Sn(II) vacancies, at the perovskite lm surface.
To verify this hypothesis, three kinds of perovskite samples
were prepared; control lms without scavenging or maltol post
treatment, lms prepared with TM-DHP reductant only, andlms prepared with both TM-DHP reductant and maltol post-

treatment. The perovskite composition used was Cs0.1FA0.6MA0.3Sn0.5Pb0.5I3 (FA ¼ formamidinium, MA ¼ methylammonium). This composition was selected by evaluating the
PL properties and valence band energy levels of a series of 25
candidate materials (Fig. S8 and S9, Table S1†). The perovskite
layers were prepared by the one step method with chlorobenzene antisolvent. SnF2 (10 mol% with respect to SnI2) andPb(SCN)2 (2 mol% with respect to PbI2) were added to theperovskite precursor solution. SnF2 additive is known tosuppress the oxidation of Sn(II) at the precursor preparation
stage,5 while Pb(SCN)2 is commonly added to mediate theperovskite crystal growth.18 The precursor concentration is
1.8 M, chosen based on previous reports on eﬃcient mixed Pb–
Sn PSCs.9,18 For the samples with Sn(IV) scavenging, 1 mol% TMDHP was added to the precursor solution as described previously.40 For the samples with maltol post treatment, 1 mg mL�1
maltol dissolved in toluene was applied to the surface of thelms by spin-coating, followed by annealing at 65 � C. Accordingly, the control, TM-DHP-treated, and both TM-DHP and
maltol treated perovskite lms were respectively prepared.
The oxidation state of Sn at the perovskite lm surface was
examined using X-ray photoelectron spectroscopy (XPS).
Fig. 2a–c show the Sn 3d signal for the three perovskite lms,
which can be deconvoluted into two components; a large main
peak, and a single shoulder on the high binding energy side.
Aer peak tting, the main peaks, centered at about 494.8 and486.3 eV, are assigned to Sn(II), while the secondary features, atabout 496.3 and 487.6 eV, are attributed to Sn(IV). The amount of
Sn(IV) content at the surface of the perovskite lms was 9% for
the control, 6% for TM-DHP-treated lms, as estimated fromthe ratio of the Sn(IV) peak to the total signal area. TM-DHP
eﬀectively scavenges Sn(IV) from the precursor materials,
resulting in less Sn(IV) in the perovskite lms. The Sn(IV) content
is reduced further, to 3%, for the TM-DHP and maltol treatedlms. The maltol helps to decrease the Sn(IV) content by protecting and passivating the surface of the perovskite lms,
making it more resistant to oxidation by the environment.
The eﬀect of the treatments on the lm morphology andcrystallinity were examined by the scanning electron microscopy (SEM) and X-ray diﬀraction (XRD), respectively. No obvious

Fig. 1 (a) Synthetic route, picture of single crystals, and ORTEP drawing of SnI(maltol) crystal structure with 50% thermal ellipsoids. (b) The crystal
packing structure of SnI(maltol). (c) Schematic illustration of the chelation between maltol molecules and undercoordinated Sn(II) species on theperovskite ﬁlm surface.

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6, and 3%, respectively. (d) XRD patterns of perovskite ﬁlms fabricated on PEDOT:PSS-coated FTO substrates. (e) Steady-state photoluminescence (PL) spectra, and (f) time-resolved photoluminescence (TRPL) decay curves of the perovskite ﬁlms fabricated on quartz substrates.
The carrier lifetime of the control, TM-DHP, and both TM-DHP and maltol treated perovskite ﬁlms is 1.3, 3.7, and 7.4 ms, respectively.

diﬀerences in grain size or roughness can be discerned from theSEM images (Fig. S10†), and the full-width at half-maximum(FWHM) of the XRD characteristic peaks are largely unaffected by the treatments (Fig. S11†). The lms treated with TMDHP, have improved crystallinity, as indicated by the stronger
intensities of the peaks at 14.5� and 28.8� , indexed to (100) and(200) planes of the perovskite, respectively (Fig. 2d). This may be
the result of the mediating inuence of TMP (tetramethylpyrazine), formed by the reaction of TM-DHP and SnF2,40 on theperovskite crystallization process.34 The intensity of the (100)and (200) peaks increased even more aer the maltol treatment,suggesting some additional improvement in lm crystallinity.
As the surface treatment involves washing the perovskite lmwith a solution of maltol dissolved in toluene, followed bya second annealing step, we speculate that the improvement incrystallinity in the treated lms could be caused by structural
reorganization during the annealing process.47–49
The treatments were found to have a considerable impact on
the charge carrier recombination dynamics, which are criticalfor achieving eﬃcient conversion of photons to electricalcharge. As shown in Fig. 2e, the PL intensity of the perovskite
lm prepared with TM-DHP is 2.2 times larger than that ofcontrol lm. Aer maltol post-treatment, the PL intensity
increases to become 4.7 times stronger than the control. The
increase in PL intensity indicates that non-radiative recombination is supressed, and, therefore, the trap states in theperovskite lms have been reduced by both the TM-DHP treatment and the maltol post-treatment.

The reduction in charge carrier recombination is conrmedby the charge carrier lifetimes, which are estimated from thetime resolved photoluminescence (TRPL) decay curves shown in
Fig. 2f. These measurements were made under a photon ux of
3.5 � 1011 photons per cm2, comparable to the incident ux
under AM1.5G. The lifetimes were found to depend on theincident light intensity,50 as shown in ESI Fig. S12 and S13.†
With Sn(IV) scavenging, the lifetime increased from 1.3 to 3.7 ms.
Aer maltol post-treatment, the lifetime reached a maximum of
7.4 ms. This is over six times longer than the value of 1.1 ms
previously reported for mixed Pb–Sn perovskite lms.7 Thisvalue, obtained for thin polycrystalline Pb–Sn perovskite layers,
is even comparable to those reported for state-of-the-art perovskite single crystals.51
Diﬀusion lengths could not be readily determined as we wereunable to estimate the charge carrier mobility from the spacecharge-limited current data.52 Instead, an approximate evaluation of the diﬀusion length was realized using reported values
for the diﬀusion coeﬃcients (D) of Pb–Sn perovskite.7 Using the
PL lifetime, t ¼ 7.4 ms, determined for our lm, and their reported values of 0.02–0.05 cm2 s�1 for the diﬀusion coeﬃcients,
pﬃﬃﬃﬃﬃ
the carrier diﬀusion length calculated from Dt, is estimatedto fall in the range of 3.8–6.1 mm. The local mobility of the holes
and electrons within individual perovskite grains can be estimated using ash-photolysis time-resolved microwave conductivity (TRMC) (Fig. S14 and S15†).53,54 The values are estimatedto be 70 cm2 V�1 s�1 and 110 cm2 V�1 s�1, respectively. Thesehigh values point to the overall high quality of the perovskite

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materials, which is also supported by the XRD and PL
experiments.
To conrm the impact of the improved charge carrier
recombination dynamics on the device performance, the corresponding PSCs were fabricated. The solar cells had an positive–intrinsic–negative structure: uorine-doped tin oxide(FTO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)/perovskite/fullerene (C60)/bathocuproine (BCP)/
silver (Ag) (Fig. 3a). The perovskite lm thickness was 800–
1000 nm. The current density–voltage (J–V) curves of the best
devices are shown in Fig. 3b, and the corresponding photovoltaic parameters are listed in Table 1. Measurements were madein inert atmosphere, under AM1.5G simulated solar radiation.
For control devices prepared without the TM-DHP or maltol
treatment, the highest PCE was 18.2% (forward scan, JSC ¼ 31.1
mA cm�2, VOC ¼ 0.78 V, and FF ¼ 0.75). With the TM-DHP but
without maltol treatment, the forward scan JSC, VOC, and FF wasslightly increased to 31.6 mA cm�2, 0.79 V, and 0.76, respectively, and the PCE reached 19.0%. Signicantly improved
performance was achieved when, in addition to TM-DHP
treatment, the perovskite layers were post-treated with maltol.
The champion PCE was 21.4% (reverse scan, JSC ¼ 33.1 mA
cm�2, VOC ¼ 0.82 V, and FF ¼ 0.79) and devices had considerably improved reproducibility (Fig. S16†). This PCE is very close
to the reported best performance for mixed Pb–Sn PSCs,
21.7%.12,13 In Fig. 3c, we can observe that the PSCs reached theTable 1

Photovoltaic parameters of the perovskite solar cells

DeviceScana

JSC (mA cm�2)

VOC (V)FF

PCE (%)

Control

Forward
ReverseForward
ReverseForward
Reverse

31.1
30.9
31.6
31.3
33.2
33.1

0.78
0.78
0.79
0.80
0.82
0.82

0.75
0.74
0.76
0.75
0.77
0.79

18.2
18.1
19.0
18.7
21.0
21.4

TM-DHP
TM-DHP + maltolaScan direction: forward and reverse denotes the scan direction from
JSC to VOC and from VOC to JSC, respectively.

highest external quantum eﬃciency (EQE) of 91.2% at 680 nm,
and the corresponding internal quantum eﬃciency (IQE) was
98.8%. The integrated JSC was 32.3 mA cm�2, somewhat lower
than the maximum value (33.2 mA cm�2) obtained from the J–V
curves. The diﬀerence is attributed to the spectral mismatch of
the solar simulator especially in near-infrared region. Considering the mismatch factor, which was calculated to be 1.027(Fig. S17†), the JSC values from the J–V curves correspond closelywith the integrated value.
To investigate the improved device performance in the viewof its electronic properties, additional characterizations of thedevices were performed. Impedance scans (Fig. 3d and S18†)
reveal a single semicircle for each device, the diameter of which

Fig. 3 (a) Schematic illustration and cross-sectional SEM image of a completed device with the architecture of FTO/PEDOT:PSS/perovskite/C60/
BCP/Ag. (b) J–V curves of the PSCs. (c) IQE, EQE, reﬂectance spectra and integrated JSC of the encapsulated champion device under AM1.5G
illumination in ambient air, no antireﬂection technique was applied for the device fabrication. (d) Complex impedance plots of PSCs measured ininert atmosphere under AM1.5G illumination. The shunt resistance across the perovskite layer was estimated at 93, 318, and 550 U cm2 for thecontrol, TM-DHP, and both TM-DHP and maltol treated PSCs, respectively. Insert shows the equivalent circuit model for ﬁtting the electrochemical impedance spectroscopy data. (e) The open-circuit voltage VOC as a function of illumination intensity with an ideality factor of 1.62,
1.60, and 1.50 for the control, TM-DHP, and both TM-DHP and maltol treated PSCs, respectively. (f) Dark current–voltage curves of the hole-only
devices with the architecture of FTO/PEDOT:PSS/perovskite/PTAA/Ag. PTAA is poly(triaryl amine).

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Chemical Scienceis equal to the parallel resistance of the equivalent circuit, rp. At
low applied voltage, rp equates to the shunt resistance acrossthe perovskite layer, estimated at 93, 318, and 550 U cm2 for thecontrol, TM-DHP, and both TM-DHP and maltol treated PSCs,
respectively. The increase in shunt resistance correlates with
the increase in output current of the PSCs, and conrms the
successively improved quality of the treated perovskite lms.
Charge carrier recombination mechanisms are reected by
the Shockley diode ideality factor, as determined by the slope of
the plot of VOC versus incident light-intensity (Fig. 3e).55,56 The
ideality factor is 1.62, 1.60 for the control and TM-DHP treateddevices, respectively, falling to 1.50 for the device treated withboth TM-DHP and maltol, indicating lower non-radiative (trapmediated) recombination rates in the maltol-treated PSCs.
To estimate the density of trap states in the lms, wemeasured the dark current–voltage (I–V) curves of the hole-onlyand electron-only devices (Fig. 3f). The voltage where thecurrent begins to sharply increase can be assigned to the traplled limit voltage (VTFL). VTFL is related to the trap density,
Ntrap, as VTFL ¼ Ntrap(eL2)/(23r30), where e is the elementarycharge of the electron, 30 is the vacuum permittivity, 3r is therelative dielectric constant of the perovskite (around 32),57 and L
is the thickness of the perovskite lm. VTFL for the perovskite
lms in the hole-only devices is 0.62, 0.54, and 0.14 V, respectively, corresponding to trap densities of 2.9 � 1015, 2.4 � 1015,
and 6.3 � 1014 cm�3. The electron trap densities for theperovskite lms modied with TM-DHP and maltol were estimated to be around 3.6 � 1014 cm�3 (Table S2, Fig. S19†). Theseelectrical measurements conrm the lower trap-state densities
in the treated perovskite lms, which leads to longer carrier
lifetimes of the treated perovskite lms, as well as improved
performance of the PSCs.

3.

Conclusions

In this study, we found that maltol, a cheap and common avor
enhancer, can coordinate to Sn(II) in SnI2 to form a stablecomplex (SnI(maltol)). Based on this strong aﬃnity of maltol for
Sn(II), we demonstrated that, when used in combination witha Sn(IV) scavenging method acting on the precursor solution,
post-treatment with maltol leads to suppressed Sn(IV) content,
decreased defect densities, and remarkably prolonged charge
carrier lifetimes in the perovskite lms, over 7 ms. A PCE of
21.4% was achieved for the champion solar cell. These highquality Pb–Sn materials achieved by the simple post-treatment
should be useful for wide variety of optoelectronic devices.

Author contributions
S. H. and A. W. conceived the idea. S. H. and K. O. performed thesynthesis and characterization of Sn complexes. S. H. and M. A.
T. conducted the XPS measurements. K. O. conducted the XRD
measurements. K. O. carried out the PL measurements withhelp of T. H., T. Y. and Y. K. R. N. and A. S. conducted the TRMC
measurements. S. H., M. A. T., and K. O. fabricated andmeasured the devices, and conducted SEM characterizations
with the help of Y. I. S. H. and K. O. carried out the PYS

measurements. R. M. conducted the impedance measurements.
S. H. conducted the SCLC measurements with the help of
R. M. M. A. T. and K. O. carried out the NMR measurements. S.
H., M. A. T., R. M., and A. W. prepared the manuscript. All
authors commented on the manuscript. A. W. supervised the
project.

Conﬂicts of interest
There are no conicts to declare.

Acknowledgements
This work was partially supported by JST-ALCA (JPMJAL1603),
JST-COI (JPMJCE1307), JST-CREST (JPMJCR16N3), and NEDO.
JSPS KAKENHI (JP19K05666, JP20K22531, JP20H00398,
JP20H05836, and JP21H04699), International Collaborative
Research Program of ICR, Kyoto University. Additional support
was received from MEXT Elements Strategy Initiative to Form
Core Research Center (JPMXP0112101001), JSPS for a Research
Fellowship for Young Scientists (JP21J14762) and the China
Scholarship Council. We thank Prof. Toshiyuki Nohira and Dr
Takayuki Yamamoto (Kyoto University) for XPS measurement,
Prof. Yuichi Shimakawa and Dr Masato Goto (Kyoto University)for XRD measurement. We thank Dr Tomoya Nakamura (Kyoto
University) for fruitful discussions. We thank Ajinomoto FineTechno Co., Inc. for providing the materials for device
encapsulation.

Notes and references
1 J. J. Yoo, G. Seo, M. R. Chua, T. G. Park, Y. Lu, F. Rotermund,
Y.-K. Kim, C. S. Moon, N. J. Jeon, J.-P. Correa-Baena,
V. Bulović, S. S. Shin, M. G. Bawendi and J. Seo, Nature,
2021, 590, 587–593.
2 J. Jeong, M. Kim, J. Seo, H. Lu, P. Ahlawat, A. Mishra, Y. Yang,
M. A. Hope, F. T. Eickemeyer, M. Kim, Y. J. Yoon, I. W. Choi,
B. P. Darwich, S. J. Choi, Y. Jo, J. H. Lee, B. Walker,
S. M. Zakeeruddin, L. Emsley, U. Rothlisberger,
A. Hagfeldt, D. S. Kim, M. Grätzel and J. Y. Kim, Nature,
2021, 592, 381–385.
3 M. Hu, M. Chen, P. Guo, H. Zhou, J. Deng, Y. Yao, Y. Jiang,
J. Gong, Z. Dai, Y. Zhou, F. Qian, X. Chong, J. Feng,
R. D. Schaller, K. Zhu, N. P. Padture and Y. Zhou, Nat.
Commun., 2020, 11, 151.
4 W. Shockley and H. J. Queisser, J. Appl. Phys., 1961, 32, 510–
519.
5 M. T. Klug, R. L. Milot, J. B. Patel, T. Green, H. C. Sansom,
M. D. Farrar, A. J. Ramadan, S. Martani, Z. Wang,
B. Wenger, J. M. Ball, L. Langshaw, A. Petrozza,
M. B. Johnston, L. M. Herz and H. J. Snaith, Energy
Environ. Sci., 2020, 13, 1776–1787.
6 A. Goyal, S. McKechnie, D. Pashov, W. Tumas, M. van
Schilfgaarde and V. Stevanović, Chem. Mater., 2018, 30,
3920–3928.
7 J. Tong, Z. Song, D. H. Kim, X. Chen, C. Chen,
A. F. Palmstrom, P. F. Ndione, M. O. Reese, S. P. Duneld,

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Open Access Article. Published on 27 September 2021. Downloaded on 6/24/2022 7:41:46 AM.
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

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O. G. Reid, J. Liu, F. Zhang, S. P. Harvey, Z. Li,
S. T. Christensen, G. Teeter, D. Zhao, M. M. Al-Jassim,
M. F. A. M. van Hest, M. C. Beard, S. E. Shaheen,
J. J. Berry, Y. Yan and K. Zhu, Science, 2019, 364, 475.
8 T. Jiang, Z. Chen, X. Chen, T. Liu, X. Chen, W. E. I. Sha,
H. Zhu and Y. Yang, Sol. RRL, 2020, 4, 1900467.
9 R. Lin, K. Xiao, Z. Qin, Q. Han, C. Zhang, M. Wei,
M. I. Saidaminov, Y. Gao, J. Xu, M. Xiao, A. Li, J. Zhu,
E. H. Sargent and H. Tan, Nat. Energy, 2019, 4, 864–873.
10 C. Li, Z. Song, D. Zhao, C. Xiao, B. Subedi, N. Shrestha,
M. M. Junda, C. Wang, C.-S. Jiang, M. Al-Jassim,
R. J. Ellingson, N. J. Podraza, K. Zhu and Y. Yan, Adv.
Energy Mater., 2019, 9, 1803135.
11 J. Xi and M. A. Loi, ACS Energy Lett., 2021, 6, 1803–1810.
12 K. Xiao, R. Lin, Q. Han, Y. Hou, Z. Qin, H. T. Nguyen, J. Wen,
M. Wei, V. Yeddu, M. I. Saidaminov, Y. Gao, X. Luo, Y. Wang,
H. Gao, C. Zhang, J. Xu, J. Zhu, E. H. Sargent and H. Tan, Nat.
Energy, 2020, 5, 870–880.
13 G. Kapil, T. Bessho, T. Maekawa, A. K. Baranwal, Y. Zhang,
M. A. Kamarudin, D. Hirotani, Q. Shen, H. Segawa and
S. Hayase, Adv. Energy Mater., 2021, 11, 2101069.
14 G. Kapil, T. Bessho, C. H. Ng, K. Hamada, M. Pandey,
M. A. Kamarudin, D. Hirotani, T. Kinoshita, T. Minemoto,Q. Shen, T. Toyoda, T. N. Murakami, H. Segawa and
S. Hayase, ACS Energy Lett., 2019, 4, 1991–1998.
15 Z. Yang, Z. Yu, H. Wei, X. Xiao, Z. Ni, B. Chen, Y. Deng,
S. N. Habisreutinger, X. Chen, K. Wang, J. Zhao,
P. N. Rudd, J. J. Berry, M. C. Beard and J. Huang, Nat.
Commun., 2019, 10, 4498.
16 M. Wei, K. Xiao, G. Walters, R. Lin, Y. Zhao,
M. I. Saidaminov, P. Todorović, A. Johnston, Z. Huang,
H. Chen, A. Li, J. Zhu, Z. Yang, Y.-K. Wang, A. H. Proppe,
S. O. Kelley, Y. Hou, O. Voznyy, H. Tan and E. H. Sargent,Adv. Mater., 2020, 32, 1907058.
17 W. Ke, C. Chen, I. Spanopoulos, L. Mao, I. Hadar, X. Li,
J. M. Hoﬀman, Z. Song, Y. Yan and M. G. Kanatzidis, J.
Am. Chem. Soc., 2020, 142, 15049–15057.
18 C. Li, Z. Song, C. Chen, C. Xiao, B. Subedi, S. P. Harvey,
N. Shrestha, K. K. Subedi, L. Chen, D. Liu, Y. Li,
Y.-W. Kim, C.-s. Jiang, M. J. Heben, D. Zhao,
R. J. Ellingson, N. J. Podraza, M. Al-Jassim and Y. Yan, Nat.
Energy, 2020, 5, 768–776.
19 R. Prasanna, T. Leijtens, S. P. Duneld, J. A. Raiford,
E. J. Wolf, S. A. Swier, J. Werner, G. E. Eperon, C. de
Paula, A. F. Palmstrom, C. C. Boyd, M. F. A. M. van Hest,
S. F. Bent, G. Teeter, J. J. Berry and M. D. McGehee, Nat.
Energy, 2019, 4, 939–947.
20 J. Tong, J. Gong, M. Hu, S. K. Yadavalli, Z. Dai, F. Zhang,
C. Xiao, J. Hao, M. Yang, M. A. Anderson, E. L. Ratcliﬀ,
J. J. Berry, N. P. Padture, Y. Zhou and K. Zhu, Matter, 2021,
4, 1365–1376.
21 E. Ruggeri, M. Anaya, K. Gałkowski, G. Delport,
F. U. Kosasih, A. Abfalterer, S. Mackowski, C. Ducati and
S. D. Stranks, Adv. Mater., 2019, 31, 1905247.
22 F. Li, X. Deng, F. Qi, Z. Li, D. Liu, D. Shen, M. Qin, S. Wu,
F. Lin, S.-H. Jang, J. Zhang, X. Lu, D. Lei, C.-S. Lee, Z. Zhu
and A. K. Y. Jen, J. Am. Chem. Soc., 2020, 142, 20134–20142.

23 A. Y. Alsalloum, B. Turedi, K. Almasabi, X. Zheng,
R. Naphade, S. D. Stranks, O. F. Mohammed andO. M. Bakr, Energy Environ. Sci., 2021, 14, 2263–2268.
24 S. Wu, Z. Li, M.-Q. Li, Y. Diao, F. Lin, T. Liu, J. Zhang, P. Tieu,
W. Gao, F. Qi, X. Pan, Z. Xu, Z. Zhu and A. K. Y. Jen, Nat.
Nanotechnol., 2020, 15, 934–940.
25 M. I. Saidaminov, I. Spanopoulos, J. Abed, W. Ke, J. Wicks,
M. G. Kanatzidis and E. H. Sargent, ACS Energy Lett., 2020,
5, 1153–1155.
26 J. Pascual, G. Nasti, M. H. Aldamasy, J. A. Smith, M. Flatken,
N. Phung, D. Di Girolamo, S.-H. Turren-Cruz, M. Li,
A. Dallmann, R. Avolio and A. Abate, Mater. Adv., 2020, 1,
1066–1070.
27 T.-B. Song, T. Yokoyama, C. C. Stoumpos, J. Logsdon,
D. H. Cao, M. R. Wasielewski, S. Aramaki and
M. G. Kanatzidis, J. Am. Chem. Soc., 2017, 139, 836–842.
28 T.-B. Song, T. Yokoyama, S. Aramaki and M. G. Kanatzidis,
ACS Energy Lett., 2017, 2, 897–903.
29 F. Wang, J. Ma, F. Xie, L. Li, J. Chen, J. Fan and N. Zhao, Adv.
Funct. Mater., 2016, 26, 3417–3423.
30 Q. Chen, J. Luo, R. He, H. Lai, S. Ren, Y. Jiang, Z. Wan,
W. Wang, X. Hao, Y. Wang, J. Zhang, I. Constantinou,
C. Wang, L. Wu, F. Fu and D. Zhao, Adv. Energy Mater.,
2021, 11, 2101045.
31 K. J. Savill, A. M. Ulatowski and L. M. Herz, ACS Energy Lett.,
2021, 6, 2413–2426.
32 L. Xu, X. Feng, W. Jia, W. Lv, A. Mei, Y. Zhou, Q. Zhang,
R. Chen and W. Huang, Energy Environ. Sci., 2021, 14,4292–4317.
33 F. Gu, S. Ye, Z. Zhao, H. Rao, Z. Liu, Z. Bian and C. Huang,
Sol. RRL, 2018, 2, 1800136.
34 S. J. Lee, S. S. Shin, Y. C. Kim, D. Kim, T. K. Ahn, J. H. Noh,
J. Seo and S. I. Seok, J. Am. Chem. Soc., 2016, 138, 3974–3977.
35 Q. Tai, X. Guo, G. Tang, P. You, T.-W. Ng, D. Shen, J. Cao,
C.-K. Liu, N. Wang, Y. Zhu, C.-S. Lee and F. Yan, Angew.
Chem., Int. Ed., 2019, 58, 806–810.
36 Z. Lin, C. Liu, G. Liu, J. Yang, X. Duan, L. Tan and Y. Chen,
Chem. Commun., 2020, 56, 4007–4010.
37 M. Ozaki, Y. Katsuki, J. Liu, T. Handa, R. Nishikubo,
S. Yakumaru, Y. Hashikawa, Y. Murata, T. Saito,
Y. Shimakawa, Y. Kanemitsu, A. Saeki and A. Wakamiya,
ACS Omega, 2017, 2, 7016–7021.
38 J. Liu, M. Ozaki, S. Yakumaru, T. Handa, R. Nishikubo,
Y. Kanemitsu, A. Saeki, Y. Murata, R. Murdey andA. Wakamiya, Angew. Chem., Int. Ed., 2018, 57, 13221–13225.
39 T. Nakamura, T. Handa, R. Murdey, Y. Kanemitsu andA. Wakamiya, ACS Appl. Electron. Mater., 2020, 2, 3794–3804.
40 T. Nakamura, S. Yakumaru, M. A. Truong, K. Kim, J. Liu,
S. Hu, K. Otsuka, R. Hashimoto, R. Murdey, T. Sasamori,
H. D. Kim, H. Ohkita, T. Handa, Y. Kanemitsu andA. Wakamiya, Nat. Commun., 2020, 11, 3008.
41 D. Luo, X. Li, A. Dumont, H. Yu and Z. H. Lu, Adv. Mater.,
2021, 33, e2006004.
42 J. Xue, R. Wang and Y. Yang, Nat. Rev. Mater., 2020, 5, 809–
827.
43 M. A. Kamarudin, D. Hirotani, Z. Wang, K. Hamada,K. Nishimura, Q. Shen, T. Toyoda, S. Iikubo, T. Minemoto,

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K. Yoshino and S. Hayase, J. Phys. Chem. Lett., 2019, 10,5277–5283.
44 W. Ke, C. C. Stoumpos and M. G. Kanatzidis, Adv. Mater.,
2019, 31, 1803230.
45 S. Shahbazi, M.-Y. Li, A. Fathi and E. W.-G. Diau, ACS Energy
Lett., 2020, 5, 2508–2511.
46 M. C. Barret, M. F. Mahon, K. C. Molloy, J. W. Steed and
P. Wright, Inorg. Chem., 2001, 40, 4384–4388.
47 J. Xue, R. Wang, K.-L. Wang, Z.-K. Wang, I. Yavuz, Y. Wang,
Y. Yang, X. Gao, T. Huang, S. Nuryyeva, J.-W. Lee, Y. Duan,
L.-S. Liao, R. Kaner and Y. Yang, J. Am. Chem. Soc., 2019,
141, 13948–13953.
48 T. Wu, Y. Wang, X. Li, Y. Wu, X. Meng, D. Cui, X. Yang and
L. Han, Adv. Energy Mater., 2019, 9, 1803766.
49 H. Zhang, Y. Wu, C. Shen, E. Li, C. Yan, W. Zhang, H. Tian,
L. Han and W.-H. Zhu, Adv. Energy Mater., 2019, 9, 1803573.
50 Y. Yamada, T. Nakamura, M. Endo, A. Wakamiya and
Y. Kanemitsu, J. Am. Chem. Soc., 2014, 136, 11610–11613.

51 Y. Liu, Y. Zhang, X. Zhu, Z. Yang, W. Ke, J. Feng, X. Ren,
K. Zhao, M. Liu, M. G. Kanatzidis and S. Liu, Sci. Adv.,
2021, 7, eabc8844.
52 L. Gao, K. Zeng, J. Guo, C. Ge, J. Du, Y. Zhao, C. Chen,
H. Deng, Y. He, H. Song, G. Niu and J. Tang, Nano Lett.,
2016, 16, 7446–7454.
53 N. Ishida, A. Wakamiya and A. Saeki, ACS Photonics, 2016, 3,
1678–1688.
54 E. M. Hutter, J.-J. Hofman, M. L. Petrus, M. Moes,
R. D. Abellón, P. Docampo and T. J. Savenije, Adv. Energy
Mater., 2017, 7, 1602349.
55 P. Caprioglio, C. M. Wolﬀ, O. J. Sandberg, A. Armin, B. Rech,
S. Albrecht, D. Neher and M. Stolterfoht, Adv. Energy Mater.,
2020, 10, 2000502.
56 T. S. Sherkar, C. Momblona, L. Gil-Escrig, J. Ávila,
M. Sessolo, H. J. Bolink and L. J. A. Koster, ACS Energy
Lett., 2017, 2, 1214–1222.
57 Q. Dong, Y. Fang, Y. Shao, P. Mulligan, J. Qiu, L. Cao and
J. Huang, Science, 2015, 347, 967.

Chem. Sci., 2021, 12, 13513–13519 | 13519© 2021 The Author(s). Published by the Royal Society of Chemistry－163－

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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
令和３年度国際共同利用・共同研究公募要領
京都大学化学研究所は、「化学に関する特殊事項の学理及び応用の研究を掌る」ために、化学を中心とする分野で基礎研究に重点を置いた先端研究に邁進してまいりました。平成２２〜３０年度の期間には、文部科学大臣から国立大学共同利用・共同研究拠点としての認定を受け、化学研究所の活性を基盤とする「化学関連分野の深化・連携を基軸とする先端・学際研究拠点」として国内外の化学関連分野の研究者との共同利用・共同研究を推し進めてまいりました。この拠点活動におけるグローバル共同利用・共同研究が評価され、平成３０年化学研究所は文部科学省から国際共同利用・共同研究拠点に認定されました。これを受けて、平成
３１年度からの国際共同利用・共同研究拠点活動においては、多様でグローバルな化学分野の共同研究を一層強力に推進すべく、さらなる事業展開を図っております。
つきましては、化学が関わる分野でご活躍の皆様のご意見・ご要望を尊重しつつ、世界の化学の基礎・応用研究を皆様とともに一層推進することを念頭に置き、下記の要領で令和 3 年度の拠点共同利用・共同研究の課題公募をさせて頂きたく存じます。
この公募に当たりましては、分野選択型（計画研究型）、課題提案型、連携・融合促進型および施設・機器利用型の四つに分けて研究課題を募集いたします。これらの課題の実施に際しては当研究所の専任教員または客員教員との共同研究を基調といたしますが、いずれの課題でも後述の共通設備・機器・資料等のご利用が可能です。なお、各課題とも、海外研究者を研究代表者あるいは研究協力者とする国際共同研究（この場合、英語フォームで申請下さい）と、国内研究者を研究代表者とする国内共同研究を実施致します。これらの点も勘案いただき、本公募要領の詳細について十分ご確認の上、期日までにご申請下さいますようお願いいたします。
京都大学化学研究所長
辻井敬亘
共同研究ステーション長 寺西利治

1．研究期間１年間（令和３年４月１日から令和４年３月３１日まで）。
2．研究課題分類
下記のような分類（型）ごとに研究課題を募集いたします。いずれの課題についても、分類ないし分野の担当者もしくは当研究所で対応する共同研究者にご一報の上、ご申請下さい。また、研究経費に関しては、
p.3 の表をご覧下さい。
2-1．分野選択型（計画研究型）研究課題
分野選択型（計画研究型）研究課題は、あらかじめ設定された分野に関して化学研究所内の研究者と共同で遂行する課題です。令和２年度は下記の５分野について課題を公募いたします。５分野を合わせて、萌芽的な課題と発展的な課題をそれぞれ２０件程度、採択の予定です。
ビーム科学分野（担当者：若杉 昌徳；wakasugi.masanori.8z@kyouto-u.ac.jp）
基本テーマ：先進量子ビームの開発と新奇診断分析手法の創出
趣旨：レーザー、X 線、電子線、イオンビームなどの量子ビームの高度化とその先端的診断分析法への応用を進めます。また、これらの量子ビームを複合的に用いて、極微細領域での超高速化学・物理現象の解明を目指します。
元素科学分野（担当者：中村 正治; masaharu@scl.kyoto-u.ac.jp）
基本テーマ：元素科学に基づく物質創製・機能創出
趣旨：元素の新たな特性を引き出し、この特性をもとに優れた機能を有する新物質を創製します。元素と社会との関わりを俯瞰した元素戦略研究も推進します。物質の機能は、構成元素の特性を相乗的に反映して発現します。この発現機構を明らかとし、望みの機能を意のままに創出することを目指します。

-1－165－

バイオ情報学分野（担当者：緒方 博之; ogata@kuicr.kyoto-u.ac.jp）
基本テーマ：バイオ情報を含む複合情報の融合解析
趣旨：ゲノムやメタゲノムに代表される最新バイオ情報に立脚して、バイオ情報がいかに生体内や自然環境における化学現象と関わっているかを明らかにし、生命システムについての化学的理解の深化を図ります。さらに、その成果を応用して、ゲノム創薬やパーソナライズド医療などへの展開も目指します。
物質合成分野（担当者：村田 靖次郎; yasujiro@scl.kyoto-u.ac.jp）
基本テーマ：複合機能材料の戦略的創製
趣旨：異種材料のハイブリッド化・複合化ならびにナノサイズ化に重点を置き、新規な機能をもつ新世代材料の創製を目指すとともに、生体の認識、応答、反応などの諸機能を担う例えば生体膜等も複合機能材料と捉え、機能物質と生命現象の化学的相関の解明も目指します。
現象解析分野（担当者：寺西 利治; teranisi@scl.kyoto-u.ac.jp）
基本テーマ：複合測定に基づく物質解析
趣旨：化学を基盤とする多種の分光学的手法・解析的手法を複合的に駆使して、天然および人工物質の構造・性質を分子レベルから巨視的レベルまで階層的に理解・記述することを目指し、一方、その結果を還元することによって新たな物質科学の枠組みを構築する取組みも目指します。
2-2．課題提案型研究課題（担当者：梶 弘典; kaji@scl.kyoto-u.ac.jp）
課題提案型研究課題は、前項１で設定した一つの分野に留まらない分野、あるいはそれ以外の分野について、化学関連分野の研究者から自由にご提案いただく課題です。萌芽的な課題と発展的な課題を、それぞれ２０件程度、採択の予定です。新分野の開拓につながるような課題を特に歓迎いたします。なお、緊急性・重要性が極めて高いと判断した課題については、前記の応募期日にかかわらず、直ちに採択することもあります。
2-3．連携・融合促進型研究課題（担当者：渡辺 宏; hiroshi@scl.kyoto-u.ac.jp）
連携・融合促進型研究課題は、化学関連分野における国内外の研究連携の強化を主目的とする共同研究課
題 で す 。 国 外 も 念 頭 に 置 く 場 合 は 、 化 学 研 究 所 の 部 局 間 国 際 学 術 交 流 締 結 先 (http://www.kuicr.
kyoto-u.ac.jp/sites/international_exchange/agreement/ 参照)との共同研究を開始する場を求めていただくことも可能です。また、この目的に沿った研究集会の開催も本課題として応募いただけます。５件程度を採択する予定です。
2-4．施設・機器利用型研究課題（担当者：倉田 博基; kurata@eels.kuicr.kyoto-u.ac.jp）
施 設 ・ 機 器 利 用 型 研 究 課 題 は 、 http://www.kuicr.kyoto-u.ac.jp/sites/research_activities/joint_research/kaken_kyodo_instr/(拠点ホームページ)に記載の共通設備・機器・資料等の利用を主とする共同研究課題です。
１５件程度を採択する予定です。

-2－166－令和３年度国際共同利用・共同研究経費概算値

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

分野選択型発展的研究

2,000

1,500

課題提案型萌芽的研究

1,000

800

課題提案型発展的研究

2,000

1,500

連携・融合促進型研究

1,000

800

施設・機器利用型研究

1,000

800

*表中の金額は目安です。予算の状況に応じた減額もありえますことをご了解下さい。
経費内での備品費、消耗品費、旅費の配分は、申請者と化学研究所の共同研究者が協議して決定下さい。特に、旅費については、地域性を勘案してご決定下さい。

3．共同研究応募方法
3-1．申請資格
国公私立大学、国公私立研究機関、独立行政法人等の専任研究者、または、これに準ずる者。
3-2．申請書記入要領
申請に当たっては、該当する募集分類・分野の担当者もしくは当研究所で対応する共同研究者と、事前に研究課題、研究内容、研究経費に関して、必ずご協議下さい。対応する共同研究者は、当研究所の専任教員
または令和２年度客員教員からお選び下さい。なお、教員のリストは下記の化学研究所ホームページをご参照下さい。
教員リスト http://www.kuicr.kyoto-u.ac.jp/sites/research_activities/chemist/
また、対応する共同研究者をお決めになれない場合は、各分類・分野の担当者に、まず、ご相談ください。
上記の表の経費上限は目安です。特に、経費内での備品費、消耗品費、旅費の配分については、当研究所で対応する共同研究者と十分にご協議の上で申請下さい。特に、旅費については、地域性を勘案してご申請下さい。
課題申請は、本要領に添付の分野選択型共同利用・共同研究申請書（様式１）、課題提案型共同利用・共同
研究申請書（様式２）、連携・融合促進型共同利用・共同研究申請書（様式３）、施設・機器利用型共同利用・共同研究申請書（様式４）に必要事項を記入し、下記の要領で、化学研究所共同研究推進室にご提出下さい。
なお、各課題とも、海外研究者を研究代表者あるいは研究協力者とする国際共同研究も実施可能です。この場合、英語フォーム（Forms 1~4）の左肩の欄にチェックを入れて、当研究所の共同研究者に提出をご依頼下さい。
<記入上の注意事項>
1. ※を付した事項は当研究所で記入します。
2. 当研究所で対応する共同研究者は必ずご記入下さい。
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３年１月１８（月）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)38-3121-3－167－

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３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４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、WEBから提出してください。なお、ファイル名は「課題番号＋代表者名（姓）」として下さい（例：2021-1 田中.doc、
2021-1 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。

-4－168－－169－

Gas sensing properties research of metal oxides

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

Investigating iron nitrides prepared by new high-pressure synthesis with Mössbauer spectroscopy

C-H Borylation and Silylation under visible-light enabled Fe-catalysis

Development of Iron-based Electrocatalysts for Electrocatalytic Conversion of Biomass into Value Added Chemicals

Iron-Catalyzed Asymmetric Carbozincation and Ring-Opening Reactions of Oxabicyclic Alkenes

若杉 昌徳

大木 靖弘

梶 弘典

島川 祐一

島川 祐一

島川 祐一

時任 宣博

中村 正治

中村 正治

中村 正治

国立研究開発法人量子科学技術研究開発機構

理化学研究所・仁科加速器科学研究センター

Hokkaido University, Institute of Low Temperature
ScienceJulius-Maximilians-Universität Würzburg, Institut für
Anorganische Chemie

Ningbo Institute of Industrial Technology (CNITECH) of
the Chinese Academy of Sciences

National Taiwan University, Center for Condensed
Matter Sciences

Centre for Science at Extreme Conditions and Schoolof Chemistry, University of Edinburgh

Institute for Inorganic Chemistry, University of Bonn

Tohoku University, Department of Chemistry

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

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

2021-6 大西 哲哉

2021-7 W. M. C. Sameera

2021-8 Todd B. Marder2021-9 Haichuan Guo2021-10 Wei-Tin Chen

2021-11 Simon D. Kloß2021-12 Rainer Streubel

2021-13 Takeaki Iwamoto

2021-14 Alakananda Hajra

2021-15 Apurba K. Das2021-16 Laksmikanta Adak

時任 宣博

小川原 亮

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

2 萌芽的 国際

2 萌芽的 国際

2 萌芽的 国際

2 発展的 国際

2 発展的 国際

2 萌芽的 国際

2 発展的 国際

2 萌芽的 国際

2 発展的 国際

2 萌芽的 国際

1 萌芽的

1 萌芽的

1 発展的

1 発展的

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

金属酸化物におけるガスセンサー性能研究

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

フッ素化三配位ホウ素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

Fe] Clusters
Clusters and its Relation to the catalytic N2-Reduction: A Computational
Electronic Structure of Biomimetic [Mo[Mo 33SS44Fe]
Computational Study
Study

理論計算による酵素模倣型[Mo3S4Fe]クラスターの電子構造解析およびN2 還元反応解析

Development of new nano-structure target for ISOL

ナノ構造を持つ ISOL 用標的の開発

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

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

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

蓄積リングのための位置感度型アクティブ標的の開発

2021-5 小平 聡

井上 峻介

分野選択型

1 萌芽的

大阪大学・レーザー科学研究所

藤井 知実

分野選択型

Synthesis and optical characterization of gold nanohelices with controllable aspect ratio

アスペクト比の制御された金ナノらせんの合成および光学特性評価

課題名（和文・英文）

2021-4 砂原 淳

国際関西大学・化学生命工学部

実施
状況

1 萌芽的

選択
分野

2021-3 老川 典夫

若杉 昌徳

分野選択型

型

理研仁科センター・実験装置開発室

倉田 博基

化研内
研究協力者

2021-2 山口 由高

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

2021-1 中川 充

課題番号化学研究所 国際共共拠点 R3年度採択課題（応募199件，採択 133件，採択率 66.8 %，国際共同研究割合44.4％）

－170－
馬見塚 拓

東京工業大学・理学院

横浜国立大学・工学研究院

名桜大学・リベラルアーツ機構

横浜国立大学・大学院工学研究院

京都市産業技術研究所・高分子系チーム

筑波大学・数理物質系化学域

岡山大学・大学院自然科学研究科

National Chiao Tung University, Department of Biological
Science and Technology/Institute of Bioinformatics &阿久津 達也 分野選択型
Systems Biology

遠藤 寿

大阪府立大学・大学院工学研究科

Monash University・Biomedicine Discovery Institute

CNRS/Genoscope/UMR8030

LS2N, CNRS UMR6004

Nagoya Institute of Technology, Depertment ofComputer Science

東邦大学・理学部情報科学科

高知大学・理工学部門

大阪大学・微生物病研究所

2021-20 佐藤 琢哉

2021-21 藪内 直明

2021-22 立津 慶幸

2021-23 山口 佳隆

2021-24 橘 洋一

2021-25 笹森 貴裕

2021-26 光藤 耕一

2021-27 Jinn-Moon Yang

2021-28 Jiangning Song2021-29 Tom Delmont

2021-30 Samuel Chaffron

2021-31 Masayuki Karasuyama2021-32 ホセ ナチェル

2021-33 長崎 慶三

2021-34 渡辺 登喜子

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

緒方 博之

緒方 博之

分野選択型

分野選択型

阿久津 達也 分野選択型

緒方 博之

阿久津 達也 分野選択型

若宮 淳志

若宮 淳志

中村 正治

中村 正治

寺西 利治

菅 大介

廣理 英基

金光 義彦

分野選択型

2021-19 桐谷 乃輔

金光 義彦

東海大学・工学部 光・画像工学科

分野選択型

2021-18 立崎 武弘

大木 靖弘

徳島大学・大学院社会産業理工学研究部

2021-17 小笠原 正道

3 萌芽的

3 発展的

3 萌芽的

3 萌芽的 国際

3 発展的 国際

3 発展的 国際

3 発展的 国際

3 発展的 国際

2 萌芽的

2 発展的

2 萌芽的

2 発展的

2 発展的

2 萌芽的

2 発展的

2 萌芽的

2 萌芽的

2 萌芽的

Development of the method for the detection of coronavirus diversity

コロナウイルス多様性検出法の開発

Comprehensive analysis of viral succession during the transition of multiple types of algal blooms

複数種の赤潮の消長過程におけるウイルス叢遷移様態の網羅的解析

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

A Study on Statistical Mashine Learning for Efficient Graph Structurred 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 associations between giant viruses and eukaryotes in the global ocean through community networks inference and mining

群集ネットワーク推定とマイニングを用いた全球海洋における巨大ウイルスの宿主生物予測

Unveiling the genomic contents of ecologically important marine giant viruses

生態学的に重要な海洋巨大ウイルスのゲノムの解明

Developing data-driven deep learning approaches for accurate identification of protease-specific substrate targets and cleavage sites

タンパク質分解酵素の標的タンパク質と切断部位の正確な予測のためのデータ駆動型深層学習方式の開発

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

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

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

Functionalization of urushiol coating film using magnetic particles

磁性微粒子を用いたウルシオール塗膜の機能発現

Development of collaborative reaction fields based on dinuclearization of mononuclear complexes

単核錯体の複核化による協働的反応場の開発

Study on the physical mechanism on novel-ternary nanoparticle formation

新奇三元系ナノ粒子形成の物理的起源に関する研究

Exploration of energy materials by high pressure synthesis technique

高圧合成法を利用したエネルギー材料の開発

Magnon-phonon excitation in multiferroic materials by intense pulses

高強度テラヘルツパルスを駆使したマルチフェロイック物質におけるマグノン・フォノン励起

Strong carrier modulation in 2D semiconducting materials by coupled molecular vibrations

微弱な分子振動モードと結合させた極薄膜半導体における励起子発光の変調

Development of THz-STM for low-temperature and high magnetic field

極低温強磁場対応THz-STM の開発

Synthesis of ferrocenyl-phosphines and their application in the preparation of Fe clusters

フェロセニル基を持つホスフィン配位子の合成とFe クラスター化反応への応用

－171－梶 弘典

村田 靖次郎 分野選択型

若宮 淳志

University of St Andrews, Organic Semiconductor
Centre, EaStCHEM School of Chemistry

Rudjer Boskovic Institute, Division of organic chemistry
and biochemistry, Laboratory for physical organic
chemistry

Department of Applied Chemistry, Graduate School ofEngineering, Osaka University

鈴鹿医療科学大学・保健衛生学部医療栄養学科

大阪大学・大学院工学研究科

大阪工業大学・応用化学科

2021-36 Markus W. Ribbe2021-37 Eli Zysman-Colman

2021-38 MARGETIC, Davor

2021-39 Akinori Saeki

2021-40 若林 成知

2021-41 武田 洋平

2021-42 平井 智康

分野選択型

分野選択型

分野選択型

分野選択型

登阪 雅聡

宗林 由樹

竹中 幹人

佐藤 健

佐藤 健

渡辺 宏

大阪大学・大学院基礎工学研究科物質創成専攻

静岡大学・グリーン科学技術研究所（および理学部）

東北大学・未来科学技術共同研究センター

Academia Sinica, Research Center for Environmental
Changes

Stony Brook University, Department of Material Science
and Chemical Engineering

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

Graduate School of Organic Materials Science,
Yamagata University

Graduate School of Organic Materials Science,
Yamagata University

神戸大学・分子フォトサイエンス研究センター

2021-44 清水 章弘

2021-45 小林 健二

2021-46 髙橋 裕

2021-47 Ho, Tung-Yuan

2021-48 Tadanori Koga

2021-49 Giovanni Ianniruberto

2021-50 Sathish K. Sukumaran

2021-51 Visit Vao-soongnern

2021-52 小堀 康博

梶 弘典

山子 茂

廣瀨 崇至

大阪大学・大学院工学研究科

2021-43 鈴木 充朗

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

村田 靖次郎 分野選択型

竹中 幹人

梶 弘典

大木 靖弘

分野選択型

大木 靖弘

University of California, Irvine, Department of Molecular
Biology and Biochemistr

分野選択型

分野選択型

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 馬見塚 拓

2021-35 茅野 光範

5 発展的

5 萌芽的 国際

5 発展的 国際

5 萌芽的 国際

5 発展的 国際

5 発展的 国際

4 萌芽的

4 発展的

4 発展的

4 発展的

4 萌芽的

4 発展的

4 萌芽的

4 発展的 国際

4 発展的 国際

4 発展的 国際

4 萌芽的 国際

3 発展的

Vibronic Effect between Photon and Energy Conversions Studied by Solid State NMR and Time Resolved EPR Spectroscopy

光エネルギー変換に対する振電効果：固体NMR と時間分解EPR の連携による解明

Molecular understanding on the structures and dynamics of end-modified polymers

末端修飾高分子の構造とダイナミクスに関する研究

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

Development of simulation scheme for wall-slip of polymers

高分子の壁面滑りを計算するシミュレーション手法の開発

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

高分子ナノコンポジットの補強メカニズムの解明

Trace metal elemental and isotopic composition in the North Pacific Ocean: sources and internal cycling (2)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(2)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 and Properties of π -Conjugated Zwitterions with Negligible Solvatochromism

ソルバトクロミズムを示さないπ共役双性イオンの合成と物性

Development of nonsymmetrical organic semiconducting molecules toward efficient photovoltaics

高効率光電変換を志向した非対称型有機半導体分子の開発

Chiral Silica with preferred-handed helical structure via chiral transfer

キラル転写に基づく新規キラルシリカの調製

Development of thermally activated delayed fluorescent materials based on through-space charge transfer using dibenzophenazine as
an electron-acceptor

ジベンゾフェナジンを電子アクセプターとするスルースペース電荷移動型熱活性化遅延蛍光材料の創製

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

Development of hole transport materials for tin-perovskite and device characterization

スズペロブスカイトに特化したホール輸送材の開発と素子評価

Exploration of Cycloaddition Properties of Guanidine Functionalized Isobenzofurans

グアジニン修飾イソベンゾフランの付加環化反応の開発

Development of new blue TADF emitters with horizontal molecular orientations

分子配向を制御した新規青色TADF 発光材料の開発

Synthesis of inorganic molecules for elucidation of biosynthetic pathways of iron-sulfur clusters

鉄硫黄クラスターの生合成過程解明に資する無機分子の合成

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開発と医学・農学への応用

－172－

松宮 由実

松宮 由実

小野 輝男

小野 輝男

小野 輝男

関西学院大学・工学部

名古屋工業大学・大学院工学研究科

北海道大学・触媒科学研究所

群馬大学・大学院理工学府

京都工芸繊維大学・繊維学系

京都大学・生命科学研究科

大阪大学・大学院理学研究科

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

MRC Laboratory of Molecular Biology

Peking University, School of Life Sciences

Tsinghua University, Department of Chemistry

Fudan University, School of Pharmacy

University of Ulsan

Korea Advanced Institute of Science and Technology,
Department of Physics

Far Eastern Federal University, School of Natural
Science

Department of Information Display

2021-55 藤原 明比古

2021-56 山本 勝宏

2021-57 飯田 健二

2021-58 園山 正史

2021-59 青木 隆史

2021-60 河内 孝之

2021-61 浦川 理

2021-62 Zhijie Zhang

2021-63 Yohei Ohashi

2021-64 Zhong, Sheng2021-65 Yan-Mei Li

2021-66 Lu Zhou

2021-67 Sanghoon Kim

2021-68 Kab-Jin Kim

2021-69 Alexander Samardak

2021-70 Jang Hyuk Kwon

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

梶 弘典

上杉 志成

上杉 志成

青山 卓史

青山 卓史

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

分野選択型

山口 信次郎 分野選択型

長谷川 健

長谷川 健

寺西 利治

竹中 幹人

竹中 幹人

宗林 由樹

京都教育大学・教育学部理学科

2021-54 向井 浩

宗林 由樹

近畿大学・理工学部

2021-53 中口 譲

発展的 国際

萌芽的 国際

発展的 国際

発展的 国際

発展的 国際

萌芽的 国際

発展的 国際

萌芽的 国際

萌芽的 国際

5 発展的

5 萌芽的

5 萌芽的

5 発展的

5 発展的

5 発展的

5 発展的

5 萌芽的

5 萌芽的

Highly efficient red thermally activated delayed fluorescence emitters with sterically hindered donor skeleton

剛直なドナー骨格を用いた赤色熱活性遅延蛍光材料の開発

Application of ferrimagnets for spintronics devices

フェリ磁性体のスピントロニクス応用

Study of characteristics of spin wave in magnetic insulator

磁性絶縁体でのスピン波研究

Orbitronics with new material systems

新規材料を用いたオービトロニクス

Site-Selective Protein Acetylation by a Small Molecule

小分子化合物による選択的タンパク質アセチル化

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

Role of Phosphoinositide Signaling in Pollen Development

花粉形成におけるホスホイノシチドシグナルの役割

Role of PX-PH-type Phospholipase Ds in Plant Intracellular Membrane Traffic

植物細胞内の膜交通におけるPX-PH タイプホスホリパーゼD の役割

Nonlinear rheological behavior of telechelic ionomer with a distribution of number of ionic stickers at the ends

鎖端のイオン性スティッカー数に分布を有するテレケリックイオノマーの非線形レオロジー

Glass Transition and Molecular Dynamics of Guest Low Mass Molecules in the Clathrate of Polymer Crystals

高分子結晶中に包接されたゲスト低分子のガラス転移と分子ダイナミクス

Identification of an active gibberellin compound in the basal land plant Marchantia polymorpha

基部陸上植物ゼニゴケにおける活性型ジベレリンの単離と同定

A spectroscopic analysis on bio-degradation processes of polymer thin film surfaces

ポリマー薄膜表面の生分解過程に関する分光学的解析

Analysis of membrane structure and properties of partially fluorinated amphiphilic molecules

部分フッ素化両親媒性分子の膜物性・構造に対するRf 鎖長依存性の解析

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

Structure analysis of polymer materials having sulfur atoms in a wet state by resonant small-angle scattering methods

テンダーX 線領域での小角共鳴散乱法による含硫黄ウェット高分子材料のナノ構造解析

Spatial distribution of nanostructures composed of sulfur element in polymer thin films

硫黄系高分子薄膜材料における硫黄元素が構成するナノ構造の空間不均一性評価

Study on transportation of metal ions through a polymer membrane containing ionic liquid

イオン液体含有高分子膜を用いた金属イオンの液膜輸送に関する研究

Effect of microplastics on distribution of trace heavy metals in seawater

海水中の微量重金属の分布及ぼすマイクロプラスチックの影響

－173－

宗林 由樹

竹中 幹人

大野 工司

辻井 敬亘

Polytechnic University of the Philippines, College of
Science, Department of Physical Sciences

Stony Brook University, Department of Material Science
and Chemical Engineering

Michigan State University, Chemical Engineering andMaterials Science

Yokohama National University, Faculty of Environment
and Information Sciences

RMIT University, School of Engineering2021-74 Abigail P. Cid-Andres2021-75 Maya K. Endoh2021-76 Robert C. Ferrier, Jr.

2021-77 Ken Nakano

2021-78 Yasuhiro Tachibana

課題提案型

水落 憲和

水落 憲和

Karlsruhe Institute of Technology (KIT), Institute ofOrganic Chemistry (IOC) and Institute of BiologicalInterfaces (IBG-2), Chair of Biochemistry at IOC

Leibniz institute for surface engineering, Leipzig,
Germany

Research School of Physics and Engineering, Australian
National University

Chinese Academy of Sciences, CAS Center for
Excellence in Molecular Plant Sciences, Institute of
Plant Physiology and Ecology

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

Division of Chemistry and Biological Chemistry, Schoolof Physical and Mathematical Sciences, Nanyang
Technological University (NTU)

CNRS, Institut Europeen des Membranes (IEM)

Hiroshima University, Physics

2021-81 Anne S. Ulrich2021-82 Gopalakrishnan Balasubramanian2021-83 Marcus W. Doherty

2021-84 Zuhua He

2021-85 Yunde Zhao

2021-86 Shingo Ito

2021-87 Mona Semsarilar

2021-88 Kensuke Homma

井上 峻介

山子 茂

山子 茂

二木 史朗

山口 信次郎 課題提案型

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二木 史朗

Nanoscopy for Nanomedicine Group, Institute for
Bioengineering of Catalonia (IBEC)

2021-80 Sílvia Pujals

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寺西 利治

Université de Strasbourg, Institut de Physique et Chimie
des Matériaux (IPCMS)
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2021-79 Jean-Pierre Bucher

寺西 利治

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栗原 達夫

College of Resources and Environment, Southwest
University2021-73 Xianzhu Dai

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University of Naples Federico II, Department of Chemical
栗原 達夫
Sciences

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2021-72 Maria Michela Corsaro

梶 弘典

Tsinghua University, Department of Chemistry2021-71 Lian Duan

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発展的 国際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

Dendritic Amphiphilic Block Copolymers as Additive for Polyvinylidenedifluoride Based Membranes

ポリビニリデンジフルオリドベースの膜の添加剤としての樹枝状両親媒性ブロック共重合体

1,3-Dipolar Cycloaddition Reactions of Cycloparaphenylenes with Azomethine Ylide

シクロパラフェニレンとアゾメチンイリドの1,3-双極子環化反応

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

Research of quantum controls in multi-qubit diamond quantum processors and quantum sensors

ダイヤモンド多量子ビット量子プロセッサーと量子センサにおける量子制御の研究

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

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

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 of semiconductor quantum dot solid films and their charge carrier dynamics

半導体量子ドット個体膜の作製とその電荷移動特性

Verification and Development of Dynamic Stiction Theory

動的固着理論の検証と展開

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

Fabrication of nanotopographical polymer surfaces for bactericidal properties-III

高分子ナノ表面構造による殺菌効果-III

Optimizing sampling devices and procedures to quantify sources of metals and microplastics in Metro Manila, Philippines’ water
resources

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

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

Development of highly efficient and stable blue organic light emitting diodes using thermally activated delayed fluorescent materials withultrafast reverse intersystem crossing

迅速な逆項間交差を有する熱活性化遅延蛍光材料を用いた高効率・高耐久青色有機EL 素子の開発

－174－高エネルギー加速器研究機構・物質構造科学研究所

大阪府立大学工業高等専門学校・環境物質化学コース

大阪大学・大学院基礎工学研究科

2021-105 倉橋 健介

2021-106 内田 幸明

2021-99 相澤 直矢

2021-104 齊藤 高志

大阪大学・大学院工学研究科

2021-98 長浜 太郎

弘前大学・大学院理工学研究科

北海道大学・工学研究院応用化学部門

2021-97 田中 雅章

2021-103 増野 敦信

名古屋工業大学・大学院工学研究科

2021-96 山田 啓介

立命館大学・生命科学部生物工学科

岐阜大学・工学部・化学・生命工学科

2021-95 諸田 美砂子

2021-102 豊竹 洋佑

国立研究開発法人産業技術総合研究所・デバイス技術
研究部門

関西大学・化学生命工学部

広島大学・大学院先進理工系科学研究科

2021-94 尾坂 格

2021-101 山崎 思乃

信州大学・医学部

2021-93 柴 祐司

豊田工業大学・大学院工学研究科

小野 輝男

大阪大学・微生物病研究所

2021-92 山崎 晶

2021-100 山方 啓

脇岡 正幸

広島大学大学院・統合生命科学研究科

2021-91 冨永 るみ

大野 工司

宗林 由樹

島川 祐一

島川 祐一

栗原 達夫

栗原 達夫

梶 弘典

梶 弘典

小野 輝男

小野 輝男

小野 輝男

上杉 志成

上杉 志成

青山 卓史

松宮 由実

名古屋大学・大学院工学研究科

2021-90 高野 敦志

若宮 淳志

Department of Materials Science and Engineering,
National Tsing Hua University, Taiwan

2021-89 Hao-Wu Lin

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発展的 国際Fine synthesis of polymer brush on nano-platelet for functional photonic LC

ポリマーブラシ付与ナノプレートの精密合成による機能性フォトニック液晶の実現

Development of Eu separation method by solid phase extraction using surfactant

界面活性剤を抽出剤として利用した固相抽出によるEu 分離法の開発

Synthesis and study of oxides with unusually high-valent cation

異常高原子価イオンを含む機能性酸化物合成とその構造物性研究

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

Functional characterization of extracellular vesicles produced by intestinal bacteria and development of their applications

腸内細菌が生産する細胞外膜小胞の機能解析と応用法の開発

Mechanism of the RISC in TADF Studied by Time-resolved Laser Spectroscopy

時間分解分光計測による熱活性化遅延蛍光における逆項間交差の機構解明

Development of thermally activated delayed fluorescence materials with nanosecondorder reverse intersystem crossing

ナノ秒オーダーの逆項間交差を示す熱活性化遅延蛍光材料の開発

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

Fe3O4/NiCo 2O4 多層膜の電子およびスピン物性の解明

Study on electronic and magnetic behavior of perpendicularly magnetized cobalt ferrite films

垂直磁化を有するコバルトフェライト薄膜の電気・磁気的挙動の解明

Study of spin dynamics in garnet nanocrystal thin films prepared by coprecipitation method

共沈法を用いて作製したガーネットナノ結晶体薄膜のスピンダイナミクスの研究

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

Development of π-conjugated polymers for high-efficiency non-fullerene solar cells

共役系ポリマーの開発と非フラーレン型太陽電池の高効率化

Self-Assembling Molecules for Improvement of Cardiomyocyte Engraftment

自己集合性分子による心筋細胞移植の効率化

Immune-Stimulatory Nano-Assemblies

免疫賦活化するナノ集合体

Study on the Regulatory Network of Plant Epidermal Cell Differentiation

植物表皮細胞の分化における制御ネットワークの研究

Investigation of relationship between molecular structure and viscoelasticparameters of model poly(alkylstyrene)s.

モデルポリアルキルスチレン類を用いた分子構造と粘弾性パラメータの相関解析

Development of Perovskite and Perovskite-like Emitters and Their Applications

ペロブスカイトと擬ペロブスカイト発光材料の開発とその応用

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二木 史朗

水落 憲和

二木 史朗

松宮 由実

倉田 博基

倉田 博基

奈良県立医科大学・医学部

名古屋大学・トランスフォーマティブ生命分子研究所

慶應義塾大学・薬学部

金沢大学・理工研究域 電子情報学系

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
水落 憲和
ンター

長谷川 健

東京工業大学・フロンティア材料研究所

明治大学・農学部

大阪大学・産業科学研究所

京都大学大学院・エネルギー科学研究科

日本女子大学・理学部数物科学科

Middle Tennessee State University, Chemistry

Centre for Science at Extreme Conditions and Schoolof Chemistry, University of Edinburgh

Osaka University, Department of Macromolecular
Science

Chiang Mai University, Industrial ChemistryCenter for Condensed Matter Sciences, National Taiwan
University2021-110 秦野 修

2021-111 桑田 啓子

2021-112 前川 大志

2021-113 徳田 規夫

2021-114 牧野 俊晴

2021-115 瀬戸 義哉

2021-116 藤塚 守

2021-117 岸本 泰明

2021-118 島田 良子

2021-119 Chengshan Wang2021-120 Yoshio Hayashi

2021-121 Tadashi Inoue

2021-122 Torranin Chairuangsri

2021-123 Ming-Wen Chu

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渡辺 宏

井上 峻介

山子 茂

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二木 史朗

中村 正治

寺西 利治

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2021-109 真島 豊

辻井 敬亘

産業技術総合研究所・機能化学研究部門

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2021-108 榊原 圭太

大野 工司

富山大学・学術研究部工学系

2021-107 源明 誠

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

電子エネルギー損失分光法による電荷密度波の電子的不安定性の研究

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

透過電子顕微鏡による電池開発のための新規機能性材料のミクロ・ナノ構造解析

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

Modulation of in-cell protein-protein interactions using mid-sized peptides

中分子ペプチドによる細胞内タンパク質−タンパク質相互作用の調節

Determine the three-dimensional structure of 13C labeled α-synuclein(61-95) in the Langmuir-Blodgett film and supported
phospholipids bilayers by p-MAIRS FT-IR

Coupling of concentration fluctuation and orientation fluctuation in mixture of nematic liquid crystal and solvent

ネマチック液晶-溶媒混合系における濃度揺らぎと配向揺らぎのカップリング

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

Switching of aromaticity/anti-aromaticity of oxidized cycloparaphenylenes

光励起に伴うシクロパラフェニレン酸化体の芳香族性・反芳香族性のスイッチング

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 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ダイヤモンド合成と量子技術開発研究

Research by atomically flat surface diamond for quantum information science and technology

原子レベル平坦表面ダイヤモンドを用いた量子情報科学研究

Cellular uptake using macropinocytosis

マクロピノサイトーシスによる細胞内取込様式

Identification of novel cellular uptake stimulation proteins

新規細胞内取込誘導タンパク質の同定

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

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

Study on water freezing with lignocellulose nanofibers and their surface modification toward functional materials

リグノセルロースナノファイバーの氷形成挙動の解明と表面修飾による機能拡張

Water in the Polymer Brush Layer: Structure and Freezing Behavior

高分子ブラシ層内の水の構造および凍結挙動の解析

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茨城大学・工学部物質科学工学科

近畿大学・理工学部

東北大学・大学院農学研究科

2021-129 吾郷 友宏

2021-130 松尾 司

2021-131 高橋 まさえ

京都工芸繊維大学・分子化学系

九州大学・先導物質化学研究所

2021-128 斉藤 光

2021-133 布施 泰朗

島根大学・総合理工学部

2021-127 宮本 光貴

福岡大学・理学部化学科

大阪大学・産業科学研究所

2021-126 家 裕隆

2021-132 長洞 記嘉時任 宣博

Rikkyo University, College of Science, Department ofChemistry2021-125 Mao Minoura

中村 正治

時任 宣博

時任 宣博

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水畑 吉行
時任 宣博

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倉田 博基

倉田 博基

梶 弘典

島川 祐一

Centre for Science at Extreme Conditions and Schoolof Chemistry, University of Edinburgh

2021-124 Kunlang Ji

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Analysis of chemical properties and origins of organic matter in lakes and soils using 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 structures of cationic aromatics bearing thiopyrylium units

チオピリリウム骨格を組み込んだカチオン型芳香族化合物の合成と構造解析

Theoretical design of planar silicene nanoribbons and search for new operating principles

平面シリセンナノリボンの理論設計と新しい動作原理の探究

Synthesis and Structural Characterization of Halostannylenes

ハロスタンニレンの合成と分子構造の解明

Elucidation of the fluorous interactions in the crystal structures of fluorinecontaining conjugated molecules by the single-crystal X-ray
structural analysis

単結晶X 線構造解析を用いた、含フッ素共役分子の結晶構造におけるフルオラス相互作用の解明

Radiative lifetime control of rare-earth codoped nanoparticles

希土類共ドープナノ粒子の寿命制御

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

Analyses of organic crystals and thin films using solid-state NMR spectroscopy

固体NMR を駆使した有機結晶および有機薄膜の分析

Synthesis and Characterization of Novel Group 16 Element Compouds

新規有機16 族元素化合物の合成と性質解明

High-pressure synthesis of potential multiferroic oxides

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

3

京都大学化学研究所 令和 3 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
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