IRCCS, Integrated
Research Consortium on
Chemical Sciences
統合物質創製化学研究推進機構
平成29年度 事業報告書

IRCCS, Integrated
Research Consortium on
Chemical Sciences
統合物質創製化学研究推進機構
平成29年度 事業報告書

目

次

１．統合物質創製化学研究推進機構について 
1-1

本機構の背景1-2

本機構の目的

1-3

本機構の組織1-4

本機構の特徴

1-5

事業計画

1-6

本機構の期待される成果と波及効果

２．メンバー 
2-1

コア研究室メンバー、連携研究室メンバー、リサーチフェロー

2-2

外部評価委員

３．平成２９年度事業報告 
3-1

第１回 統合物質若手の会

3-2

第３回 統合物質国内シンポジウム

3-3

第１回 統合物質国際シンポジウム

1

27

37

1
統合物質創製化学研究推進機構について

1-1
本機構の背景

１−１ 本機構の背景
革新的な機能性物質の発見と創造が、科学と科学技術に飛躍的な発展をもたらしてきた。その根幹を担ってきたのが、原子・分子レベルで物質を探求し、創造しつづけてきた「ものづくり」の化学、すなわち物質創製化学である。豊かな物質に彩られた現代社会の恒常的発展を維持し、我が国の科学技術立国としての地位を揺るぎないものとするためにも、次世代の飛躍を約束する新たな機能性物質群を創造していかねばならない。特に、緊迫するエネルギー・環境問題の解決や最先端バイオ・情報技術の進展を図り、科学技術全般の国際的競争力を高めるためにも、革新的な機能性物質群の創造と、それらの合理合成法の開拓に向けた新学術基盤の構築が急務である。化学者に課せられた任務は極めて重い。
次世代の機能性物質創製の鍵を握るのが、物質を構成する元素、分子、分子集合体という階層性の理解と制御であると考えられている。元素により特徴づけられる多種類の原子が結合を作ることにより分子が形成され、さらに分子が集積することにより分子集合体へと組織化され、それぞれの階層に特有の性質や機能がある。生体物質の構造に例えると、個々の原子の特性を基礎とし（元素）、その機能を発揮する最小単位となるタンパク質や核酸が構成され（分子）、これらがさらに集積してウイルスや細胞内組織であるミトコンドリア（分子集合体）となる。高度に機能化された革新的な物質を創製するためには、全ての階層における構成単位を創製する術を学び、その機能を解明しなければならない。
本事業に参画する京都大学・名古屋大学・九州大学・北海道大学の４研究組織は、それぞれ「元素」「分子」「集合体」「触媒」をキーワードとした強力な中核的国際研究拠点として認知されている。本事業の前身となる「統合物質創製化学推進事業 − 先
導的合成の新学術基盤構築と次世代中核研究者の育成（〜 年度）」においては、４研究組織のそれぞれがストロング・ポイントをもつ各物質階層を中心に、個別に蓄積されてきた物質合成における知識と知恵を融合・深化させるとともに、物質合成概念の統合にも取り組んだ。すなわち、古典的な化学反応を利用した「化学的物質合成」
ともに、高温超伝導体や発光材料、半導体などの開発に利用されてきた「物理的物質
合成」や、生命体が穏和な条件下に日常的に行っている精巧かつ高効率な「生命物質合成」にも学ぶことによって、持続型経済社会を実現する、環境に調和した新たな「物質創製概念」の創出を実践した。
「物質階層の統合」と「物質合成概念の統合」を合4

言葉として、各研究機関の知識と経験を融合・深化させて新たな物質創製化学を遂行した結果、天然窒素還元酵素における機能中心構造の全合成、カーボンナノチューブ
構造の化学合成、低環境負荷の鉄触媒による液晶材料の合成、強誘電性と強磁性が共存するマルチフェロイック物質の開発など、革新的な研究成果が生まれた。さらに、若手研究者に自由闊達な研究環境と、大学の垣根を越えた共同研究や情報交換の機会を与えたことによって、物質創製化学の未来を切り開く力量ある次世代中核研究者の育成を実現した。本事業は、この  大学間連携事業をさらに組織化・システム化した「新機構」を設立し、社会のニーズに応える「統合物質創製化学」を推進する。
















5

1-2
本機構の目的

１－２．本機構の目的
新物質創製は、化学結合の形成のための新しい方法論や、機能の発現のための物質構築論などを探求する極めて基礎的な基盤学術である一方、その成果は、新触媒や新材料開発はもちろん、イノベーション創成を通じてエネルギー・資源から環境・創薬に至る極めて広い範囲に適用される。ここでは、基礎と応用が直結し（縦糸）、また化学を中心として物理から生命科学までの多くの研究分野の協力が必須である（横糸）。すなわち、物質と情報そして人が集結することが何より重要な分野と言えよう。
しかしながら、我が国の物質創製研究は極めて高い国際競争力をもつにもかかわらず、
新物質創製を総合的かつ戦略的に進める機関・組織は、残念ながら我が国には存在しない。基礎と応用を結ぶ縦糸と多様な分野を結ぶ横糸を組み合せ、近年長足の進歩を遂げたナノ計測や計算化学を取り込んだ統合的な研究組織の構築が急務である。その一方で、現在のひっ迫した財政の下では、多くの面積とポストを必要とする新研究所
設立のような事業は現実的ではない。物質創製の学術を継承・発展させ、迫りくる環境問題などの重点課題を解決し、また新産業創出を成すためには、産官学連携や国際


図１

8



連携を前面に出し、責任あるマネージメント体制を持ちながらも、最小限の面積とポストの獲得で遂行できる、大学間連携を基盤とした「統合物質創製化学研究推進機構」
は、必要かつタイムリーな事業である。
図１に統合物質創製化学研究推進機構の概念図を示す。本機構事業に参画する名古屋大学・京都大学・九州大学・北海道大学の４研究組織は、「分子」、「元素」、「集合体」、「触媒」の化学研究において、それぞれに特色ある強力な中核的国際研究拠点として認知されているが、以下に示すそれぞれのストロング・ポイントを活かしながら、物質の階層構造を縦断する研究連携を実現する。
名古屋大学：無機化学から有機化学にわたる分子性物質の合成と機能の発現、さらには不斉反応を含む分子触媒の開発研究において卓越した成果をあげてきた。最近
では、生物無機化学やナノ炭素科学分野においても世界をリードする。
京都大学：元素の特性の解明と、それに基づく機能創出の化学において先導的な研究成果をあげている。機能性元素科学という新しい研究パラダイムを提唱し、分子性物質から凝縮系物質に至る様々な革新的新物質群の出現を促してきた。
九州大学：複雑な分子集合体・集積体を構築する新概念を提出し、多くの機能性集積体の合成研究を通してナノサイエンス・テクノロジー研究に先鞭をつけた。最近
では、核酸ナノマシンやナノハイブリッド材料の創出などで顕著な成果を挙げる。
北海道大学：触媒化学において世界を先導する中核的研究拠点である。触媒元素・分子のナノ・ミクロ集積・集合化学の研究を推進し、資源高度利用触媒、環境触媒、バイオ利用触媒、燃料電池・電極触媒、光触媒などで多くの成果を挙げる。
さらに本研究推進機構では、基礎研究を中心とする一方、「新反応・新触媒」
、「マテ
リアル」
、
「エネルギー・資源」、「ケムバイオ」という、応用展開を意識した  つの出口を設定して基礎と応用を直結させる。その上で、産官学連携や国際連携を組織的に取り込み、新しい研究システムや研究支援体制、人材育成システムを取り入れた、社会に開かれた新組織である。物質創製における我が国の研究の厚みを継承し、新学術・新産業の創出と後継人材の育成を両立させながら、持続可能な社会の発展を導く。





9

1-3
本機構の組織

１－３．本機構の組織
本機構事業では、１－２で説明した機構研究の概念を実現するため、全く新しい大
学間連携のフレームワークを構築する。一般論だが、これまでの大学間ネットワーク
事業が抱える問題点としは、
① 高い大学間の壁
② 出口設定が難しく、研究目標を立てにくい③ 平等主義によるガバナンス不足
④ 縦割り（大学別）の研究支援と人材育成支援
⑤ 外部意見が反映されにくい⑥ 連携のメリットがネットワーク内に閉じる
などが挙げられる（図２）。最大の問題点は⑥で、連携のメリットが社会発信されず、また社会の要請による事業という意識も希薄であった。ネットワーク形成のような大学強化事業は、社会からの認知によってはじめて達成されるもので、本研究推進
機構事業においては、成果、情報、人材がネットワークの外側に輩出される外部発信型の連携を目指している。研究推進機構の組織図を図３に示すが、以下、運営体制、統括研究部門、研究支援部門についてその概要を説明する。


図２

12



運営体制
本事業推進に全責任を負う機構長を置く。機構長は、国内の学識経験者（〜 名）
や理化学研究所などの連携機関から派遣された委員、本事業の実行委員から構成される運営委員会を組織する。運営委員会は、連携事業計画の策定と成果の取纏めを行う。
運営委員会で制定された事業計画は、研究統括部門の研究プラットホーム・リーダーから構成される実行委員会によって遂行される。
統合研究部門
機構長および運営委員会のリーダーシップの下、応用という研究の出口を意識した
統合研究部門（新反応・新触媒、マテリアル、エネルギー・資源、ケムバイオの４研
究プラットホーム）を設置する。各プラットホームには、連携大学から１研究室ずつ選抜した４研究室と、産官学・海外から招聘した連携客員研究室を設置して共同研究を実施する。各プラットホームにおける研究内容は以下の通りである。

13



新反応・新触媒研究：連携４大学の固体触媒（北大）、分子触媒（名大）、元素触媒（京大）、分子集合体触媒（九大）の研究チームの共同研究によって、ゼロエミ
ッション・カップリング反応の開発など、必要なものを必要なだけグリーンにつく
りだす化学を発展させ、炭素ナノ材料や医薬品の革新的合成に展開する。
マテリアル研究：炭素材料、ナノ粒子、有機物、無機固体、金属錯体、高分子に至る物質群の開発は、機構４大学が世界を先導している分野である。その研究は多岐にわたるが、例えば４大学が開発する新規光機能性分子を超分子化することによって、既存の細胞イメージングから、分子イメージングや更には機能イメージングへと発展させる。
エネルギー・資源研究：エネルギー・資源問題は化学が取り組むべき緊急課題である。金属ナノ粒子・界面の機能化（北大、名大）や革新的ナノカーボン材料開発（名大）を通じて、新しい燃料電池や太陽電池を開発する（北大、京大、九大）。X 線
吸収スペクトル計測（北大、名大）などによって反応機構を押さえながら、ユビキ
タス元素が生み出すグリーンエネルギーを創製する。
ケムバイオ研究：人工酵素を実現するための基本設計の確立は、生命科学における主題の一つである。生体分子合成（九大）とナノクラスター導入技術（京大）、ミューテーション技術（名大）を組み合わせ、計算シミュレーション（九大）を道しるべとしながら、機能をつくりこんだ人工酵素の合成にまで発展させる。
各研究プラットホームの構成は以下の通りである。
プラットホーム名リーダー

コア研究室メンバー

新反応・新触媒

中野環（北大）唯美津木・伊丹健一郎（名大）、中村正治（京大）、永島英夫・國信洋一郎（九大マテリアル

島川祐一（京大） 清水研一（北大）、山口茂弘（名大）、高原淳・友岡克彦（九大）

エネルギー・資源

阿 波 賀 邦 夫 （ 名 福岡淳（北大）、小澤文幸・村田靖次郎（京
大）

ケムバイオ

大）、佐藤治（九大）

吉澤一成（九大） 長谷川淳也（北大）、阿部洋（名大）、二木史朗（京大）各プラットホームにグループリーダーを置き、各分野の連携研究の推進に責任をもつ。
さらに、各プラットホームでは若手研究者を特任助教や博士研究員として雇用する。

14



これらの若手研究は、共通若手エース人事システムにより採用される。若手研究者の登竜門として機構を位置づけ、切磋琢磨による人材育成によって外部のパーマネン
ト・ポジションに送り出す。
本機構内に限定せず、統合的な共同研究を促進するため、融合創発研究を実施する。
共同研究提案を行い、運営委員会の審査を経て採択課題を決定し、実施する。また、
年度末に研究成果について報告書を作成し、運営委員のレビューを受けるものとする。
概ね毎年  件程度を実施する。
統括支援部門名古屋大学物質科学国際研究センター内に設置し、センターに付設の化学測定機器室を用いて本事業の研究を支援するとともに、国際シンポジウム等の開催に必要な外国人研究者招聘に関わる事務手続き、本事業の研究成果の取纏め、ポスターの作成、ホームページの管理などの広報活動を担当する。具体的には、以下の支援を行う。
① 外部発信・国際発信：機構の研究成果を、 や種々のメディアなどを通じて国際的に広報する。
② 共同研究コーディネ-ト：機構研究全体を見渡して、新しい共同研究を萌芽させる。
③ 知財発掘と管理：機構研究全体を見渡して、知財獲得を支援する。
④ 若手キャリアパス支援：求職情報を若手に流布し、キャリアパスセミナーを実施する。
⑤ 会議・シンポジウム開催支援：オープン参加型シンポなどを広報、支援する。

15

1-4
本機構の特徴

１－４．本機構の特長
社会に開かれた新機構は、以下の５つの特長を持つ。
① 戦略的なガバナンスに基づく融合研究：機構長のリーダーシップの下、応用という研究の出口を意識した統合研究部門（新反応・新触媒、マテリアル、エネ
ルギー・資源、ケムバイオの４研究プラットホーム）を設置し、各プラットホームには、連携大学から１研究室ずつ選抜した４研究室と、産官学・海外から招聘した連携客員研究室を設置して共同研究を実施する。更に融合研究部門を設置し、産官学や国際連携の場とする。大学間の壁を乗り越え、かつ開かれた研究組織を構築する。
② イノベーション創出とグローバル化（図４）：研究部門を横断的に支援するため統括支援部門を設置し、マネージメント教員、プロジェクト支援員などを配置する。共同研究コーディネート、知財獲得、国際発信、若手人材育成などを、大学間の壁を取り払って行う。理化学研究所などを連携機関として加え、イノベーション創出などを活性化する。
③ 外部発信型連携：新しい産官学連携と国際連携のパラダイムを構築する。オープン参加型の成果報告会などを開催することによ

図５って、研究成果・研究情報
・人材を、産業界、官界、学界、海外に対して外向きに発信・輩出する。
④ 共通若手エース人事シス
テム（図５）：大学院生から若手研究者まで、各階層のニーズに合わせた人材育成を行う。特任助教や研

18

図４



究員の人事ついては、共通若手エース人事システムを採用する。すなわち、連携大学共通の選考委員会を設置して人選する。機構の研究活動を人材ショーケースとして利用して若手のキャリアパス形成を支援すると共に、レクチャーシ
ップ派遣や招聘により国際的人脈形成を促す。若手研究者の登竜門として機構を位置づけ、切磋琢磨による人材育成によって外部のパーマネント・ポジションに送り出すことにより、物質創製分野における新たな人材育成モデルを実現する。
⑤ ナノ計測と計算化学の支援：ナノ計測と計算化学の支援の下、合理的な物質創製研究を展開する。
以上、基礎研究を重視しながらも、応用という研究の出口を意識した４テーマに各大学から１研究室を送り込む形で統合研究部門を形成することによって、互いの研究の強みを補完する研究体制を敷く。ガバナンスを効かした機構運営によって招聘される、理化学研究所などからの客員研究室の存在は、産官学との結びつきを強化すると共に、機構組織の流動性を高めるだろう。この上で、大学の壁を越えた統括支援部門
による効率的な知財発掘や国際発信によって、新機構のビジビリティは必然的に高まる。このように、社会を意識した機構の研究活動は、院生や若手研究者の人材ショー
ケースとして作用し、前述した共通若手エース人事システムは人材の流動性を必然的に生み出す。











19

1-5
事業計画



１－５．事業計画
本事業のロードマップを図６に示す。


図６














22

1-6
本機構の期待される成果と波及効果



１－６．本事業の期待される成果と波及効果
１）本事業がめざす物質階層の統合と物質合成概念の統合により、総合的な物質観に基づく多彩な物質創製法が創出される。それらは、生体機能、電子機能、光機能、触媒機能などの有用機能をもつ機能性物質群を創造するための新学術基盤の構築へと展開される。
２）革新的な機能性物質群の創製は、材料科学分野に革新をもたらす。これまでの物
質合成では、ナノテクノロジーで多用される熱力学支配による自己組織化が指導原理として用いられてきた。これに対して、本事業では、準安定物質の合成法の開拓により、自己組織化を超えた新規機能性物質群の創製法が開発されるものと期待される。
これにより、高圧合成と薄膜技術の融合による非平衡物質群の創製、人工超格子をもつ特異な高次構造体の合成、光磁気特性を示す新規錯体や有機発光素子の開発、酵素反応の解明と生命機能の理解に資する人工酵素の合成などが達成され、最先端のバイ
オ・情報技術へと応用・展開される。
３）縦糸（基礎と応用）と横糸（多様な分野）が結ばれ、産官学及び国際的に開かれた物質創製化学研究が実施され、物質創製化学の新しい学術基盤が構築される。その結果、環境に優しい新触媒開拓、新規機能電子物質に基づく骨太イノベーション、更には新医薬品や生体活性物質開発が成される。これらは持続可能な文明社会の構築に大きく貢献する。
４）高度な研究機能をもつ国際研究拠点の有機的連携により、多くの若手研究者に広範な学問領域を統合した卓越した研究環境を提供することができる。このような環境
は、幅広い知識と複眼的思考力を備えた中核研究者の養成に必要不可欠な要件である。
本事業では、若手研究者を統合研究フェローとして処遇し、自由で創造的な研究環境を提供する。これにより、物質創製化学の将来を担う中核研究者を多数育成できるものと期待される。また、国際研究拠点の連携は、我が国の学術的先進性と国際競争力を確保するためにも重要であり、多くの若者に、海外の一流研究者と切磋琢磨する機会を提供し、国際的な研究者として成長するためのインセンティブを与える。
５）本申請が提案する新機構のスキームの有効性は、物質創製化学分野にだけ限定されない。このスキームにより、参加大学の強みを生かして我が国の学術を結集できる
ほか、大学間連携のメリットが産官学連携や国際連携を通じて外向きに発信されることにより、社会からの支持も得られる。この効果は、新国立研究所の設立にも匹敵す24

る。このような外向きリンクの大学間連携事業のパイロットプログラムとして、他分野への波及効果やインパクトも大きい。
６）事業計画終了後は、新物質創製を総合的かつ戦略的に進める研究システムという枠組みは残しながらも、統括研究部門における研究テーマや参加研究室を全面的に見直し、また現在の連携  大学以外からの参加を促してオールジャパン体制をつくり、更に進んだ物質創製最先端研究を進める。

25

2
メンバー

2-1
コア研究室メンバー、連携研究室メンバー、
リサーチフェロー

● 機構長
機構長

巽和行
 名古屋大学物質科学国際研究センター特任教授

北海道大学
新反応・新触媒研究プラットホーム メンバー一覧
＜コア・連携研究室＞
朝倉清高 教授（基礎研究系・触媒表面研究部門）
長谷川淳也 教授（基礎研究系・触媒理論研究部門）
福岡 淳 教授（基礎研究系・物質変換研究部門）
清水研一 教授（基礎研究系・触媒材料研究部門）
大谷文章 教授（基礎研究系・光触媒科学研究部門）
高橋 保 教授（基礎研究系・分子触媒研究部門）
中野 環 教授（基礎研究系・高分子機能科学研究部門）
西田まゆみ 教授（実用化推進系・研究開発部門）
＜リサーチフェロー＞…平成  年  月末現在
SIDDIKI, S. M. A. Hakim 特任助教（基礎研究系・触媒材料研究部門）
YANG, Shubin 研究員（基礎研究系・光触媒科学研究部門）
LUO, Qian 研究員（基礎研究系・分子触媒研究部門）








30


巽和行
 名古屋大学物質科学国際研究センター特任教授


● 北海道大学

新反応・新触媒研究プラットホーム

北海道大学

メンバー一覧

新反応・新触媒研究プラットホーム メンバー一覧
＜コア・連携研究室＞
朝倉清高 教授（基礎研究系・触媒表面研究部門）
長谷川淳也 教授（基礎研究系・触媒理論研究部門）
福岡 淳 教授（基礎研究系・物質変換研究部門）
清水研一 教授（基礎研究系・触媒材料研究部門）
大谷文章 教授（基礎研究系・光触媒科学研究部門）
高橋 保 教授（基礎研究系・分子触媒研究部門）
中野 環 教授（基礎研究系・高分子機能科学研究部門）
西田まゆみ 教授（実用化推進系・研究開発部門）
＜リサーチフェロー＞…平成  年  月末現在
SIDDIKI, S. M. A. Hakim 特任助教（基礎研究系・触媒材料研究部門）
YANG, Shubin 研究員（基礎研究系・光触媒科学研究部門）
LUO, Qian 研究員（基礎研究系・分子触媒研究部門）








31

● 名古屋大学

エネルギー・資源研究プラットホーム

名古屋大学

メンバー一覧

エネルギー・資源研究プラットホーム メンバー一覧
＜コア・連携研究室＞
阿波賀邦夫教授（物性化学）
山口茂弘教授（機能有機化学）
伊丹健一郎教授（有機化学）
唯美津木教授（無機化学）
阿部洋教授（生物有機化学）
野依良治特別教授・斎藤進教授（分子触媒化学）
田中健太郎教授（分子組織化学）
菱川明栄教授（光物理化学）
篠原久典教授（物理化学）
渡辺芳人教授（生物無機化学）

＜リサーチフェロー＞…平成  年  月末現在
西川剛（機能有機化学）
澤口加奈（無機化学）
:X<DQJ（物性化学）
辻厳一郎（生物有機化学）
6DZDQW'LQHVK1DQDML（有機合成化学）
/L<XDQPLQJ（有機化学）
'DWWDWUD\D%%DJDO（有機合成化学）
阿部奈保子（生物有機化学）







32

● 京都大学
マテリアル研究プラットホーム

京都大学

メンバー一覧

マテリアル研究プラットホーム メンバー一覧
＜コア・連携研究室＞
中村正治教授（有機分子変換化学）
島川祐一教授（先端無機固体化学）
小澤文幸教授（錯体触媒変換化学）
金光義彦教授（光ナノ量子物性化学）
村田靖次郎教授（構造有機化学）
二木史朗教授（生体機能設計化学）
時任宣博 教授（有機元素化学）

＜リサーチフェロー＞
GELDSETZER, Jan 特定研究員（有機分子変換化学）
後藤真人研究員（先端無機固体化学）
阿波連知子研究員（光ナノ量子物性科学）
GUO, Jing-Dong 研究員（有機元素化学）















33



● 九州大学

ケムバイオ研究プラットホーム

九州大学

メンバー一覧

ケムバイオ研究プラットホーム メンバー一覧
＜コア・連携研究室＞
吉澤 一成 教授（反応・物性理論分野・先導物質化学研究所）
佐藤 治 教授（分子物質化学分野・先導物質化学研究所）



國信 洋一郎 教授（機能分子化学分野・先導物質化学研究所）

友岡 克彦 教授（集積分子機能分野・先導物質化学研究所）
永島 英夫 教授（クラスター分子化学分野・先導物質化学研究所）
高原 淳 教授（複合分子システム分野・先導物質化学研究所）

＜リサーチフェロー＞…平成  年  月末現在
6+(1*4816X 特任助教（分子物質化学分野・先導物質化学研究所）
河崎 悠也 特任助教（集積分子機能分野・先導物質化学研究所）




34

2-2
外部評価委員● 外部評価委員

外部評価委員岩村秀
 東京大学名誉教授

岩澤康裕
 電気通信大学燃料電池イノベーション研究センター長特任教授

上村大輔
 神奈川大学特別招聘教授

江崎信芳
 放送大学京都学習センター所長

大峰巌
 分子科学研究所名誉教授

新海征治
 九州大学高等研究院特別主幹教授
玉尾皓平 理化学研究所グローバル研究クラスタ長

36

3
平成29年度事業報告

3-1
第１回 統合物質若手の会ķĒŘxņ}¢ĥĪÚţúõ (IRCCS)ĬP ĿÐcŹnáƐºÏ 29 (2017) » 7 ç 28 á(ų) ƒ29 á()cƐ(N;O$Ĕ±TnƐķĒŘxņ}¢ĥĪÚţúõ

40�����
�� 29 � 7 � 28 �(�)14:00–14:30 ����14:30–14:36 ������ ������Kunio AWAGA, ������ ����� � � � � ����� ����Hiroshi NAKA, ������ �������
������� �����Hirokazu KOBAYASHI, ������
14:36–14:48 �����Atsushi TAHARA, ����� ������
���������������� 8 �������������������������
���
14:48–15:00 �����Katsuhiko TAKEUCHI, ����� ������
�������������(0)�� �
15:00–15:12 ����Zhongyue ZHANG, ������ �������
��������������: ������������������������
15:12–15:24 �����Takashi TOYAO, ������ ������
�����������������������
15:24–15:45 ��������� ����Haruka OMACHI, ������ ������
15:45–16:30 �����Koji HARANO, �������������� �������������� ������
���������������������������������
16:30–16:36 ���������� �����Shinji KANEGAWA, ����� ������
16:36–16:48 ����Mai TAKASHIMA, ������ ������
�����������������������������������������
16:48–17:00 ����Jieun JUNG, ������ ������
�������������������������������������������
���
17:00–17:12 ����Yuta TSUJI, ����� ������
����������������������
17:12–17:24 �����Kenichi KAWANO, ����� ������
����������������������������������������

41

17:24–17:45 ���������� ����Hiroshi NAKA, ������ ������
17:45–18:30� ����Masaki KITA, ���������������� ��������������������������
18:30–19:00 ������������
19:00–20:00 ��
20:00–22:00 ��������������
�� 29 � 7 � 29 �(�)������ �������
09:00–09:30
��� �� 1 “Important Research Areas in the Coming 25 Years”
09:30–09:45
�������
09:45–10:15
10:15–10:30

��� �� 2 “Solutions Using IRCCS Frameworks”�������

10:30–11:00 ��������� ������Yuichiro AIBA, ������ ������
11:00–11:12 �����Yasuaki KIMURA, ������ ������
���������������������������
11:12–11:24 ����Haijun LI, ������ ���������
����������������������������������������
11:24–11:36 �����Yuuya KAWASAKI, ����� ��������
��������DACN����������� �����Katsuhiko TAKEUCHI, ����� ������
11:36–11:48 ����Daisuke KAN, ����� �������
�������������������������
11:48–12:00 ������Soichiro OGI, ������ ������
����������������������
12:00–12:30 ������ ������Yoichiro KUNINOBU, ����� ���� � � � � ��� ����������� � � � � ��

42

Asst.Prof. Naka, Nagoya

Asst. Prof. Omachi, Nagoya

Prof. Awaga, Observer

Invited lecture, Dr. Harano, The University of Tokyo

Invited lecture, Prof. Hara, Nagoya

Asst. Prof. Zhang, Nagoya

43

Asst. Prof. Toyao, Hokkaido

Asst. Prof. Takashima, Hokkaido

DinnerMixer

Self-introduction

Self-introduction

Self-introduction

44

Meeting

Breakfast

Round-table discussion

Round-table discussion

Round-table discussion

Round-table discussion

45

Asst. Prof. Kawano, Kyoto

Assoc. Prof. Kan, Kyoto

Prof. Kuninobu, ObserverGroup photo

Inuyama castle

46

3-2
第３回 統合物質国内シンポジウム⤫ྜ≀㉁๰〇໬Ꮫ◊✲᥎㐍ᶵᵓ ➨ 3 ᅇᅜෆࢩ࣏ࣥࢪ࣒࢘ࠕ≀㉁๰〇໬Ꮫࡢ᪂₻ὶࠖᖹᡂ 29 ᖺ 10 ᭶ 30 ᪥㸦᭶㸧㹼31 ᪥㸦ⅆ㸧㸦ி㒔኱Ꮫ໬Ꮫ◊✲ᡤ ඹྠ◊✲Ჷ 1 㝵 ኱ࢭ࣑ࢼ࣮ᐊ㸧
10 ᭶ 30 ᪥㸦᭶㸧
13:00~13:10 㛤఍ࡢ㎡
13:10~13:40 ◊✲ሗ࿌ ி㒔኱Ꮫ ୰ᮧ ṇ἞ ᩍᤵ   ࠕ໬Ꮫ㈨※ࢆά⏝ࡍࡿ᭷ᶵྜᡂ໬Ꮫࡢ㛤ᣅࠖ㸦᪂཯ᛂ࣭᪂ゐ፹◊✲ࣉࣛࢵࢺࣇ࢛࣮
࣒㸧

13:40~14:10 ◊✲ሗ࿌ ໭ᾏ㐨኱Ꮫ Ᏻ⏣ ཭ὒ ෸ᩍᤵ   ࠕSupported Ionic Liquid Phase ࢆ⏝࠸ࡓ㏫ࢩࣇࢺ཯ᛂࠖ
㸦᪂཯ᛂ࣭᪂ゐ፹◊✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

14:10~14:40 ◊✲ሗ࿌ ஑ᕞ኱Ꮫ బ⸨ ἞ ᩍᤵࠕ㟁Ꮚ⛣ື࡟ࡼࡿཎᏊ౯␗ᛶ≀㉁ࡢศᴟไᚚࠖ
㸦࢚ࢿࣝࢠ࣮࣭㈨※◊✲ࣉࣛࢵࢺࣇ
࢛࣮࣒㸧

14:40~15:00 ఇ᠁
15:00~15:30 ◊✲ሗ࿌ ྡྂᒇ኱Ꮫ ኱⏫ 㑈 ຓᩍࠕ༙ᑟయᛶ༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ㧗ຠ⋡ศ㞳ἲࡢ㛤Ⓨ࡜ⷧ⭷ࢺࣛࣥࢪࢫࢱ
࡬ࡢᛂ⏝ࠖ㸦࢚ࢿࣝࢠ࣮࣭㈨※◊✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

15:30~16:00 ᣍᚅㅮ₇ ᒸᒣ኱Ꮫ ோ⛉ ຬኴ ෸ᩍᤵࠕ࣮࢝࣎ࣥࢼࣀࢩ࣮ࢺ〇㐀ἲࡢ☜❧࡜⏝㏵㛤ᣅ 㸫ゐ፹࡟╔┠ࡋ࡚࣮ࠖ

16:00~16:40 ࢩ࣮ࣙࢺࣉࣞࢮࣥࢸ࣮ࢩࣙࣥ ྛ኱Ꮫ 3 ྡ㸦1 ே 3 ศ㸧
16:40~18:00 ࣏ࢫࢱ࣮ࢭࢵࢩࣙࣥ
18:00~19:30 ஺ὶ࣭ࣇ࣮ࣜࢹ࢕ࢫ࢝ࢵࢩࣙࣥ

48

10 ᭶ 31 ᪥㸦ⅆ㸧
10:00~10:30 ◊✲ሗ࿌ ໭ᾏ㐨኱Ꮫ 㛗㇂ᕝ ῟ஓ ᩍᤵ   ࠕ⣔㛫஺ᕪࡢィ⟬໬Ꮫࠖ㸦ࢣ࣒ࣂ࢖࢜◊✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

10:30~11:00 ◊✲ሗ࿌ ஑ᕞ኱Ꮫ ሷ⏣ ῄோ ෸ᩍᤵࠕ㔞Ꮚ໬Ꮫࢆ⏝࠸ࡓゐ፹◊✲㸸࣓ࢱࣥάᛶ໬ࡢ཯ᛂᶵᵓࢆ୰ᚰ࡟ࠖ
㸦ࢣ࣒ࣂ࢖࢜◊     ✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

11:00~11:30 ᣍᚅㅮ₇ ศᏊ⛉Ꮫ◊✲ᡤ ᳳᒣ ൤ᜨ ෸ᩍᤵࠕࣁࣟࢤࣥ⤖ྜ࡜࣌ࣝࣇࣝ࢜ࣟ࢔࣮࡛ࣜࣝᣅࡃྜᡂ໬Ꮫࠖ

11:30~13:00 ᫨㣗
13:00~13:30 ᣍᚅㅮ₇ ி㒔኱Ꮫ࢚ࢿࣝࢠ࣮⌮ᕤᏛ◊✲ᡤ ୰⏣ ᰤྖ ෸ᩍᤵ
ࠕDNA ࢼࣀᵓ㐀యୖ࡟㓝⣲ࢆ㓄⨨ࡋࡓศᏊࢥࣥࣅࢼ࣮ࢺࠖ

13:30~14:00 ◊✲ሗ࿌ ྡྂᒇ኱Ꮫ ᩪ⸨ 㐍 ᩍᤵࠕ㑄⛣㔠ᒓゐ፹ࢆ⏝࠸ࡿ෌⏕ྍ⬟㈨※ࡢỈ⣲໬࡜⬺Ỉ⣲໬ࠖ㸦࣐ࢸࣜ࢔ࣝ◊✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

14:00~14:30 ◊✲ሗ࿌ ி㒔኱Ꮫ Ỉ⏿ ྜྷ⾜ ෸ᩍᤵ   ࠕ㔜࠸ࣇ࢙ࢽࣝ࢔ࢽ࢜ࣥࡢ໬Ꮫࠖ
㸦࣐ࢸࣜ࢔ࣝ◊✲ࣉࣛࢵࢺࣇ࢛࣮࣒㸧

14:30~14:40 㛢఍ࡢ㎡

49

࣏ࢫࢱ࣮ࢭࢵࢩࣙࣥ
㸨ኴᏐࡣࢩ࣮ࣙࢺࣉࣞࢮࣥࢸ࣮ࢩࣙࣥࡢⓎ⾲⪅P01 Synthesis of weakly acidic carbon catalyst by Diels-Alder addition of maleic anhydride on
activated carbon.
   ‫ۑ‬Lina Mahardiani, Abhijit Shrotri, Atsushi Fukuoka࠙໭኱ࠚP02 [Fe4] and [Fe6] Hydride Clusters Supported by Phosphines: Synthesis and Application to theCatalytic Silylation of N2.
   ‫ۑ‬Yasuhiro Ohki, Ryoichi Araake, Mizuki Tada, Yoichi Sakai࠙ྡ኱ࠚP03 ࣅࢫ㸦ࣇ࢙ࣟࢭࢽࣝ㸧ࢤ࣑ࣝࣞࣥࡢྜᡂ࡜ᛶ㉁   ‫ۑ‬㕥ᮌ⿱Ꮚࠊ➲᳃㈗⿱ࠊ᫬௵ᐉ༤࠙ி኱ࠚ
P04 ྾╔Ỉࡢ᥋╔⏺㠃࡟ཬࡰࡍᙳ㡪࡟㛵ࡍࡿ⌮ㄽⓗ⪃ᐹ   ᮧ⏣⿱ᖾࠊ⏣୰ᏹᫀࠊ‫୍⃝ྜྷۑ‬ᡂ࠙஑኱ࠚ
P05 Synthesis of cubane-type [Mo3S4Fe] clusters supported by cyclopentadienyl ligands andtheir application in the N2 activation.
   ‫ۑ‬Ryota Hara, Mami Kachi, Keisuke Uchida, Mizuki Tada, Yoichi Sakai, Yasuhiro Ohki࠙ྡ኱ࠚP06 1.3-ࢪࢤ࣐ࣝ-2-ࢩࣛ࢔ࣞࣥࡢྜᡂ࡜ࡑࡢᵓ㐀   ‫Ⳣۑ‬ཎ▱⣫ࠊ➲᳃㈗⿱ࠊ᫬௵ᐉ༤࠙ி኱ࠚ
P07 Low temperature oxidation of trace Ethylene with a hydrophobic SBA-15 supported Pt
catalyst.
   ‫ۑ‬Shazia Satter Sharmin, Kiyotaka Nakajima, Atsushi Fukuoka࠙໭኱ࠚP08 Photocatalytic Oxidation of Benzene to Phenol Using Dioxygen and Water.
   ‫ۑ‬Jieun Jung, Ji Won Han, Yong-Min Lee, Wonwoo Nam, Shunichi Fukuzumi࠙ྡ኱ࠚP09 ࢤ࣐ࣝ࠾ࡼࡧࢫࢱࣥࢼ࣋ࣥࢮࢽࣝ࢔ࢽ࢜ࣥࡢྜᡂ࡜ᵓ㐀   ‫⸨ۑ‬᳃リ⧊ࠊỈ⏿ྜྷ⾜ࠊ᫬௵ᐉ༤࠙ி኱ࠚ
P10 ஧᰾㖡㓟⣲㘒యࢆ⏝࠸ࡓ࣓ࢱࣥ㓟໬཯ᛂゐ፹ࡢ⌮ㄽⓗタィ   ‫ۑ‬ᇼඃኴࠊᐑす┿⏤Ꮚࠊሷ⏣ῄோࠊᑠᑎᨻேࠊྜྷ⃝୍ᡂ࠙஑኱ࠚ

50

P11 Development of Highly Active Ruthenium Catalysts for Hydrogenation of Carboxylic Acids.
   ‫ۑ‬Shota Yoshioka, Masayuki Naruto, Ke Wen, Susumu Saito࠙ྡ኱ࠚP12 ࢔࣑ࣝࢽ࣒࢘̽㕲㘒యࡢྜᡂ࡜ᛶ㉁   ᰗ⃝㐩ஓࠊ‫ۑ‬Ỉ⏿ྜྷ⾜ࠊ᫬௵ᐉ༤࠙ி኱ࠚ
P13 Synthesis of Helical Polyurethanes from (R)-1,10-Bi(2-naphthol) and Diisocyanates.
   ‫ۑ‬Heshuang Dai, Yue Wang, Tamaki Nakano࠙໭኱ࠚP14 Trifluoroacetic Acid–Water Mixture for Rapid Conversion of Esters to Carboxylic Acids.
   ‫ۑ‬Tomomi Banno, Hiroyuki Okabe, Ryoji Noyori, Hiroshi Naka࠙ྡ኱ࠚP15 Modification of Lipid Packing State by Amphipathic Peptides with Curvature Inducibility.
   Tomo Murayama, ‫ۑ‬Kenichi Kawano, Shiroh Futaki࠙ி኱ࠚP16 ࣇ࣮ࣞࢡ࣮࣎ࣝᙧ≧ࢱࣥࢢࢫࢸࣥ㓟ࣅࢫ࣐ࢫගゐ፹ᚤ⢏Ꮚ࡟࠾ࡅࡿከ㟁Ꮚ⛣ືᶵᵓࡢゎ᫂   ‫ۑ‬㧗ᓥ⯙ࠊᇼᬕ⳯ࠊ኱㇂ᩥ❶࠙໭኱ࠚ
P17 ࢪ࢖ࣥࢻࣟ࢝ࣝࣂࢰ࣮ࣝ࡜ࢧࣝࣇ࢙ࣥ࠿ࡽ࡞ࡿࢪࣕ࢖࢔ࣥࢺ࣐ࢡࣟࢧ࢖ࢡࣝࢆ⏝࠸ࡓศᏊㄆ㆑   ‫ۑ‬ᆏ⏣༟ஓࠊἙ㔝ៅ୍㑻ࠊ⏣୰೺ኴ㑻࠙ྡ኱ࠚ
P18 ⁐⾑࣌ࣉࢳࢻࢆᨵኚࡋࡓ࢚ࣥࢻࢯ࣮࣒୙Ᏻᐃ໬࡮ࣉࢳࢻࡢ㛤Ⓨ࡜ᢠయࡢ⣽⬊ෆ㏦㐩   ‫⛅ۑ‬ᰘ⨾Ἃ✑ࠊṊෆᩄ⚽ࠊᕝཱྀ⚈ṇࠊᆏᮏ೺ኴ㑻ࠊ஧ᮌྐᮁ࠙ி኱ࠚ
P19 ࣍࢘⣲໬ 2-ࣇ࢙ࢽࣝࣆࣜࢪࣥ㢮ࡢᅛ┦┦㌿⛣࡜ࡑࡢᶵᵓゎ᫂   ‫ྜྷۑ‬㉺⿱௓ࠊ㡲ᓮ⿱ྖࠊᑠᆏ⏣⪔ኴ㑻ࠊᅧಙὒ୍㑻࠙஑኱ࠚ
P20 ㉸ศᏊᆺ࣏ࣝࣇ࢕࣭ࣜࣥࣇࢱࣟࢩ࢔ࢽࣥ❅⣲ᯫᶫ㕲஧᰾㘒య࡟ࡼࡿゐ፹ⓗ࣓ࢱࣥ㓟໬཯ᛂ   ‫ۑ‬᳃⏣೺ኴ㑻ࠊᒣ⏣Ὀஅࠊ୕ཎࡢࡒࡳࠊ㧗㇂ගࠊ໭Ἑᗣ㝯ࠊ஭ᕝ࿴ᐉࠊ཭ᒸඞᙪࠊ⏣୰೺ኴ㑻࠙ྡ኱ࠚ
P21 Engineering of sequence-specific RNA binding proteins based on PUF proteins.
   ‫ۑ‬Kouki Shinoda, Miki Imanishi, Shiroh Futaki࠙ி኱ࠚ

51

P22 Antimicrobial mechanism of bi-metal modified titania photocatalyst: enhanced activity byinteraction between gold and silver.
   ‫ۑ‬Maya Endo, Zhishun Wei, Bunsho Ohtani, Ewa Kowalska࠙໭኱ࠚP23 ⇕ࢩࣙࢵࢡࢱࣥࣃࢡ㉁㜼ᐖᛶ⎔≧࣌ࣉࢳࢻ࡜ MoS2 ࢼࣀࢩ࣮ࢺ࡟ࡼࡿຠ⋡ⓗࡀࢇ⣽⬊ග⇕⒪ἲ   ‫ۑ‬᭷Ᏻ┿ஓࠊJing Mu, Xiao Zhang, Ying Huang, Edwin Kok Lee Yeow, Hua Zhang, Bengang
Xing࠙ྡ኱ࠚ
P24 ࢖࣑ࢲࢰ࣮ࣝ⦰⎔࣋ࣥࢰࢳ࢔ࢪ࢔ࢰ࣮ࣝ㦵᱁ࢆ⏝࠸ࡓ㏆㉥እ྾཰Ⰽ⣲ࡢ㛤Ⓨ   ‫ۑ‬ᒸᓮಟᖹࠊᮧ⏣⌮ᑦࠊⱝᐑ῟ᚿࠊᮧ⏣㟹ḟ㑻࠙ி኱ࠚ
P25 Theoretical Study on Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double
Bonds.
   ‫ۑ‬㉿㯪᫂࠙໭኱ࠚ
P26 P450BM3 ࡢ᪂つ෌ᵓᡂᡭἲࡢ㛤Ⓨ࠾ࡼࡧ࣐ࣥ࢞ࣥ㘒యࡢᑟධ࡟ࡼࡿ཯ᛂᛶࡢᨵኚ   ‫ۑ‬኱ᮧ្ኴࠊឡሙ㞝୍㑻ࠊⲮྖ㛗୕ࠊΏ㎶ⰾே࠙ྡ኱ࠚ
P27 ȧᣑᙇᆺ࢟ࣀࣜࣀ࣮ࣝ㓄఩Ꮚࢆ⏝࠸ࡓ㔠ᒓ㘒యࡢྜᡂ࡜ᛶ㉁   ‫ۑ‬ሯᑿᫀᾈࠊᮧ⏣⌮ᑦࠊⱝᐑ῟ᚿࠊᮧ⏣㟹ḟ㑻࠙ி኱ࠚ
P28 TTFs-SCO ࣁ࢖ࣈࣜࢵࢺศᏊ⤖ᬗࡢྜᡂ࡜≀ᛶ   ‫ۑ‬㔠ᕝៅ἞ࠊ⚟ᮏెᘯࠊబ⸨἞࠙஑኱ࠚ
P29 ⥳⮋⳦ࡢ࣒࣊㍺㏦⺮ⓑ㉁」ྜయ (PhuUV-PhuT) ࡟㛵ࡍࡿ◊✲   ‫ۑ‬ᴬཎ࠼ࡾ࠿ࠊⲮྖ㛗୕ࠊΏ㎶ⰾே࠙ྡ኱ࠚ
P30 ࣌ࣉࢳࢻࢹࣥࢻࣟࣥࢳ࣮࢜ࣛࢺಟ㣭㔠ࢡࣛࢫࢱ࣮ࡢගゐ፹ᶵ⬟   ‫ୖۑ‬㔝ுࠊ☾㷂຾ᘯࠊ▼ᶫᖾ඾ࠊ㧗㇂ගࠊ୰ᮧṇ἞࠙ி኱ࠚ
P31 㓟໬ࢭ࣒ࣜ࢘ゐ፹ࢆ⏝࠸ࡓ஧㓟໬Ⅳ⣲࡜࣓ࢱࣀ࣮ࣝ࠿ࡽࡢࢪ࣓ࢳ࣮ࣝ࢝࣎ࢿ࣮ࢺྜᡂ
࡟㛵ࡍࡿ⌮ㄽⓗ◊✲   ‫ۑ‬ᮡᒣ฼⾜࠙໭኱ࠚP32 ࢤࢫࢺໟ᥋ఏᑟᛶ໬ྜ≀ࡢఏᑟᶵᵓ࡟㛵ࡍࡿ⌮ㄽ◊✲   ‫ۑ‬ᯘᣅࠊᅵ᪉ඃ࠙ྡ኱ࠚ

52

P33 㕲ゐ፹㕥ᮌ-ᐑᾆ࢝ࢵࣉࣜࣥࢢ཯ᛂ࡟ࡼࡿȘ-࢔࣮ࣜࣝࣉࣟࣆ࢜ࣥ㓟㢮ࡢ୙ᩧྜᡂ   ‫ۑ‬ዟᅬᬛ⤮⨾ࠊᒾᮏ㈗ᐶࠊ࢔ࢲࢡ ࣛࢡࢫ࣑࢝ࣥࢱࠊ⚄ᑗྜྷࠊ୰ᮧṇ἞࠙ி኱ࠚ
P34 ➨୍ཎ⌮ィ⟬࡟ࡼࡿ㓟໬ࢭ࣒ࣜ࢘ゐ፹ࡢᶵ⬟ゎᯒ   ‫ۑ‬୰ᒣဴ࠙໭኱ࠚ
P35 RISM with DMRG-CASPT2 for calculating near infrared dyes.
   ‫ۑ‬Ryosuke Shimizu, Takeshi Yanai, Yuki Kurashige, Daisuke Yokogawa࠙ྡ኱ࠚP36 ࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ㧗㑅ᢥⓗ┤᥋ⓗ࢔࣮ࣜࣝ໬㔜ྜ㸸1,2-ࢪࢳ࢚ࢽ࢚ࣝࢸࣥྵ᭷ DA࣏࣐࣮ࣜࡢྜᡂ   ‫⬥ۑ‬ᒸṇᖾࠊ᳃⏣ⴥ᭶ࠊᕷཎᬸᏊࠊᑠ⃝ᩥᖾ࠙ி኱ࠚ
P37 Tuning orbital angular momentum by a dynamic bond in a cobalt (II) complex.
   ‫ۑ‬Shengqun Su, Osamu Sato࠙஑኱ࠚP38 ࣇ࢙࣒ࢺ⛊࣮ࣞࢨ࣮ࣇ࢕࣓ࣛࣥࢺ࡟ࡼࡿẼ┦Ⅳ໬Ỉ⣲/Ar ࣇ࣮ࣟ⣔࡟࠾ࡅࡿ఍ྜ཯ᛂ㐣⛬ࡢほ   ‫ۑ‬ᶫࣨ㇂࠿ࡍࡳࠊ⃝ᮌ⨾㔛ࠊᯇ⏣᫭Ꮥࠊ⳻ᕝ᫂ᰤ࠙ྡ኱ࠚ
P39 Pd ࢼࣀࢡࣛࢫࢱ࣮ゐ፹ࡢᵓ㐀࡜࣮࢝ࣂ࢖ࢻᙧᡂ   ‫ۑ‬ᮅ಴Ύ㧗࠙໭኱ࠚ
P40 EUV ບ㉳࡟ࡼࡿ Xe ከ㟁Ꮚࢲ࢖ࢼ࣑ࢡࢫࡢ᫬㛫ศゎග㟁Ꮚィ   ‫ۑ‬Ἑ㎶ెႛࠊᶫࣨ㇂࠿ࡍࡳࠊఅ㇂⍞✑ࠊᯇ⏣᫭ᏕࠊᙪᆏὈṇࠊ⳻ᕝ᫂ᰤ࠙ྡ኱ࠚ
P41 ᖹ㠃ᅄゅᙧⓑ㔠(0)㘒యࡢᵓ㐀࡜≀ᛶ࡟ཬࡰࡍ⿵ຓ㓄఩Ꮚࡢຠᯝ   ‫➉ۑ‬ෆ຾ᙪࠊ⏣ཱྀᘅ⮧ࠊ㇂ᕝ୍ᖹࠊᯇᑿྖࠊ⏣୰ᏹᫀࠊྜྷ⃝୍ᡂࠊᑠ⃝ᩥᖾ࠙ி኱ࠚ
P42 ࢡࣜࢵࢡ཯ᛂ⣲Ꮚ DACN ࢆ⏝࠸ࡓศᏊ㐃⤖ἲࡢ㛤Ⓨ   ‫ۑ‬Ἑᓮᝆஓࠊ㟷ᒣៅࠊ᯽ᮌ೺ࠊ஭ᕝ࿴ᐉࠊ཭ᒸඞᙪ࠙஑኱ࠚ
P43 ྍどගゐ፹ࢆ⏝࠸ࡓ⬺Ⅳ㓟ᆺ sp3 Ⅳ⣲࢔࣑ࣀ໬཯ᛂࡢ㛤Ⓨ   ۵ᴬཎ㝧ኴࠊఀ⸨Ụ㔛ࠊᮧୖ្ࠊఀ୹೺୍㑻࠙ྡ኱ࠚ
P44 ࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ㧗㑅ᢥⓗ┤᥋ⓗ࢔࣮ࣜࣝ໬㔜ྜ㸸2,2'-ࣅࢳ࢜ࣇ࢙ࣥྵ᭷ DA ࣏࣐࣮ࣜࡢྜᡂ   ‫ۑ‬ᒣୗ⳯᦬ࠊ⬥ᒸṇᖾࠊ᳃⿱ᶞࠊすཎᗣᖌࠊᑠ⃝ᩥᖾ࠙ி኱ࠚ

53

P45 㓟⣲ࣉࣛࢬ࣐ฎ⌮࡟ࡼࡾㄪ〇ࡋࡓ TiO2(110)ᢸᣢ㔠ࢼࣀ⢏Ꮚࢧ࢖ࢬࡢ≉␗࡞ᢸᣢ㔞౫Ꮡᛶ   㧗ⲡᮌ㐩ࠊ㛵⪽ྐࠊᮌᕤ῟ࠊ୕㍯ᐶᏊࠊ‫ۑ‬ᮅ಴Ύ㧗࠙໭኱ࠚ
P46 ගᯫᶫ཯ᛂࢆ⏝࠸ࡓඹ᭷⤖ྜᛶ᭷ᶵࢼࣀࢳ࣮ࣗࣈࡢ᪂つྜᡂἲ   ‫ۑ‬ᡞ㇂඘ᑑࠊ๓⏣ᯝṌࠊఀ⸨ⱥேࠊఀ୹೺୍㑻࠙ྡ኱ࠚ
P47 ග㟁ὶࣅ࣮ࢺศග࡟ࡼࡿࣁࣟࢤࣥ໬㖄࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụࡢග㟁ὶ⏕ᡂᶵᵓࡢ◊✲   ‫⏣ۑ‬ཎᘯ㔞ࠊⱝᐑ῟ᚿࠊ㔠ග⩏ᙪ࠙ி኱ࠚ
P48 8 ᪘㑄⛣㔠ᒓ㘒యࢆ⏝࠸ࡓ௚⨨᥮࢔ࣝࢣࣥࡢỈ⣲໬࡟㛵ࡍࡿ⌮ㄽ◊✲   ‫⏣ۑ‬ཎ῟ኈࠊ◁⏣♸㍜ࠊ⏣୰ᏹᫀࠊሷ⏣ῄோࠊྜྷ⃝୍ᡂࠊỌᓥⱥኵ࠙஑኱ࠚ
P49 Controlled fabrication of graphene liquid cells for real-time TEM imaging of liquids.
   ۵Yoshimasa Michiya, Yutaka Ohno, Hisanori Shinohara, Ryo Kitaura࠙ྡ኱ࠚP50 ࣁࣟࢤࣥ໬㖄࣌ࣟࣈࢫ࢝࢖ࢺࢼࣀ⢏Ꮚ࡟࠾ࡅࡿගບ㉳ࢲ࢖ࢼ࣑ࢡࢫ   ‫‮ۑ‬ᮏ㒓࠙ி኱ࠚ
P51 ࣓ࢱࣥάᛶ໬ゐ፹ In/SiO2 ࡢ XAFS ゎᯒ   ‫ۑ‬Ọᯇఙ୍ࠊすᕝ♸ኴࠊⴗཎோᚿࠊ஭Ἴ㞝ኴࠊᒣ୰୍㑻ࠊᮅ಴Ύ㧗࠙໭኱ࠚ
P52 Concise Synthesis of MoS2 Nanoribbon using Inner Space of Carbon Nanotubes.
   ۵Motoki Aizaki, Haruka Omachi, Hisanori Shinohara࠙ྡ኱ࠚP53 Sn ࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺ࡟ᑐࡍࡿ SnCl2 ῧຍࡢຠᯝ   ‫ۑ‬㜿Ἴ㐃▱Ꮚ࠙ி኱ࠚ
P54 ᢸᣢ Pt ゐ፹࡟ࡼࡿ 2 ⣭࢔ࣝࢥ࣮ࣝ࡜࢔࣑ࣀ࢔ࣝࢥ࣮ࣝ࠿ࡽࡢ 2,5-஧⨨᥮ࣆ࣮ࣟࣝࡢྜᡂ   ‫ۑ‬ΎỈ◊୍ࠊA.S. Touchy, 㫽ᒇᑿ㝯ࠊS.M.A. Hakim Siddiki࠙໭኱ࠚ
P55 CNT-Template Synthesis of Graphene Nanoribbon and Extraction by Chemical Oxidation.
   ۵Yuka Oka, Haruka Omachi, Hisanori Shinohara࠙ྡ኱ࠚP56 Excitonic properties in CH3NH3PbX3 (X = I and Br) single crystals.
   ‫ۑ‬Le Phuong Quang࠙ி኱ࠚ

54

P57 ࢖ࣀ࣮ࣛࢺࢆ⏝࠸ࡓࢺࣜࣉࢳࢭࣥࡢ࣏࣡ࣥࢵࢺྜᡂ࡜ࡑࡢኚ᥮   ‫ۑ‬ᒾ⏣㝯ᖾࠊྜྷỌ㐩㑻ࠊ⸨ཎ໶ࠊ῝ぢᣅேࠊ᪂⸨඘࠙஑኱ࠚ
P58 Development of Anti-cancer Agents based on Synthetic Lethality by LATS Mutation.
   ‫ۑ‬Nguyen Hong Nhung, ᮌᮧᗣ᫂ࠊᮧୖඃᏊࠊ㜿㒊ὒ࠙ྡ኱ࠚ
P59 1 ගᏊ࠾ࡼࡧ 2 ගᏊⓎගບ㉳ศගࢆ⏝࠸ࡓ CH3NH3PbX3 (X = I, Br, Cl)༢⤖ᬗࡢࣂࣥࢻ➃㏆ഐ࡛ࡢගᏛ≉ᛶࡢ◊✲   ‫ۑ‬ᒣ⏣⌶ඔ࠙ி኱ࠚ
P60 Photo-induced b-Elimination Leading to a Vinyl Monomer.
   Hassan Nageh, Liming Zhao, Akira Nakayama, Jun-ya Hasegawa, Yue Wang, ‫ۑ‬Tamaki
Nakano࠙໭኱ࠚP61 ࣟࢱ࢟ࢧࣥᵓ㐀ᙧᡂ࡟ࡼࡿ᪂つ࢔ࣥࢳࢭࣥࢫἲࡢ㛤Ⓨ   ‫ۑ‬ᐩ⏣㈗ᚿࠊ㜿㒊ዉಖᏊࠊᮌᮧᗣ᫂ࠊ㜿㒊ὒ࠙ྡ኱ࠚ
P62 ࣁࣟࢤࣥ໬㔠ᒓ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụ࡟࠾ࡅࡿග࢟ࣕࣜ࢔෌⤖ྜ࠾ࡼࡧ㍺㏦ᶵᵓ
   ‫⏣༙ۑ‬ᓅே࠙ி኱ࠚ
P63 Photo-transformation and Polymerization of (R)-1,10-Bi(2-naphthol).
   ‫ۑ‬Yue Wang, Zhaoming Zhang, Tamaki Nakano࠙໭኱ࠚ
P64 ᢠ࢘࢖ࣝࢫάᛶࢆᣦྥࡋࡓ 2'-E-ࢳ࢜᰾㓟ࡢ㛤Ⓨ   ‫∦ۑ‬಴⚽㞝ࠊᮌᮧᗣ᫂ࠊ㜿㒊ὒ࠙ྡ኱ࠚ
P65 ༢୍ FAPbBr3 ࢼࣀ⢏ᏊࡢⓎගࢲ࢖ࢼ࣑ࢡࢫ   ‫ۑ‬㙑⏣┤ᶞ࠙ி኱ࠚ
P66 ⇕㌿⛣࡟ࡼࡿ㧗ḟᵓ㐀ኚ໬࡜ග࢔ࢡࢳ࢚࣮ࣗࢱ⬟ࡢࢫ࢖ࢵࢳࣥࢢ   ‫ۑ‬஬ᓥ೺ኴࠊ㇂ᩥ㒔࠙஑኱ࠚ
P67 ࢤࢫࢺศᏊᤄධ࡟ࡼࡿ㹋㹍㹄ࡢ≀ᛶኚ໬   ‫ۑ‬ᒣᮏ⚈ᖹࠊᙇ୰ᓅࠊ㜿Ἴ㈡㑥ኵ࠙ྡ኱ࠚ
P68 CsPb(Br1-xIx)3 ࢼࣀ⢏Ꮚ࡟࠾ࡅࡿࣂ࢖࢚࢟ࢩࢺࣥ࡜ࢺࣜ࢜ࣥࡢࢲ࢖ࢼ࣑ࢡࢫ   ‫ۑ‬୰ཎ⪽ᚿ࠙ி኱ࠚ

55

P69 㓄఩Ꮚኚ᥮࡟ᇶ࡙ࡃỈ⇕ྜᡂ ZnO ࢼࣀ࣡࢖ࣖࡢᡂ㛗ಁ㐍࣓࢝ࢽࢬ࣒ཬࡧศᏊ㆑ู࢚ࣞ
ࢡࢺࣟࢽࢡࢫ࡬ࡢᒎ㛤   ‫ۑ‬㛗ᓥ୍ᶞࠊ㓇஭኱ᶞࠊ஭ୖᬦⱥࠊ୰ᮧ༓ᯞࠊYong He, 㔠஭┿ᶞࠊGouzhu Zhang, 㧗ᶫ⥘ᕫࠊ➉⏣⢭἞ࠊᰗ⏣๛࠙஑኱ࠚ
P70 ࢩࣛࢪࢳ࢚ࣀ࣮ࣟࢲ࣑ࣥࡢྜᡂ࠾ࡼࡧ㏆㉥እ⺯ග≉ᛶ   ‫ۑ‬ᮌᮧዉኸ࠙ྡ኱ࠚ
P71 ᗄఱᏛⓗࣇࣛࢫࢺ࣮ࣞࢺ᱁Ꮚࢆࡶࡘ 3d 㑄⛣㔠ᒓ໬ྜ≀ࡢᵓ㐀࡜☢ᛶ   ‫ۑ‬ᚋ⸨┿ேࠊ㰺⸨㧗ᚿࠊᓥᕝ♸୍࠙ி኱ࠚ
P72 ᣑᙇᆺࢤ࣐ࣝ࣌ࣜࢧ࢖ࢡࣜࣥࡢྜᡂ࠾ࡼࡧ≀ᛶ   ‫ۑ‬㇂ᮏ⿱ᶞࠊ᳃῟ኴࠊ⸨ཎኴ㑻ࠊᇉෆ႐௦୕࠙ዉⰋඛ➃኱ࠚ
P73 ◲㯤ࢆྵࡴ୰ဨ⎔⦰⎔ࢳ࢜ࣇ࢙ࣥ࡟ࡼࡿ π 㟁Ꮚ⣔ࡢศᏊ㓄ྥไᚚ   ‫ۑ‬᪩ᕝ㞞኱ࠊ῝⃝ឡᏊࠊᡞ⏣㞝భࠊᒣཱྀⱱᘯ࠙ྡ኱ࠚ
P74 ࣑ࢫࢺ CVD ἲ࡟ࡼࡿࢫࢬ㓟໬≀㏱᫂ᑟ㟁ᛶ࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷ࡢస〇   ‫⩚୹ۑ‬ὈஅࠊⳢ኱௓ࠊᓥᕝ♸୍࠙ி኱ࠚ
P75 ஺ᕪࢩࢡࣟࣇ࢓ࣥᆺࢻࢼ࣮ࡢ࢖࢜ࣥࣛࢪ࢝ࣝሷ࡟࠾ࡅࡿ㟁Ꮚ≀ᛶ   ‫ۑ‬Ẋෆ኱㍤ࠊᯇୗᮍ▱㞝ࠊ㜿Ἴ㈡㑥ኵࠊⳢཎṇ࠙ྡ኱ࠚ

56

Opening, Prof. Tokito

Prof. Nakamura, Kyoto

Chair, Prof. Yamaguchi

Assoc. Prof. Yasuda, Hokkaido

Prof. Sato, Kyushu

Asst. Prof. Omachi, Nagoya

57

58

Invited lectuer, Assoc. Prof. Nishina, Okayama

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

Short presentation

59

Short presentation

60

Poster session

Poster session

Participants

Discussion

Director of IRCCS, Prof. Tatsumi

Group photo

3-3
第１回 統合物質国際シンポジウム

Jan. 24th-26th, 2018

Chikushi Campus, Kyushu University, Fukuoka, Japan
IRCCS The 1st International SymposiumJan. 24th-25th

The 2nd Base Metal Catalysis SymposiumJan. 25th-26th

Invited Lecturers
IRCCS Session

Base Metal Session

Prof. Ren-Gen Xiong

Prof. Paul J. ChirikProf. Ning Jiao

Prof. Jonathan Clayden

Prof. Karl Kirchner

Prof. Shaozhong Ge

Vienna University of Technology,
Austria

National University of Singapore,
SingaporeProf. Hairong Guan

Prof. Nobuaki Kambe

University of Cincinnati, USA

Osaka University, Japan

Prof. Audrey Moores

Prof. Takashi Ohshima

Southeast University, P. R. China
University of Bristol, UK

IRCCS / Base Metal Joint Session

Prof. Rinaldo Poli

CNRS, Laboratoire de Chimie de
Coordination, France

Prof. Eiichi Nakamura

Princeton University, USA

McGill University, Canada

Peking University, P. R. China

Kyushu University, JapanThe University of Tokyo, Japan
Contribution from IRCCS members
Prof. Ken-ichi Shimizu
Prof. Kentaro Tanaka
Hokkaido University, Japan

Nagoya University, Japan

Prof. Shiroh FutakiProf. Katsuhiko Tomooka

Dr. Zhiyi SongDr. Soichiro Ogi

Dr. Takahiro Iwamoto

Dr. Tomoyasu Hirai

Hokkaido University, Japan

Nagoya University, Japan

Kyoto University, Japan
Kyoto University, Japan

Kyushu University, Japan
Kyushu University, Japan

Image: by Vecter Art

Dazaifu Tenmangu

Photo: Provided by Dazaifu City

62

Fukuoka City

Photo: Provided by Fukuoka City

Chikushi Campus

Supported byContact

Integrated Research Consortium on Chemical Sciences (IRCCS)
Japan Science and Technology Agency (JST)Institute for Materials Chemistry and Engineering, Kyushu University
Research and Education Center for Advanced Energy Materials, Devices,and Systems, Kyushu University
Research and Education Center of Carbon Resources, Kyushu University

IRCCS The 1st International Symposium
Kazunari Yoshizawa
E-mail: kazunari@ms.ifoc.kyushu-u.ac.jp
Phone: +81-92-802-2529

The 2nd Base Metal Catalysis Symposium
Hideo Nagashima
E-mail: nagasima@cm.kyushu-u.ac.jp
Phone: +81-92-583-7819

Secretary officeE-mail: irccs-crest@cm.kyushu-u.ac.jp
Phone&Fax: +81-92-583-7839

http://jointproject-cscri.rcms.nagoya-u.ac.jp/
http://irccs-crest.cm.kyushu-u.ac.jp/

IRCCS-JST CREST Joint Symposium“Chemical sciences facing difficult challenges”[Part I] Jan. 24th-25th, IRCCS The 1st International Symposium[Part II] Jan. 25th-26th, The 2nd Base Metal Catalysis Symposium
Chikushi Hall, Chikushi Campus, Kyushu University, Fukuoka, Japan

January 24th (Wed.)
12:00–13:00

Registration

13:00–13:10

Opening Remarks(Chair: Osamu Sato, Kyushu University)

13:10–13:50[IL-1] Ren-Gen Xiong (Southeast University, P. R. China)“Ceramic-like Molecular Ferroelectrics”

13:50–14:10[YR-1] Tomoyasu Hirai (Kyushu University, Japan)“Synthesis and Characterization of Novel Polymer Brush with Well-controlled
Stereoregularity”(Chair: Tamaki Nakano, Hokkaido University)

14:10–14:30[YR-2] Soichiro Ogi (Nagoya University, Japan)“Seed-initiated Supramolecular Polymerization of π-Conjugated Molecules”

14:30–15:00[SR-1] Shiroh Futaki (Kyoto University, Japan)“Cytosolic Antibody Delivery by Lipid-sensitive Endosomolytic Peptide”

15:00–15:20

Break(Chair: Kazunari Yoshizawa, Kyushu University)

15:20–15:50[SR-2] Kentaro Tanaka (Nagoya University, Japan)“Molecular Architectures towards Soft Materials and Switching Molecular
Systems”

63

15:50–16:10[YR-3] Zhiyi Song (Hokkaido University, Japan)“Lithiation of Palladated Dihydropentacene: New Route for Introduction of
Substituents from Both of Electrophiles and Nucleophiles to Pentacene”(Chair: Shigehiro Yamaguchi, Nagoya University)

16:10–16:30[YR-4] Takahiro Iwamoto (Kyoto University, Japan)“Iron-Catalyzed anti-Selective Carbosilylation of Internal Alkynes”

16:30–17:00[SR-3] Katsuhiko Tomooka (Kyushu University, Japan)“Chemistry of Medium-sized Unsaturated Heterocycles”

17:00–18:30

Poster Session 1 (P-001 ~ P-091)

18:40–20:10

BanquetJanuary 25th (Thu.)(Chair: Yuichi Shimakawa, Kyoto University)
09:20–09:50[SR-4] Ken-ichi Shimizu (Hokkaido University, Japan)“Cooperative Heterogeneous Catalysis for Selective Transformations of Carboxylic
Acid Derivatives, CO2 and Hydrocarbons”

09:50–10:10

Short Talk 1[ST-1] Hajime Hojo (Kyushu University, Japan)[ST-2] Hiroshi Yoshida (Kumamoto University, Japan)(Chair: Yasuhiro Uozumi, Institute for Molecular Science)

10:10–10:50[IL-2] Audrey Moores (McGill University, Canada)“Sustainable Nanoparticles and Surface Plasmon Resonance enhanced
Hydrogenation Catalysis”

10:50–11:10

Break(Chair: Satoshi Hata, Kyushu University)

11:10–11:30

64[IL-3] Mitsuhiro Murayama (Virginia Tech, USA)
“Dynamic Observation on the Propagation of a Nanoscale Crack in an Industrial

Aluminum Alloy: an Application of in-situ Electron Tomography System to an
Engineering Material”(Chair: Jun-ichiro Hayashi, Kyushu University)
11:30–12:30[PL-1] Eiichi Nakamura (The University of Tokyo, Japan)“Atomic Resolution Electron Microscopy for Organic Chemists”

12:30–13:30

Lunch Break(Chair: Katsuhiko Tomooka, Kyushu University)

13:30–14:10

14:10–14:50[IL-4] Jonathan Clayden (University of Bristol, UK)“Naturally Inspired Solutions in Synthesis: Reactivity, Relays and Receptors”(Chair: Hisashi Shimakoshi, Kyushu University)
Short Talk 2[ST-3] Yoichi M. A. Yamada (RIKEN, Japan)[ST-4] Ryoichi Kuwano (Kyushu University, Japan)

14:10–14:50(Chair: Hiroshi Furuno, Kyushu University)
Short Talk 3[ST-5] Masaya Sawamura (Hokkaido University, Japan)[ST-6] Masanari Kimura (Nagasaki University, Japan)(Chair: Mitsuru Shindo, Kyushu University)

14:50–15:30[IL-5] Takashi Ohshima (Kyushu University, Japan)“Direct Catalytic Asymmetric Addition of Various Nucleophiles to N-Unprotected
Ketimines”

15:30–15:50

Break(Chair: Toru Oishi, Kyushu University)

15:50–16:30

16:30–17:00[IL-6] Ning Jiao (Peking University, P. R. China)“Base Metal Catalyzed Oxygenation and Nitrogenation Reactions”(Chair: Seiji Shirakawa, Nagasaki University)
Short Talk 4[ST-7] Hikaru Takaya (Kyoto University, Japan)[ST-8] Yasuhiro Arikawa (Nagasaki University, Japan)

65

[ST-9] Yoshihito Shiota (Kyushu University, Japan)(Chair: Takashi Ohshima, Kyushu University)
17:00–17:40[IL-7] Rinaldo Poli (CNRS, Laboratoire de Chimie de Coordination, France)“Copper and Iron-catalyzed Processes Involving Radicals”

17:40–19:10

Poster Session 2 (P-070 ~ P-140)

January 26th (Fri.)(Chair: Ryoichi Kuwano, Kyushu University)
09:20–10:00

10:00–10:30[IL-8] Hairong Guan (University of Cincinnati, USA)
“Iron- and Cobalt-Catalyzed Hydrogenation of Esters and Nitriles”(Chair: Yusuke Sunada, The University of Tokyo)
Short Talk 5[ST-10] Kouki Matsubara (Fukuoka University, Japan)[ST-11] Hisashi Shimakoshi (Kyushu University, Japan)[ST-12] Sachie Arae (Kumamoto University, Japan)

10:30–10:50

Break

10:50–11:10(Chair: Takashi Nishikata, Yamaguchi University)
Short Talk 6[ST-13] Yoshiaki Nakao (Kyoto University, Japan)[ST-14] Naohiko Yoshikai (Nanyang Technological University, Singapore)(Chair: Hideo Nagashima, Kyushu University)

11:10–12:10[PL-2] Paul J. Chirik (Princeton University, USA)
“New Opportunities in Synthesis with Iron and Cobalt Catalysts”

12:10–13:40

Lunch Break & Poster Session 3 (P-070 ~ P-140)(Chair: Yoshiaki Nakao, Kyoto University)

13:40–14:20

66[IL-9] Karl Kirchner (Vienna University of Technology, Austria)“New Chemistry Based on Non-Precious Metal Pincer Complexes”

(Chair: Naohiko Yoshikai, Nanyang Technological University)
14:20–15:00[IL-10] Shaozhong Ge (National University of Singapore, Singapore)“Cobalt-Catalyzed Hydrofunctionalization of Unsaturated Hydrocarbonds”

15:00–15:20

Break(Chair: Shigeki Sasaki, Kyushu University)

15:20–16:00[IL-11] Nobuaki Kambe (Osaka University, Japan)“Cross- and Multicomponent-Coupling Reactions Catalyzed by Base Metals”

16:00–16:10

Closing Remarks

67

IRCCS, The 1st International Symposium

68

Prof. Nagashima, Organiser

Prof. Sato, Kyushu

Discussion

Prof. Shimakawa, Kyoto

Asst. Prof. Hirai, Kyushu

Asst. Prof. Ogi, Nagoya

Prof. Futaki, Kyoto

Chair, Prof. Nakano, Hokkaido

Chair, Prof. Yoshizawa, Kyushu

Prof. Tanaka, Nagoya

Chair, Prof. Yamaguchi

Prof. Tomooka, Kyushu

69

70

Poster session

Poster session

Director of IRCCS, Prof. Tatsumi

Committee member, Prof. Iwamura

Banquet

Comittee member, Prof. Tamao

Regio and Chemoselective Conversions Controlled bySpecific Atomic Arrangement of Ordered Alloys
Masayoshi, Miyazaki,1 Shinya Furukawa,2 Takayuki Komatsu1
1 Department of Chemistry, Tokyo Institute of Technology, Tokyo, Japan, 2 Institute for Catalysis, Hokkaido
University, Hokkaido, Japan,
Introduction

Conclusion
The aim of this study

Selective Catalysis governed by specific surface atomic arrangement of ordered alloys(1) Seteroselective alkene isomerization (Z to E) by H2(2) Chemoselective
nitroarene hydrogenation

Discovery of the 3rd example ofthis unique surface chemistry:(3) Regioselective hydrogenation
system using ordered alloys

Combined with Pd3Pb alkyne
semihydrogenation catalyst

Target reaction
Hydrogenation of asymmetric
diene to monoene¾ Regio and chemoselective hydrogenation of dienes tomonoenes can be achieved using RhBi/SiO2 with high yield.
¾ The combination of one-dimensionally aligned Rh allays
and steric hindrance of large Bi atoms allows preferential
adsorption of terminal C=C moiety.

H2

One-dimentionally aligned Rh allows
one-atom hydrogenation for isomerization

Selective one-pot synthesis of (E)-alkenes
from alkynes with 1 atm H2 at 25πC.

Concave Rh and convex In sites can recognize end-on
adsorption of nitroarenes and allows its hydrogenation.

ChemCatChem, 2015, 7, 3472.

ACS Catal., 2016, 6, 2121.

Chem. Sci., 2016, 7, 4476.

Catalyst survey

Substrate scope of RhBi/SiO2

RhBi/SiO2 gave 2-hexanewith 90% yield.
RhBi showed the best regio andchemo selectivities(lowest ȴ^1+2 and r1h/r2h values)
Chemoselectivity: ȴ^1+2
decrease in alkenes selectivity
during the reaction

selective

Kinetic studies
Reaction orders

Regioselectivity: r1h/r2hrelative formation rate of
1-hexene to that of 2-hexene

Crystal structureof RhBi

Characterization

Table 1. Hydrogenation of various dienes using RhBi/SiO2time conv.
sel.
Entry
substrate
product
/h
(%)
(%)
1

5.5

95

90

2

20

99

88

3
4

HO

HO

+

+

5
6

6

85

89

9

90

95

18
10

97

80

83

90

9

10

TEM & STEM images of RhBi/SiO2

intra

Reaction condition
catalyst: 50 mg (Rh 3 wt%)
Substrate: 0.5 mmol
solvent: AcOEt 5 ml
H2 pressure: 1 atm
temperature: 70C
conversion: @0.5 h
selectivity: @95% conv.

M. Miyazaki, S. Furukawa,* T. Komatsu,*
J. Am. Chem. Soc., 2017, 139, 18231.

interHydrogenation of 1,4-hexadiene over various catalysts

selective

No heterogeneous catalyst has been achieved
this type of reaction with high yields.

Reaction condition: catalyst: 10 mg, substrate: 0.2 mmol, temp.: 25ȗC,solvent: THF 5 mL

The corresponding inner alkenes were obtained with high yields
for not only intramolecular but also intermolecular fashions.

DFT Calculations

Small nanoparticles (ca. 3 nm) of single crystals
of intermetallic RhBi were formed.

FT-IR spectra of adsorbed COTransition state structure

RhBi(110) planer = k PH21.0 [diene]о0.4
Based on the following kinetic model,
this result indicates that the ratedetermining step is a surface reaction(H diffusion or attack).
Kinetic model based on a LangmuirHinshelwood-type mechanism
Considering a Langmuir-Hinshelwood type mechanism for the dienehydrogenation, the reaction steps are descrobed as follows:Hଶ + ߪ ֎ 2 H ȉ ߪ
S+ߪ ֎ Sȉߪ2Hȉߪ+Sȉߪ ֎ Pȉߪ+ ߪPȉߪ ֎ P+ߪ: H2 adsorption: diene adsorption: surface reaction: alkene desorption

Rh-H distance at TS
terminal C=C < inner C=C

Optimized structure of adsorbed
1,4-hexadiene

Energy diagram of 1,4-hexadiene hydrogenation
H attack toinner C=C

where, S, P, and ʍ are reactant diene, product alkene, and adsorption
site, respectively.
Assuming that the surface reaction is the rate determining step, theoverall reaction rate can be expressed as follows:

H attack to inner C=C iskinetically unfavorable‫ߠ݇ = ݎ‬ୌ ଶ ߠୗ

Besides, other steps can be regarded to be in equilibrium. Therefore, theequilibrium constants are defined as follows:‫ܭ‬ଵ = ߠୌ ଶ /ܲୌమ 1 െ ߠ‫ܭ‬ଶ = ߠୗ /[S] 1 െ ߠ‫ܭ‬ସ = [P] 1 െ ߠ /ߠ୔

where, k, ߠ௑ , and (1 െ ߠ) are the rate constant of surface reaction,
coverage of X, and percentage of vacant site: 1 െ (ߠୌ + ߠୗ + ߠ୔ ),respectively. Here, the coverages are expressed as follows using thecorresponding sticking probabilities, kX:
ߠୌ = ʹ݇ୌమ ܲୌమ 1 െ ߠߠୗ = ݇ୗ [S](1 െ ߠ)
ߠ୔ = ݇୔ [P](1 െ ߠ)1െߠ =Based on these, the overall reaction rate can be descried as follows:݇‫ܭ‬ଵ ‫ܭ‬ଶ ܲୌమ [S]‫=ݎ‬(1 + ʹ‫ܭ‬ୌమ ܲୌమ + ‫ܭ‬ୗ [S] + ‫[ ୔ܭ‬P])ଶ

XRD patterns of RhM/SiO2

H attack toterminal C=C

1
1 + ʹ‫ܭ‬ୗ ܲୌమ + ‫ܭ‬ୗ [S] + ‫[ ୔ܭ‬P]

When adsorption of H2 and diene are very weak and strong, respectively(‫ܭ‬ୌమ ܲୌమ ‫ ا‬1, ‫ܭ‬ୗ [S] > 1) and assuming low diene conversions ([P]~0),
this equation is approximated simply as follows:࢑ࡷ૚ ࡷ૛ ࡼࡴ૛ [ࡿ]࢘=(૚ + ࡷࡿ [ࡿ])૛

Theoretical values (by DFT) of the vibratonalfrequencies of CO on RhBi(110) and (102) agreed
finely with the experimental values, supporting theexposure of these planes.

Regioelectivity vs. atomic radius of M
¾ The larger the second atom is,
the higher the regioselectivity is.

This equation indicates the first-order dependence of r on ܲୌమ and thatthe reaction order of [S] ranges from о1 to 1. Considering ‫ܭ‬ୗ [S] > 1, thereaction order of [S] inclines to the negative side. This strongly agrees
with the experimental reaction orders (1.0 and о0.4 for ܲୌమ and [P],respectively), supporting the validity of this kinetic model.

¾ More clear relationship wasobserved among RhM with onedimentionally aligned Rh.

A first-order dependence of H2 pressure on reaction rates generally
suggests the following situations, (1) diffusion (or dissolving) limiting, (2)adsorption limiting, and (3) surface reaction limiting. However, thenegative order of reactant diene and the low KIE value observed for D2
excludes (1) and (2), respectively. Therefore we conclude that thesurface reaction is rate-limiting.

The regioselectivity relies on the
bulkiness of M and one-dimentionalalignment of Rh atoms.

The desired ordered alloy phases were successfully
formed with high phase-purity.

71

Machine Learning Prediction of Adsorption Energies on Metal Alloys
for Effective Utilization of Methane
Takashi Toyao,a,b Satoru Takakusagi,a Ichigaku Takigawa,c Ken-ichi Shimizu,a,b
aInstitute for Catalysis, Hokkaido university, N-21, W-10, Sapporo 001-0021, Japanb Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, 615-8520, Kyoto, Japanc Graduate School of Information Science and Technology, Hokkaido University, N-14, W-9, Sapporo 060-0814, Japan

Introduction

This study

Brønsted-Evans-Polanyi relation

We have predicted adsorption energies of CH4 related species (CH3, CH2, CH, C,
and H) on the Cu-based alloys toward efficient utilization of CH4.
Eact
Eact

Machine-learning prediction of the d-band center for metals and bimetals

Potential energy

Previous study

Eact : Activation energy

GEr

GEr : Reaction energy

Reaction coordinate

GEads

Linear relationship between activation energy and dissociative chemisorption energy

Utilization of CH4

Partial oxidation reaction
CH4→ CH3OH
Coupling reaction
CH4→

C 2 H 4 , C2 H 6 , C6 H 6

The key is how to produce CH3 species
and prevent successive formation of CH2 species

H. Schwarz, Angew. Chem. Int. Ed. 2011, 50, 10096
X. Bao et al., Science, 2014, 344, 616

Takigawa, K. Shimizu, K. Tsuda, S. Takakusagi, RSC Advances, 2016, 6, 52587
Highlighted in Chemistry World

Methods and results

The process employed to discover new materials for specific applications typically utilizes
screening of large compound libraries. In this approach, the performance of a compound iscorrelated to the properties of elements referred to as descriptors. In the effort described
below, we developed a simple and eﬃcient machine learning (ML) model for predicting
adsorption energies of CH4 related species, namely CH3, CH2, CH, C, and H on the Cu-based
alloys. The developed ML model predicted the DFT-calculated adsorption energies with 12
descriptors, which are readily available values for the selected elements. The predictive
accuracy of 4 regression methods (ordinary linear regression by least squares (OLR), random
forest regression (RFR), gradient boosting regression (GBR), and extra tree regression(ETR)) with diﬀerent numbers of descriptors and diﬀerent test-set/training-set ratios were
quantitatively evaluated using statistical cross validations. Among 4 types of regression
methods, we have found that ETR gave the best performance in predicting the adsorptionenergies with the average root mean squared errors (RMSE) below 0.3 eV. Strikingly, despite
its simplicity and low computational cost, this model predicts well the adsorption energies on a
range of Cu-based alloy models (46 in total number) as calculated by using DFT. In addition,
we show the ML prediction for the differences in the adsorption energies of CH3 and CH2 on
the same surface. This would be of great importance especially when designing the selective
catalytic reaction processes to suppress the undesired over reactions. The accuracy andsimplicity of the developed system suggest that adsorption energies can be readily predictedwithout time-consuming DFT calculations, and eventually, this would allow us to predict thecatalytic performances of the solid catalysts.

DFT-calculated adsorption energies of CH3, CH2, CH, C, and H

Machine learning methods
䕺 Ordinary linear regression by least squares (OLR): Linear model䕺 Random forest regression (RFR): Non-linear model䕺 Gradient boosting regression (GBR): Non-linear model䕺 Extra trees regression (ETR): Non-linear model

Computational methods for DFT calculations
䘟 Vienna ab initio simulation package (VASP)䘟 Perdew−Burke−Ernzerhof (PBE) generalized gradient functional䘟 Cutoff energy = 400 eV䘟 3 㽢 3 surface unit cell with 4 atomic layers
䘟 1 surface- and centered-atom-exchanged Cu(111)䘟 15 Å vacuum height䘟 The bottom 2 layers were ﬁxed at the corresponding bulk positions

Correlation of descriptors

Evaluation of descriptor importance for ETR
Screening of predictive ML methods using adsorption energies of CH 3

Prediction of adsorption energies of CH3 with 4 ML methods

The robust ML prediction performance remained constant even when using even only 3 descriptors. The top 3 descriptors of the doped
metal include its group in the periodic table, surface energy, and melting point.

Prediction of values of ECH3-ECH2 for CH4 utilization

Training error / eV

Test error / eV



OLR

RFR

GBR

ETR


mean
sd
(min, max)
0.15
0.01
(0.10, 0.18)
0.09
0.01
(0.07, 0.11)
0.00
0.00
(0.00, 0.00)
0.00
0.00
(0.00, 0.00)

mean(min, max)
0.27
(0.15, 0.47)
0.24(0.14, 0.40)
0.24(0.13, 0.38)
0.24(0.13, 0.38)

sd
0.07
0.06
0.05
0.06

The three nonlinear methods (RFR, GBR, and ETR) showed better prediction performance than the OLR method. The three methods
gave almost the same predicting accuracy. ETR and RFR are known to be less hyperparameter sensitive than GBR, and thus we can
avoid demanding hyperparameter tuning. Moreover, the training time for ETR is considerably smaller than RFR and GBR because ETR
is based on random-splitting trees. We therefore concluded that the ETR model is the best choice for prediction of the adsorptionenergies explored in this study.

Prediction of adsorption energies of CH2, CH, C, and H

The initial step of the OCM reaction is the formation of CH3 species.
Once the formation of the CH3 species is initiated on a catalytic
surface, gas-phase reactions ensue. The radical species thus formed
are expected to recombine to form ethane. In addition, the CH3
species is a key intermediate for a partial oxidation reaction of
methane to methanol. Consequently, it is important for both OCM andmethanol synthesis (via partial oxidation of methane) to stabilize theCH3 species and to avoid further dehydrogenation to CH2, CH, and C
and hence to undesired coke or COx formation.
 For the catalysts design, therefore, creating surfaces on which the CH3 species adsorbs more strongly than does the CH2 species is
crucial. For this reason we compared the adsorption energies of CH 3 and CH2 on the Cu-based alloy surfaces. The difference in theadsorption energies of CH3 and CH2, obtained by subtraction of the adsorption energies of CH3 from those of CH2 (ECH3-ECH2) arepresented above. If our hypothesis is correct, elements that show small ECH3-ECH2 values (e.g., Te, Sn, and Mg) are the best-suited doping
metals. On the contrary, elements that show large ECH3-ECH2 values (e.g., Cr, V, and Mo) could generate Cu surfaces that induce theundesired reactions of methane.

Conclusions
9 DFT-calculated adsorption energies of CH3, CH2, CH, C, and H on Cu-based alloys (46 in total
number for each adsorbate) were predicted by machine learning methods by using 12
descriptors, which are readily available values for the selected elements
9 Among 4 types of regression methods (ordinary linear regression by least squares (OLR),
random forest regression (RFR), gradient boosting regression (GBR), and extra tree regression(ETR)), ETR gave the best performance in predicting the adsorption energies with the averageroot mean squared errors (RMSE) below 0.3 eV.
9 ML prediction for the differences in the adsorption energies of CH3 and CH2 on the same surface
was also presented for practical use to design the selective catalytic reaction processes tosuppress the undesired over reactions.

72

Proof of multielectron transfer processes in heterogeneous photocatalysis

Mai Takashima,1,2 Haruna Hori,2 Shugo Takeuchi2, Mai Takase3 and Bunsho Ohtani1,21Institute for Catalysis and 2Graduate School of Environmental Science, Hokkaido University,
3Graduate School of Engineering, Muroran Institute of Technology

commercial titania

flake ball-shaped bismuth tungstate¾ 4 kinds of commercial titaniaz small anatase; Ishihara Sangyo ST-01 (4 nm): SAz small rutile; Tayca MT-150A (13 nm): SRz large anatase; Fluka (170 nm): LAz large rutile; Showa Denko Ceramics ST-G2 (360 nm):LR¾ photocatalytic activity tests
O2 system; 2H2O + 4h+ ĺ 4H + + O2 with IO3- or Fe3+

2

2

0

1

0
SR 30

0.1

10

0.2

20

20
10
0

10

50

0
LA 30

6
4
2
0
10

0.3
1

2

0
2
1
0

0.5

20

1.0

10

10

1

0

LR

5
0

0

6
4
2
0

200
0.01 0.02 0.03
1

100
0

0.3

2

0.5
0
r/ȝPRO h-1 cm-2

0.2

0

1

100 502
IL/W cm-2

0

3

SA

2

2
1
0
20
10
10

4

0.1

10

SA 30

1

2
0.1 0.2 0.3 0.4 0.5
2

0
150
100

1

0.6

0
20

0
LR 150100

0.02 0.04 0.06
1
2
IL/W cm-2

4

50
3

6

8

80 mW

-5
0.5

0.5

-7

WML

1

-9

1
2
0

-2

(d)

-2

2

-5

0

-7

FB
-9

-11
-4

10

1

1

8

2

4 mW

50
LA

0

ln (I /mW)
4
6

2

10

1
SR

0.4

20

0

-2

-5

2

2

0.2

-4

ln (r/μmol h-1)

2
1
0

light intensity dependency
(c)

(b)

ln (r/μmol h-1)(a)

¾ hydrothermal synthesis
z Bismuth Nitrate(Bi䠄NO3)3䠖5.0 mmol)z Sodium Tungstate (Na2WO4䠖2.75 mmol)
9 hydrothermal synthesis (433 K, 20 h)
9 calcination (773 K for 3 h in air)
9 wet milling (a planetary ball mill, 500 rpm for 6 h)
¾ photocatalytic activity tests
CO2 system; CH3COOH + 2O2ĺ 2CO2 + 2H2O

0

2
0.5

-6

2

FB

-7

0.5

1

-8

1

-9
1

2

500FB
3
4
ln (I /mW)

5

6

2

4

6

8

-11

IL-dependent oxygen
evolution rates ofcommercial titania using(a) IO3– and (b) Fe3+ aselectron accepter anddouble-logarithmic plots of
I-dependent acetic-aciddecomposition rates of (c)FB, WML and (d) 500FB.

kinetic model
1/Ĳ2
TiO2
ILȥĳ

1/Ĳ1

h+
h+
TiO2(h+h+)
k

ILȥ2ĳ

h+ e- IO3-/Fe3+
TiO2(h+)r=

H 2O 2
fast

IL : light intensityȥ : photoabsorption
efficiency
ȥ2 : photoabsorption
efficiency <TiO2(h+)>ĳ: quantum efficiency ofe- capturek : rate constantsr =O2rutileacceptork IL 2ȥȥ2ĳ2

size
/nm

SR

13

IO3−

1

80

1

(1/Ĳ1) (k + 1/Ĳ2 + (k + 1/Ĳ2) IL ȥ2ĳ)

SR

13

Fe3+

13

190

0.4

rutile

size
/nm

(ĳ)

Ithr/mW(ȥ¶ĳ¶Ĳ )at lower I,
at higher I,

r = IL 2ȥȥ2ĳ2Ĳ1
r = IL ȥĳ

I thr = 1 /ȥ2ĳĲ1

IO3-

(ĳ)

Ithr/mW(ȥ¶ĳ¶Ĳ )

SR

13

1

80

1

SR
calcined at 973 K

69

10

20

4.0

LR

350

22

<1

> 80

(reaction step)<BWO> + hv ĺ < BWO(1e)>< BWO(1e)> + hv ĺ < BWO(2e)><BWO(1e)> ĺ <BWO>< BWO(2e)> + RH ĺ <BWO> + R• kr
R• + O2 ĺ RO2•RO2࣭+ RH ĺ RO2H + R•
2RO2• ĺ RO4R

(rate),ȥ0ĭ,ȥ1ĭ [BWO(1e)]kd [BWO(1e)][BWO(2e)][RH]
ki [R•][O2]
kp [RO2•][RH]
kt [RO2•]2

0.5
I 2ȥ0 ȥ1ĭ2
I2
ȥ0 ȥ1ĭ2 0.5
kd + I ȥ1 ĭ + kp[RH]kt
kd+ Iȥ1ĭ

(

direct holereaction)()

radical chain reaction withperoxy radical as a chain carrier(description)
first excitation
second excitation
deactivation
radical formation
initiation
propagation
termination

BWO> : photocatalyst, RH : substrate
I : light intensity
ȥ0 : photoabsorption efficiency of <BWO>
ȥ1 : photoabsorption efficiency <BWO(1e)>ĭ: quantum efficiency of e--h+ production
k : rate constants

at lower I ĺI ȥ1ĭ << kd
r = I 2ȥ0 ȥ1 ĭ2kd-1 + k3[RH](I 2ȥ0 ȥ1 ĭ2kd-1kt-1)0.5 ĺ(Į/kd0.5) I
at higher I ĺI ȥ1ĭ >> kd
r = I ȥ0ĭ + kp[RH](I ȥ0ĭkt-1)0.5 ĺ(Į/(ȥ1ĳ)0.5) I 0.5

Ithr = kd(ȥ1ĭ)-1Conclusion
Light-intensity dependences of rates for photocatalytic wateroxidation and oxygen reduction were studied using commercial
titania and laboratory-made bismuth tungstate powders under highintensity 365-nm UV-LED photoirradiation and processes ofmultielectron (mainly two-electron) transfer reaction were supported
based on kinetic models.
[1] S. Takeuchi, M. Takashima, M. Takase and B. Ohtani, Chem. Lett., accepted[2] H. Hori, M. Takashima, M. Takase and B. Ohtani,Catal. Today, in press (10.1016/j.cattod.2018.01.001)

73

Multielectron Oxygen Reduction on Copper(I) oxide-Loaded Titaniumoxide Photocatalysts in Decomposition of Organic Compounds
Peng Wang and Bunsho Ohtani
Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan
Email: wang.p@cat.hokudai.ac.jp

Introduction
ADVANTAGES:
Low cost
High chemical stability

(b)

(a)

DISADVANTAGES:
Large band gap (3.0-3.2 eV)

TiO2 Ultraviolet light absorption (3-5 %)Photocatalytic reactions

Absence of specific reaction site toaccumulate excited electrons (rutile)

Research
Objectives
Photoabsorption

Photocatalytic
activity

Fig. 4 SEM images of titania and FCPsloaded titania.

• Loading amount: 2 wt%• Good interaction• XRD, UV-vis, EDS: copper(I)oxide (data not shown)

Fig. 5 (a) Photocatalytic activity of FCPs in CO2 system;(b) Photocatalytic activity of titania and FCPs-loaded
titania in CO2 system.

Photocatalytic activity:• r-c, r-co and r-o: low activity• FCPs-loaded titania > titania• c-S > co-S > o-S > S

Role of FCPs
Fig. 1 Mechanism of titania in photocatalytic reactions.
Fig. 6 SEM images of titania (STG2) and FCPs-loaded titania.

Experimental

(b)

(c)

Fig. 7 (a) XRD patterns of titania (STG2) and FCPs-loaded titania; (b) Photocatalytic activity of titania
and FCPs-loaded titania in CO2 system; (c) Photocatalytic activity of titania, Pt-loaded titania, copper(I)oxide-loaded titania(denoted as b-S, mixed by mortar) and FCPs-loaded titania in CO2 system.
Fig. 2 3-D geometry models of faceted copper(I) oxide polyhedrons. (a) cube; (b)cuboctahedron; (c) octahedron.

Faceted Cu2O particles (FCPs)

Photocatalytic activity:• r-c-S > r-co-S > r-o-S > S, {100} facet is the most active facet• r-c-S > b-S, better interaction by in-situ one-pot wet chemical synthesis• Cubes (c): six {100} facets• r-c-S > Pt-S, suppress electron/hole recombination• Cuboctahedrons (co): eight {111} and six {100} facets• Multielectron oxygen reduction ( two or four)• Octahedrons (o): eight {111} facets
Room temperature: r-c, r-co and r-o.
FCPs-loaded titania: c-S, co-S, o-S, r-c-S, r-co-S and r-o-S.

Results and Discussions
Fig. 8 Schematic diagram of possible
oxygen reduction reactions of titania.

Fig. 9 Light intensity dependent-photocatalytic
activity of titania (blue) and r-c-S (red).

Two-electron oxygen reduction,ȥĭ<PC> + hQ ĺ <PC> (e㸫),ȥ¶ĭ<PC> (e㸫) + hQ ĺ <PC>**<PC> + RH ĺ <PC> + R࣭k1
R࣭+ O2 ĺ RO2࣭k2
RO2࣭+ RH ĺ RO2H + R࣭
k3
2RO2࣭ĺ RO4R
k4
<PC> (e㸫) ĺ <PC>k5
<PC>㸸photocatalyst
I 㸸 light intensityĭ㸸quantum efficiencyk 㸸 rate constant
RH㸸 reactive substrateȌ 㸸absorption efficiency (<PC>)Ȍ’ 㸸absorption efficiency (<PC> (e-))

Fig. 3 SEM images of faceted Cu2O particles (FCPs).

• Cube ĺ Cuboctahedron ĺ Octahedron• Low temperature: small particle size

Acknowledgements and References

The author (pw) acknowledges the financial support from JSPS Postdoctoral Fellowship Program for Overseas Researchers.
(1) Abe R.; Takami H.; Murakami N.; Ohtani B. J. Am. Chem. Soc. 2008, 130, 7780
(2) Zhang, D.; Zhang, H.; Guo; L. Zheng, K.; Han X.; Zhang Z. J. Mater. Chem. 2009, 29, 5220-5225

74

Crystalline characteristics and photocatalytic activity of decahedralshaped anatase titania particles
Kenta Kobayashi,1 Mai Takashima,1,2 Mai Takase3 and Bunsho Ohtani1,2

1Graduate School of Environmental Science and 2Institute for Catalysis, Hokkaido University,
3Graduate School of Engineering, Muroran Institute of Technology

䕔Decahedral anatase titania particles (DAP)(001)
high surface energy(101)
thermodynamically stablehigh-level photocatalytic activity

crystalline phase transition
anataserutileeffect of particles fusion on(metastable state)(stable state)䞉transition behavior
䞉photocatalytic activity

phase transition occurred from(001) facet showing lower stability
Chem. Mater, 26, 1014 (2014)

䕔Effect of fusion on DAP properties

degree of fusion

SSA crystalline anatase rutile non crystal activity activity
(%)
(%)
(%)
(CO2)
/m2 g-1 size/nm(H2)86.39 2.45
11.16
nf-DAP
14.3
73.8
115
264
86.72 7.40
5.88
f-DAP
13.7
55.7
97
187
78.28 6.65
15.07
reference 97.5
11.7(100) (100)samplephase transition
temperature/K
1205
1150
990

transition
NCP
rate/K-1-1.09
1.32-0.7344.19-0.721-

anatase-rutile phase transition

number of composition
particles (NCP)=

number of particles
number of group

photocatalytic activity

distance fromtube to foil

7.5 cm

5.5 cmfusion causedby latticedefects or impurity

grain boundary leading to crystalline defects
and high interface energy
f-DAP show
small crystalline size

high amountof electron trap density
derived grain boundary

higher NCP,
lower phasetransition temperature

progression of phasetransition easily
by grain boundary

effect of particles fusion decreasingphase transition temperature and photocatalytic activity
future plan

• Investigation of energy-resolved distribution of electron traps

䕔Experimental
DAP preparation by gas-phase reaction
TiCl4 + O2 ĺTiO2 + 2Cl2

Photocatalytic activity test
CH3COOH+2O2ĺ2CO2+2H2O photocatalytic activity evaluated
CH3OHĺH2+HCHO
with rate of production liberation
light source
reference photocatalyst

PHUFXU\ODPS Ȝ!nm)
FP-6 (Showa Denko Ceramics)

Temperature programed XRD measurement
Temperature condition

increasing rate
2 K min-1
measurement rate 573-1523 K

XRD measurement condition
scanning ratescanning range

10㼻min-1
10-90㼻

75

X-ray diffraction analysis on thermal anatase-rutile transformation of titania particles
Bob John,1 Mai Takashima1,2 and Bunsho Ohtani11,2(Graduate School of Environmental Science,1 Institute for Catalysis,2 Hokkaido University)

Anatase-rutile transition (ART)ART<Purpose>what governs
anatase-rutile(ART) transition¾important in materialscience¾kinetically controlled¾unknown mechanism¾different behaviour
depending on thephysical/structuralproperties

metastable
form

Analysis of ART by temperature-programmed XRD
OAP-18OAPs
FP-6

ST-0 &
ST-21

OAP
P25

¾ 2ș: 10-90˅
¾ rate: 2 K min-1¾ scan rate: 10 K min-1¾ temperature: 573 -1523 K¾OAP: octahedral
anatase particles¾hydrothermally (HT)synthesized¾6, 9, 12 & 18: HT
times (hrs)

Crystallite size analysis
crystallite size = Scherrer
equation¾2ș 25.2 for anatase {101}plane¾2ș 27.2 for rutile {110}planeOAP- 6

R sizeOAP -9OAP- 12
OAP- 18

A size%R

A size%A%R%X

R size X% ST-01
X: OAP-9% FP-6

R sizeST-01

R sizeR size FP-6

%R
A size ST-01

76

A size X

A size FP-6

Conclusion¾ ART was successfully studied by programmed
XRD method.
¾ OAP has higher thermal stability¾ crystallite size of anatase increase withtemperature¾ ART process: amorphous-anataseÆrutile(smaller anataseÆrutile
larger anataseÆ rutile)

Excited-state Aggregate Formation of A Near-infrared DyezƵĞtĂŶŐĂ͕ZŽŶŐ tĂŶŐď͕dĂŵĂŬŝEĂŬĂŶŽĂΎ
Ă/ŶƐƚŝƚƵƚĞ ĨŽƌĂƚĂůǇƐŝƐ;/dͿ͕'ƌĂĚƵĂƚĞ^ĐŚŽŽůŽĨŚĞŵŝĐĂů^ĐŝĞŶĐĞƐĂŶĚŶŐŝŶĞĞƌŝŶŐ͕ĂŶĚ/ŶƚĞŐƌĂƚĞĚZĞƐĞĂƌĐŚŽŶƐŽƌƚŝƵŵŽŶŚĞŵŝĐĂů^ĐŝĞŶĐĞƐ;/Z^Ϳ͕,ŽŬŬĂŝĚŽhŶŝǀĞƌƐŝƚǇ͕:ĂƉĂŶΎͲŵĂŝů͗ƚĂŵĂŬŝ͘ŶĂŬĂŶŽΛĐĂƚ͘ŚŽŬƵĚĂŝ͘ĂĐ͘ũƉďKŶ ůĞĂǀĞĨƌŽŵŽůůĞŐĞŽĨŚĞŵŝƐƚƌǇĂŶĚDŽůĞĐƵůĂƌŶŐŝŶĞĞƌŝŶŐ͕WĞŬŝŶŐhŶŝǀĞƌƐŝƚǇ͕ŚŝŶĂďƐƚƌĂĐƚ͗ ǇĞƐ ƚŚĂƚ Ğŵŝƚ ůŝŐŚƚ ŝŶ ƚŚĞ ŶĞĂƌ ŝŶĨƌĂͲƌĞĚ ;E/ZͿ ƌĞŐŝŽŶ ĂƌĞ ŝŵƉŽƌƚĂŶƚ ŝŶ ŵĞĚŝĐŝŶĂů ĂŶĚ ƉŚǇƐŝŽůŽŐŝĐĂů ĨŝĞůĚƐ ďĞĐĂƵƐĞ
ƚŚĞǇ ĐĂŶ ďĞ ĂƉƉůŝĞĚ ĨŽƌ ĚŝĂŐŶŽƐŝƐ ĂŶĚ ŝŵĂŐŝŶŐ ŽĨ ƚŝƐƐƵĞƐ ĚƵĞ ƚŽ ƚŚĞ ĨĂĐƚ ƚŚĂƚ ǁĂƚĞƌ ĂŶĚ ŚĞŵŽŐůŽďŝŶ ĚŽ ŶŽƚ ƐĞƌŝŽƵƐůǇ
ŝŶƚĞƌĨĞƌĞ ƚŚƌŽƵŐŚ ƐĐĂƚƚĞƌŝŶŐ ĂŶĚ ĂďƐŽƌďĂŶĐĞ ŝŶ ƚŚĞ ƌĂŶŐĞ ŽĨ ĂƌŽƵŶĚ ϳϬϬͲϵϬϬ Ŷŵ͘ ϯ͕ϯΖͲŝĞƚŚǇůƚŚŝĂƚƌŝĐĂƌďŽĐǇĂŶŝŶĞ ŝŽĚŝĚĞ
;d/Ϳ ŝƐ Ă ƌĞƉƌĞƐĞŶƚĂƚŝǀĞ ĞǆĂŵƉůĞ ĂŵŽŶŐ ƐƵĐŚ ĚǇĞƐ ĂŶĚ ŚĂƐ ďĞĞŶ ƐƚƵĚŝĞĚ ĨƌŽŵ ǀĂƌŝŽƵƐ ǀŝĞǁ ƉŽŝŶƚƐ͘ /Ŷ ƚŚŝƐ ǁŽƌŬ͕ ǁĞŝŶǀĞƐƚŝŐĂƚĞĚ ĞǆĐŝƚĞĚͲƐƚĂƚĞ ƉƌŽƉĞƌƚŝĞƐ ŽĨ d/ ŝŶ ƐŽůƵƚŝŽŶ ĂŶĚ ĨŽƵŶĚ ƚŚĂƚ d/ ĨŽƌŵƐ Ăƚ ůĞĂƐƚ ƚǁŽ ĚŝƐƚŝŶĐƚŝǀĞ ĞǆĐŝƚĞĚͲƐƚĂƚĞ
ĂŐŐƌĞŐĂƚĞƐ ǁŚŽƐĞ ƐƚƌƵĐƚƵƌĞƐ ĂŶĚ ĐŽŶƚĞŶƚƐ ǀĂƌǇ ĚĞƉĞŶĚŝŶŐ ŽŶ ĐŽŶĐĞŶƚƌĂƚŝŽŶ ĂŶĚ ƐŽůǀĞŶƚ͘ ^ƵĐŚ Ă ƉŚĞŶŽŵĞŶŽŶ ŚĂƐ ďĞĞŶƌĞƉŽƌƚĞĚ ŽŶůǇ ĨŽƌ Ă ƐǇƐƚĞŵ ŽŶ ƚŚĞ ƐƵƌĨĂĐĞ ŽĨ ŐŽůĚ ďƵƚ ŝƐ ƵŶƉƌĞĐĞĚĞŶƚĞĚ ŝŶ Ă ŚŽŵŽŐĞŶĞŽƵƐ ƐǇƐƚĞŵ ŝŶĐůƵĚŝŶŐ ƐŽůƵƚŝŽŶ͘ϭ/ŶƚƌŽĚƵĐƚŝŽŶ
¾ /ŶƚĞŶƐĞŶĞĂƌͲŝŶĨƌĂƌĞĚĂďƐŽƌƉƚŝŽŶĂŶĚĞŵŝƐƐŝŽŶ
¾ ,ŝŐŚĨůƵŽƌĞƐĐĞŶĐĞƋƵĂŶƚƵŵǇŝĞůĚͲͲ KƉƚŝĐĂůďŝŽůŽŐŝĐĂůƉƌŽďĞ
ͲͲ &ůƵŽƌĞƐĐĞŶĐĞŝŵĂŐŝŶŐ

ϮŵŝƐƐŝŽŶĂŶĚǆĐŝƚĂƚŝŽŶ^ƉĞĐƚƌĂŽĨd/ŝŶDĞK, ĂŶĚŝŶD^KWŚŽƚŽƉŚǇƐŝĐĂů WƌŽƉĞƌƚŝĞƐ

% LQ 0H2+([FLWDWLRQ VSHFWUDŵŝƐƐŝŽŶĂŶĚǆĐŝƚĂƚŝŽŶ^ƉĞĐƚƌĂŽĨd/ŝŶƚK, ĂŶĚŝŶ,ϮK

D >>'7&,@

MonomeremissionHP  QP

HP  QP
HP  QP

E >'7&,@
 PJ   P/

H[  QP

HP  QP
HP  QP






:DYHOHQJWK QP 0 0 0 
:DYHOHQJWK QP)LJ 89VSHFWUDRI'7&,LQ(W2+ $ DQGLQ+2 % DWGLIIHUHQW FRQFHQWUDWLRQVHP  QP
H[  QP

ŐŐƌĞŐĂƚŝŽŶŽĨd/HP  QP

G >'7&,@  [  0
 PJ   P/

:DYHOHQJWK QP>'7&,@>'7&,@>'7&,@

 0

HP  QP



D
E
F



H[  QP

 [  0HP  QP
HP  QP

F >'7&,@  [  PJ   P/

F >'7&,@

$ LQ (W2+ [  0H[  QP

 [  0ďƐŽƌďĂŶĐĞ^ƉĞĐƚƌĂŽĨd/ŝŶƚK, ĂŶĚŝŶ,ϮK

H[  QP

E >'7&,@(PLVVLRQ VSHFWUD
F  [  0)LJ(PLVVLRQDQGH[FLWDWLRQVSHFWUDRI'7&,LQ'062 $ DQGLQ0H2+ % 
DWGLIIHUHQWFRQFHQWUDWLRQVHP  QP

 [  0

E  0

H[  QP

1RUPDOL]HG,QWHQVLW\

1RUPDOL]HG,QWHQVLW\

Excimeremission
Monomer% LQ +2
emission
D >'7&,@  [  0
 PJ   P/

D  0 / PRO FP$ LQ (W2+

ExcimeremissionH[  QP

HP  QP
HP  QP






:DYHOHQJWK QP)LJ,QWHQVLW\ZHLJKWHG*DXVVLDQGLVWULEXWLRQRISDUWLFOH
VL]HRI'7&,REWDLQHGWKURXJKG\QDPLFOLJKWVFDWWHULQJLQ(W2+
D DQGLQ+2 E )LJ (PLVVLRQ EOXH DQGH[FLWDWLRQ JUHHQDQGUHG VSHFWUDRI'7&,LQ(W2+$ DQGLQ+2 % DWGLIIHUHQW FRQFHQWUDWLRQVϯŽŶĐůƵƐŝŽŶƐ

¾ d/ ƐŚŽǁƐ ŵŽŶŽŵĞƌ ;ϲϬϬͲϳϬϬ ŶŵͿ ĂŶĚ ĞǆĐŝŵĞƌ ;ϳϱϬͲϴϱϬ ŶŵͿ ĞŵŝƐƐŝŽŶƐ͘¾ d/ ŝƐ ƉƌŽƉŽƐĞĚ ƚŽ ĨŽƌŵ SͲƐƚĂĐŬĞĚ ĂŐŐƌĞŐĂƚĞƐ ŝŶ ƚK, Ăƚ ĂůůĐŽŶĐĞŶƚƌĂƚŝŽŶƐ ĂŶĚ ĂůƐŽ ŝŶ ,ϮK Ăƚ ůŽǁĞƌ ĐŽŶĐĞŶƚƌĂƚŝŽŶƐ ĂŶĚ ƵŶƐƚĂĐŬĞĚ
ĂŐŐƌĞŐĂƚĞƐ ŝŶ ,ϮK Ăƚ ŚŝŐŚĞƌ ĐŽŶĐĞŶƚƌĂƚŝŽŶƐ͘¾ /Ŷ ƚK,͕ SͲƐƚĂĐŬĞĚ ĂŐŐƌĞŐĂƚĞƐ ǁŝƚŚ ǀĂƌŝŽƵƐ ƐƚƌƵĐƚƵƌĞƐ ǁŝƚŚ ĚŝĨĨĞƌĞŶƚ
ĞǆĐŝƚĂƚŝŽŶ ĞŶĞƌŐŝĞƐ ĂƌĞ ƌĞƐƉŽŶƐŝďůĞ ĨŽƌ ƚŚĞ ĞǆĐŝŵĞƌ ĞŵŝƐƐŝŽŶ͘ /Ŷ ,ϮK ĂƚǁŝƚŚ ƌĂƚŚĞƌ ƵŶŝĨŽƌŵ
ůŽǁĞƌ ĐŽŶĐĞŶƚƌĂƚŝŽŶƐ͕ SͲƐƚĂĐŬĞĚ ĂŐŐƌĞŐĂƚĞƐ
ƐƚƌƵĐƚƵƌĞ ĂƌĞ ƌĞƐƉŽŶƐŝďůĞ ĨŽƌ ƚŚĞ ĞǆĐŝŵĞƌ ĞŵŝƐƐŝŽŶ͘ /Ŷ ďŽƚŚ ĐĂƐĞƐ͕ ƚŚĞŵŽŶŽŵĞƌ ĞŵŝƐƐŝŽŶ ŵĂǇ ĂƌŝƐĞ ĨƌŽŵ ŝƐŽůĂƚĞĚ d/͘
¾ /Ŷ ,ϮK Ăƚ ŚŝŐŚĞƌ ĐŽŶĐĞŶƚƌĂƚŝŽŶƐ͕ ƵŶƐƚĂĐŬĞĚ ĂŐŐƌĞŐĂƚĞƐ ĂƐ ǁĞůů ĂƐ ŝƐŽůĂƚĞĚ
d/ ŵĂǇ ĐŽŶƚƌŝďƵƚĞ ƚŽ ďŽƚŚ ŵŽŶŽŵĞƌ ĂŶĚ ĞǆĐŝŵĞƌ ĞŵŝƐƐŝŽŶƐ͘)LJ3URSRVHGEDVLFDJJUHJDWHVWUXFWXUHVRI'7&,

ϰ &ƵƚƵƌĞWůĂŶƐ
¾ ^ƚƵĚŝĞƐ ŽŶ ƉŚŽƚŽƉŚǇƐŝĐĂů ƉƌŽƉĞƌƚŝĞƐ ŽĨ d/ ŝŶ ƚŚĞ ƉƌĞƐĞŶĐĞ ŽĨĐŚŝƌĂů ŵŽůĞĐƵůĞƐ ĂƌĞ ƵŶĚĞƌ ǁĂǇ ƚŽ ŵĂǆŝŵŝǌĞ ƚŚĞ ĨƵŶĐƚŝŽŶ ŽĨd/ ƚŚƌŽƵŐŚ ĐŚŝƌĂůŝƚǇ ĞĨĨĞĐƚƐ ŝŶ ďŝŽ ŝŵĂŐŝŶŐ ĂƉƉůŝĐĂƚŝŽŶƐ͘77

Synthesis and Properties of Antioxidant Polymers
Shunta Asada, Yue Wang, and Tamaki Nakano*

Institute for Catalysis (ICAT), Graduate School of Chemical Sciences and Engineering, and Integrated ResearchConsortium on Chemical Sciences (IRCCS), Hokkaido University, N 21, W 10, Kita‐ku, Sapporo 001‐0021, Japan＊tamaki.nakano@cat.hokudai.ac.jp
Abstract: 4‐Vinyldiphenylamine (VDPA) was prepared and polymerized under free‐radical and cationic conditions to leadvinyl polymers as antioxidant materials. The polymers were suggested to possess partially branched structure which may
have been created through chain‐transfer to the amino group of the monomer or a unit in polymer chain. The polymers
reacted with 1,1‐diphenylpicrylhyrazyl (DPPH) as a free‐radical oxidant model at high efficiency, and the efficiency was
higher for the polymers than that of diphenyamine (DPA). It is intriguing that a polymer exhibited a higher reactivity
compared with a corresponding small molecule.

Introduction
Natural antioxidants (flavonoids)

Artificial antioxidants

Example of antioxidant polymer

Radical‐trapping mechanism

OH
OH
HO

O

HO

t-Bu

t-Bu
H3CO

OH
OH

R1

CH3

R2
n

Tea Catechin

n

OH

R1

OH

DPA

BHT

OH

Persimmon Tannin

OCH3
OCH3

HO

OH
OH

K. Zhan, H. Ejima, N. Yoshie, ACS Sustain.
Chem. Eng. 2016, 4, 3857−3863

Monomer and Polymer Synthesis

VDPA
THF

CHCl3

water

Poly(VDPA)
TMSNH

Cationic polymn.
0.19M

Branch10%Cationic polymn.
0.10M

8%

Radical polｙmn.
[M]/[I]=100

15%

NH

HN

N
z

Partially branched structure

Radical polymn.
[M]/[I]=20

9

y

x

15%

8

7

6

5
4
/ppm

3

2

1

0

Figure 1. 1H NMR spectra of poly(VDPA)s prepared under
different conditions. [400 MHz, r.t., CDCl3]

Antioxidant Properties

Purple(max 517 nm)

Partially ‐Stacked Conformation

A. DPPH + poly(VDPA)(cationic polymn.)

Pale yellow
Stabilization of radical by a ‐stacked conformation

B. DPPH + DPA

Figure 2. Absorbance at 517 nm‐vs.‐reaction time plots.

Conditions: [DPPH] = 789µM, [poly(VDPA) (cationic polymn., Mn 11,710)] =202μM,[poly(VDPA) (radical polymn., Mn 4,430)] =201μM, [DPA] = 199µM, cell path = 1 mm.

Figure 3. Changes in UV‐vis spectra of a THF
solution of DPPH on addition of poly(VDPA)(cationic polymn., Mn 11,710) (A) and DPA (B).

8

Conditions: [DPPH] = 789 µM, [Cationic poly(VDPA)] = 202 μM, [DPA]= 199 µM, cell path = 1 mm.

Conclusions
 Poly(VDPA) was prepared as a novel antioxidant, polymeric material.
 Poly(VDPA) efficiently reacted with DPPH as an oxidant model where
stabilization of radical species through a partially ‐stacked conformation
may have a role.

7

/ppm

6

5

Figure 4. 1H NMR spectra of DPA (top) and poly(VDPA)(bottom). [400 MHz, r.t., CDCl3, TMS].

Future plans Studies on effects of molar mass and stereo structure ofpoly(VDPA) on antioxidant properties.
 Synthesis and properties of VDPA‐styrene copolymers and
VDPA‐containing polymer gels.
 ESR studies on radical stabilization effects of poly(VDPA).

78

WŽůǇƵƌĞƚŚĂŶĞƐĂƐDĂĐƌŽŵŽůĞĐƵůĂƌ>ŝŐĂŶĚƐĨŽƌĂƚĂůǇƚŝĐZĞĂĐƚŝŽŶƐ
ŬŝŚŝƌŽ<ŝŵƵƌĂ͕ϭ ,ĂƌƵŬĂ ,ĂǇĂŵĂ͕ϭ :ƵŶͲǇĂ ,ĂƐĞŐĂǁĂ͕ϭ͕Ϯ ,ĂƐƐĂŶEĂŐĞŚ͕ϭ zƵĞtĂŶŐ͕ϭ͕Ϯ EĂŽĨƵŵŝ EĂŐĂ͕ϯDĂǇƵŵŝEŝƐŚŝĚĂ͕ϭ͕Ϯ ĂŶĚdĂŵĂŬŝEĂŬĂŶŽϭ͕ϮΎϭ/ŶƐƚŝƚƵƚĞĨŽƌĂƚĂůǇƐŝƐ;/dͿĂŶĚ'ƌĂĚƵĂƚĞ^ĐŚŽŽůŽĨŚĞŵŝĐĂů^ĐŝĞŶĐĞƐĂŶĚŶŐŝŶĞĞƌŝŶŐ͕,ŽŬŬĂŝĚŽhŶŝǀĞƌƐŝƚǇ͕EϮϭ͕tϭϬ͕<ŝƚĂͲŬƵ͕^ĂƉƉŽƌŽϬϬϭͲϬϬϮϭ͕:ĂƉĂŶ͖Ϯ/ŶƚĞŐƌĂƚĞĚZĞƐĞĂƌĐŚŽŶƐŽƌƚŝƵŵŽŶŚĞŵŝĐĂů^ĐŝĞŶĐĞƐ;/Z^Ϳ͖ϯ'ƌĂĚƵĂƚĞ^ĐŚŽŽůŽĨ^ĐŝĞŶĐĞĂŶĚŶŐŝŶĞĞƌŝŶŐ͕^ŚŝďĂƵƌĂ/ŶƐƚŝƚƵƚĞŽĨdĞĐŚŶŽůŽŐǇ͕ϯͲϳͲϱdŽǇŽƐƵ͕<ŽƚŽͲŬƵ dŽŬǇŽϭϯϱͲϬϬϲϭ͕:ĂƉĂŶͲŵĂŝů͗ƚĂŵĂŬŝ͘ŶĂŬĂŶŽΛĐĂƚ͘ŚŽŬƵĚĂŝ͘ĂĐ͘ũƉďƐƚƌĂĐƚ͗ /ƌ;/ͿͲĐĂƚĂůǇǌĞĚ ĚŝƌĞĐƚ ďŽƌǇůĂƚŝŽŶ ŽĨ ĂƌŽŵĂƚŝĐ ĐŽŵƉŽƵŶĚƐϭ ǁĂƐ ĐŽŶĚƵĐƚĞĚ ŝŶ ƚŚĞ ƉƌĞƐĞŶĐĞ ŽĨ ƉŽůǇƵƌĞƚŚĂŶĞƐ ƉƌĞƉĂƌĞĚ ďǇƉŽůǇĐŽŶĚĞŶƐĂƚŝŽŶ ŽĨ ϰ͕ϰ͛ͲďŝƐ;ŚǇĚƌŽǆǇůŵĞƚŚǇůͿͲϮ͕Ϯ͛ͲďŝƉǇƌŝĚǇů ǁŝƚŚ ϭ͕ϲͲĚŝŝƐŽĐǇĂŶĂƚŽŚĞǆĂŶĞ͕ ϭ͕ϰͲĚŝŝƐŽĐǇĂŶĂƚŽďĞŶǌĞŶĞ͕ ϭ͕ϰͲĚŝŝƐŽĐǇĂŶĂƚŽͲϯͲŵĞƚŚǇůďĞŶǌĞŶĞ͕ ĂŶĚ ďŝƐ;ϰͲŝƐŽĐǇĂŶĂƚŽƉŚĞŶǇůͿŵĞƚŚĂŶĞ͘ dŚĞ ƉŽůǇŵĞƌ ƉƌĞƉĂƌĞĚ ĨƌŽŵ ϭ͕ϲͲĚŝŝƐŽĐǇĂŶĂƚŽŚĞǆĂŶĞ ƐŚŽǁĞĚ ďĞƐƚ ĂĐƚŝǀŝƚŝĞƐ
ƵŶĚĞƌ ŵŽƐƚ ĐŽŶĚŝƚŝŽŶƐ͘ dŚĞ ďŽƌǇůĂƚŝŽŶ ƌĞĂĐƚŝŽŶ ƐǇƐƚĞŵƐ ǁŝƚŚ ƚŚĞ ƉŽůǇŵĞƌƐ ǁĞƌĞ ďŝƉŚĂƐŝĐ ǁŚĞƌĞ ƚŚĞ ƚŽƉ ĂŶĚ ďŽƚƚŽŵ ůĂǇĞƌƐ ĐŽŶƚĂŝŶĞĚƚŚĞ ƉƌŽĚƵĐƚ ĂŶĚ ƚŚĞ ƉŽůǇŵĞƌͲďĂƐĞĚ ĐĂƚĂůǇƐƚƐ͕ ƌĞƐƉĞĐƚŝǀĞůǇ͘ ƵĞ ƚŽ ƚŚĞ ƉŚĂƐĞ ƐĞƉĂƌĂƚŝŽŶ͕ ƚŚĞ ƉƌŽĚƵĐƚ ŝƐŽůĂƚŝŽŶ ĂŶĚ ĐĂƚĂůǇƐƚ ƌĞĐǇĐůĞ ǁĞƌĞƌĞĂĚŝůǇ ƉĞƌĨŽƌŵĞĚ ƚŚƌŽƵŐŚ ƐŝŵƉůĞ ĚĞĐĂŶƚĂƚŝŽŶ͘ϭͿ d͘ /ƐŚŝǇĂŵĂ͕ :͘ dĂŬĂŐŝ͕ <͘ /ƐŚŝĚĂ͕ E͘ DŝǇĂƵƌĂ͕ E͘ Z͘ ŶĂƐƚĂƐŝ͕ :͘ &͘ ,ĂƌƚǁŝŐ͕ :͘ ŵ͘ ŚĞŵ͘ ^ŽĐ͘ ϮϬϬϮ͕ ϭϮϰ͕ ϯϵϬͲϯϵϭ͘WŽůǇŵĞƌŝǌĂƚŝŽŶ

ĂƚĂůǇƚŝĐƌĞĂĐƚŝŽŶ͗ŝƌĞĐƚďŽƌǇůĂƚŝŽŶ

ĞŶǌĞŶĞ

&ŽƌŵĂƚŝŽŶŽĨƉŽůǇŵĞƌ ĐŽŵƉůĞǆŶŝƐŽůĞ

7DEOH  'LUHFW ERU\ODWLRQ RI EHQ]HQHD
5HDFWLRQ IRU  K

5HDFWLRQ IRU  K

<LHOG  E 721<LHOG  E 721

ϭ͘Ϭ
Ϭ͘ϴ



ES\











%+0%



3RO\













ďƐ

5XQ /LJDQG

Ϭ͘ϲ
Ϭ͘ϰ



3RO\











3RO\









Ϭ͘Ϯ



3RO\









Ϭ͘Ϭ

D%HQ]HQH  P/ >,U&O &2' @  P0
 PRO RI %SLQ  %SLQ 
P0 QRQDQH LQWHUQDO VWDQGDUG  P0 WLPH  K WHPS  R&
E(VWLPDWHG E\ *& PDVV VSHFWURVFRS\ XVLQJ QRQDQH DV LQWHUQDO VWDQGDUG

ϯϬϬ

ϰϬϬ

ϱϬϬ

ϲϬϬ

tĂǀĞŶƵŵďĞƌ;ĐŵͲϭͿ

ϳϬϬ

ϴϬϬ

/ŶƚĞƌͲĐŚĂŝŶ,ͲďŽŶĚŝŶŐ

ĂƚĂůǇƐƚƌĞĐǇĐůĞ

,ͲďŽŶĚĞĨĨĞĐƚƐ

ŚĂŝŶƐŽĨƚŶĞƐƐ

ϱϬ
ϰϬ
ϯϬ
ϮϬ
ϭϬ
Ϭ

WŽůǇŵĞƌŵŽƌƉŚŽůŽŐǇ

;ͿWŽůǇͲϭ

ϭ

Ϯ

ϯ

ϰ

ϱ

ϲ

&ŝŐ͘ϯ͘dKEƐŝŶƌĞĐǇĐůŝŶŐƚŚĞWŽůǇͲϭͲ/ƌĐĂƚĂůǇƐƚĨŽƌďĞŶǌĞŶĞďŽƌǇůĂƚŝŽŶ ĐŽŶĚƵĐƚĞĚƵŶĚĞƌƚŚĞĐŽŶĚŝƚŝŽŶƐŽĨƌƵŶϯŝŶdĂďůĞϮĨŽƌϮϰŚ͘Ă͘WŽůǇͲϰͲ/ƌď͘,DͲ/ƌ&ŝŐ͘ϰ͘WŚŽƚŽŐƌĂƉŚŝĐŝŵĂŐĞƐŽĨƌĞĂĐƚŝŽŶƐǇƐƚĞŵƐǁŝƚŚĂŶŝƐŽůĞǁŝƚŚƉŽůǇͲϰ ;ƌƵŶϲŝŶdĂďůĞϱͿ;ĂͿĂŶĚǁŝƚŚ,D ;ƌƵŶϮŝŶdĂďůĞϱͿ͘;ͿWŽůǇͲϮŽŶĐůƵƐŝŽŶƐ͗;ͿWŽůǇͲϯ;ͿWŽůǇͲϰ&ŝŐ͘ϳ͘^DŝŵĂŐĞƐŽĨWŽůǇͲϭ;Ϳ͕WŽůǇͲϮ;Ϳ͕WŽůǇͲϯ;Ϳ͕ĂŶĚWŽůǇͲϰ;Ϳ͘΀ŵĂŐŶŝĨŝĐĂƚŝŽŶ㽢 ϭϬ͕ϬϬϬ΁ 3RO\ SHUIRUPHG EHWWHU WKDQ WKH RWKHU WKUHH SRO\PHUV WKH IDFW WKDW WKLV SRO\PHU KDV D 7J ORZHU WKDQ WKDWRI WKH FDWDO\WLF UHDFWLRQ DQG KLJKHU WHQGHQF\ RI +ERQG IRUPDWLRQ PD\ EH UHVSRVLEOH IRU WKH SHUIRUPDQFH
 7KH o,VRPHU ZDV SUHIHUHQWLDOO\ JHQHUDWHG LQ WKH UHDFWLRQ ZLWK DQLVROH LQ WKH HDUO\ VWDJHV RI UHDFWLRQ 7KH UHDFWLRQ V\VWHPV LQYROYLQJ WKH SRO\PHU FDWDO\VWV DUH ELSKDVLF ZKHUH SURGXFW LVRODWLRQ DQG FDWDO\VW
UHFRYHU\ ZHUH FRQGXFWHG WKURXJK VLPSOH GHFDQWDWLRQ RU FHQWULIXJH
 &DWDO\VW UHF\FOH ZDV FRQILUPHG IRU WKH SRO\,U V\VWHP ZLWK EHQ]HQH DV VXEVWUDWH

79^ǇŶƚŚĞƐŝƐĂŶĚ^ƚƌƵĐƚƵƌĞŽĨŚŝƌĂůWŽůǇĞůĞĐƚƌŽůǇƚĞƐĨŽƌ'ĞŶĞĞůŝǀĞƌǇ
EŝŶŽĂǀƌĂĚĂƐŚǀŝůŝ͕ϭ͕Ϯ zƵĞtĂŶŐ͕ϭ ZĂŵĂǌ <ĂƚƐĂƌĂǀĂ͕Ϯ dĂŵĂŬŝEĂŬĂŶŽϭ͕Ύϭ/ŶƐƚŝƚƵƚĞĨŽƌĂƚĂůǇƐŝƐ;/dͿĂŶĚ/ŶƚĞŐƌĂƚĞĚZĞƐĞĂƌĐŚŽŶƐŽƌƚŝƵŵŽŶŚĞŵŝĐĂů^ĐŝĞŶĐĞƐ;/Z^Ϳ͕,ŽŬŬĂŝĚŽhŶŝǀĞƌƐŝƚǇ͕E

Ϯϭ͕tϭϬ͕<ŝƚĂͲŬƵ͕^ĂƉƉŽƌŽϬϬϭͲϬϬϮϭ͕:ĂƉĂŶϮ/ŶƐƚŝƚƵƚĞŽĨŚĞŵŝƐƚƌǇĂŶĚDŽůĞĐƵůĂƌŶŐŝŶĞĞƌŝŶŐ͕ŐƌŝĐƵůƚƵƌĂůhŶŝǀĞƌƐŝƚǇŽĨ'ĞŽƌŐŝĂ͕<ĂŬŚĂ ĞŶĚƵŬŝĚǌĞ hŶŝǀĞƌƐŝƚǇĂŵƉƵƐ͕ϮϰϬĂǀŝĚŐŚŵĂƐŚĞŶĞďĞůŝ ůůĞǇ͕dďŝůŝƐŝϬϭϱϵ͕'ĞŽƌŐŝĂ
㸨ƚĂŵĂŬŝ͘ŶĂŬĂŶŽΛĐĂƚ͘ŚŽŬƵĚĂŝ͘ĂĐ͘ũƉďƐƚƌĂĐƚ͗ 'ĞŶĞ ĚĞůŝǀĞƌǇ͕ Ă ƚĞĐŚŶŝƋƵĞ ƚŽ ŝŶƚƌŽĚƵĐĞ ĨŽƌĞŝŐŶ E ŝŶƚŽ Ă ĐĞůů͕ ĐĂŶ ďĞ ƉĞƌĨŽƌŵĞĚ ƵƐŝŶŐ ĂŶ ĂƌƚŝĨŝĐŝĂů ǀĞĐƚŽƌ ŵĂƚĞƌŝĂů
ŝŶĐůƵĚŝŶŐ ƐǇŶƚŚĞƚŝĐ ƉŽůǇĞůĞĐƚƌŽůǇƚĞƐ͘ /Ŷ ƚŚŝƐ ǁŽƌŬ͕ ǁĞ ƐƚƵĚŝĞĚ ƚŚĞ ƐƚƌƵĐƚƵƌĞƐ ĂŶĚ ďĂƐŝĐ ƉƌŽƉĞƌƚŝĞƐ ŽĨ ƉŽůǇĞůĞĐƚƌŽůǇƚĞƐ ĐŽŶƐŝƐƚŝŶŐŽĨ ĂƌŐŝŶŝŶĞͲ ĂŶĚ ƐƉĞƌŵŝŶĞͲďĂƐĞĚ ŵŽŶŽŵĞƌŝĐ ƵŶŝƚƐ ŝŶ Ă ƐĂůƚ ĨŽƌŵ ǁŝƚŚ ƉͲƚŽůƵĞŶĞƐƵůĨŽŶŝĐ ĂĐŝĚ ĂƐ ĐĂŶĚŝĚĂƚĞƐ ŽĨ Ă ŶŽǀĞů ƐǇŶƚŚĞƚŝĐ
ŐĞŶĞ ǀĞĐƚŽƌ͘ dŚĞ ƉŽůǇŵĞƌƐ ǁĞƌĞ ĨŽƵŶĚ ƚŽ ĨŽƌŵ ĐŚŝƌĂů ĐŽŵƉůĞǆ ǁŝƚŚ ŵĞƚŚǇů ŽƌĂŶŐĞ ǁŚŽƐĞ ƐƚƌƵĐƚƵƌĞ ǁĂƐ ŝŶǀĞƐƚŝŐĂƚĞĚ ďǇĐŝƌĐƵůĂƌ ĚŝĐŚƌŽŝƐŵ ;Ϳ ĂŶĚ ƵůƚƌĂ ǀŝŽůĞƚ ;hsͿ ƐƉĞĐƚƌŽƐĐŽƉŝĐ ĂŶĂůǇƐĞƐ͘WŽůǇŵĞƌŝǌĂƚŝŽŶ

DŽŶŽŵĞƌ^ǇŶƚŚĞƐŝƐ
+ 2

7V+2+1

2



n

2

2

&+ 


1+2+7V



&+ 

+1

m 7V2+1

7V2+1

1+

21

2

$UJ


6S
2

2
\

12

2

'0$(W1 R& K& [  & [ 
2
+ +
1
2
[

 RU 
^ĐŚĞŵĞ ϭ͘ ^ǇŶƚŚĞƐŝƐ ŽĨ ŵŽŶŽŵĞƌƐ͘

[2

&+ 

2



2

2 + +
1
&+ 

+1

7V2+11+
1+



7V2+1+27V
11+27V

1
+27V

1+
1+

7V2+1++27V1+1n1+27V

2 [2

1
+

m

1+

$UJLQLQH DQGRU 6SHUPLQHEDVHG 3RO\HOHFWURO\WH

EDZŶĂůǇƐŝƐ

1+27V+1

WŽůǇ;ƌŐϱϬͲ^ƉϱϬͲϮͿ ǁĂƐ ƌĞĂĐƚĞĚ ǁŝƚŚ Ă ƐŵĂůů ĂŵŽƵŶƚ ŽĨ ϭ͕ϲͲĚŝŝƐŽĐǇĂŶĂƚŽŚĞǆĂŶĞ ůĞĂĚŝŶŐ ƚŽ ƉŽůǇ;ƌŐϱϬͲ^ƉϱϬͲϮͿ Ύ͘

+1
7V2+1

T S

T

[F

62+

T

P

1+27VWŽůǇŵĞƌͲDĞƚŚǇůKƌĂŶŐĞŽŵƉůĞǆĂƚŝŽŶ

+27V
1
1+27V
1
+27V
R

ED
R

S

&+

3RO\ $UJ6S&T^ĐŚĞŵĞ Ϯ͘ ^ǇŶƚŚĞƐŝƐ ŽĨ ƉŽůǇĞůĞĐƚƌŽůǇƚĞƐ͘

R E
D
\]

F G
H

T S

62+
1+

2+

1+

7V2+1

7V2+1

R

2

2
1+

62+

S

+2

S
3RO\ $UJ 6S&

F[

3RO\ $UJ6S&

02
023RO\ $UJ6S&F
PG R E D$ H \E]

&+

D
E
F



3RO\ $UJ6S&&ŝŐ͘ Ϯ͘ ďƐŽƌďĂŶĐĞ ƐƉĞĐƚƌĂ ŽĨ ƉŽůǇ;ƌŐϱϬͲ^ƉϱϬͲϮͿ ;Ϭ͘Ϭϭ DͿ ;ĂͿ͕ DK ;Ϭ͘ϬϬϬϯ DͿ ;ďͿ͕ĂŶĚ Ă ŵŝǆƚƵƌĞ ŽĨ ƚŚĞ ƉŽůǇŵĞƌ ĂŶĚ DK;΀ƵŶŝƚ΁ͬ΀DK΁ с ϭͬϭͿ ;ĐͿ ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘

3RO\ $UJ6S&

3RO\ $UJ6S&

T

F G
H

S
3RO\ 6S&

T S 3RO\ $UJ&




F
[

SSP



&ŝŐ͘ ϯ͘ ďƐŽƌďĂŶĐĞ ƐƉĞĐƚƌĂ ŽĨ ŵŝǆƚƵƌĞƐŽĨ ƉŽůǇ;ƌŐϱϬͲ^ƉϮϬͲϮͿ ĂŶĚ DK ǁŚĞƌĞ
΀DK΁ с Ϭ͘Ϭϭ Őͬ> Ăƚ ΀ƉŽůǇŵĞƌ΁ͬ΀DK΁ сϭϬͬϭ ;ĂͿ͕ ϭϬϬͬϭ ;ďͿ͕ ĂŶĚ ϱϬϬͬϭ ;ĐͿ;ǁĞŝŐŚƚ ƌĂƚŝŽͿ ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘



R

&+

E
R

P



D




E
\] D




&ŝŐ͘ ϰ͘ ďƐŽƌďĂŶĐĞ ƐƉĞĐƚƌĂ ŽĨ ŵŝǆƚƵƌĞƐ ŽĨ
DK ĂŶĚ ƉŽůǇŵĞƌƐ Ăƚ ΀DK΁ с Ϭ͘ϭ Őͬ> ĂŶĚ΀ƉŽůǇŵĞƌ΁ с ϭ͘Ϭ Őͬ> ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘







:DYHOHQJWKQP&ŝŐ͘ ϱ͘  ƐƉĞĐƚƌĂ ŽĨ ŵŝǆƚƵƌĞƐ ŽĨ DKĂŶĚ ƉŽůǇŵĞƌƐ Ăƚ ΀DK΁ с Ϭ͘ϭ Őͬ> ĂŶĚ΀ƉŽůǇŵĞƌ΁ с ϭ͘Ϭ Őͬ> ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘dŚĞŶŽǀĞů͕ĐŚŝƌĂůƉŽůǇĞůĞĐƚƌŽůǇƚĞƐǁĞƌĞƐƵĐĐĞƐƐĨƵůůǇƉƌĞƉĂƌĞĚĂŶĚĨŽƵŶĚƚŽĨŽƌŵĐŚŝƌĂůĐŽŵƉůĞǆǁŝƚŚŵĞƚŚǇůŽƌĂŶŐĞƉŽƐƐŝďůǇƚŚƌŽƵŐŚŝŽŶŝĐŝŶƚĞƌĂĐƚŝŽŶŽƌ;ƉĂƌƚŝĂůͿĂŶŝŽŶĞǆĐŚĂŶŐĞ͘

80>3RO\ $UJ6S& @>02@&ŝŐ͘ ϲ͘ :Žď͛Ɛ ƉůŽƚ ĨŽƌ ŵŝǆƚƵƌĞƐ ŽĨƉŽůǇ;ƌŐϱϬͲ^ƉϱϬͲϮͿ ĂŶĚ DK Ăƚ ΀ƌŐ ĂŶĚ^Ɖ ƵŶŝƚƐ΁ н ΀DK΁ с Ϭ͘ϬϬϭϲ D ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘

















































ŽŶĐůƵƐŝŽŶƐ

&ŝŐ͘ ϭ͘ Ϯ ,Ͳ, K^z ;ůĞĨͿ ĂŶĚ ϭ ϭ, EDZ ƐƉĞĐƚƌĂ ŽĨ ŵŽŶŽŵĞƌƐ ĂŶĚ ƉŽůǇŵĞƌƐ
;ϰϬϬ D,ǌ͕ D^KͲĚϲ͕ ƌ͘ƚ͘Ϳ͘&ŝŐ͘ ϳ͘ :Žď͛Ɛ ƉůŽƚ ĨŽƌ ŵŝǆƚƵƌĞƐ ŽĨƉŽůǇ;ƌŐͲϮͿ ĂŶĚ DK Ăƚ ΀ƌŐ ƵŶŝƚ΁ н
΀DK΁ с Ϭ͘ϬϬϭϲ D ŝŶ ,ϮK ;ϭͲŵŵ ĐĞůůͿ͘ŽŶƚƌŽůŽĨ^ƵƌĨĂĐĞ/ŶŚŽŵŽŐĞŶĞŝƚǇĂŶĚŝƚƐĂƚĂůǇƚŝĐWƌŽƉĞƌƚŝĞƐ͘+XDQJ+XDDQG .L\RWDND$VDNXUD /ŶƐƚŝƚƵƚĞĨŽƌĂƚĂůǇƐŝƐ͕,ŽŬŬĂŝĚŽhŶŝǀĞƌƐŝƚǇ͕^ĂƉƉŽƌŽϬϬϭͲϬϬϮϭ͕:ĂƉĂŶ
DVNU#FDWKRNXGDLDFMS+LJKSHUIRUPDQFHFDWDO\VWVDUHRIWHQFRPSRVHGRIWZRRUPRUHDFWLYHSKDVHVZKLFKDUHEHOLHYHGWRLQWHUDFWZLWKHDFKRWKHUDWWKHPHVRVFRSLFVFDOHVWUXFWXUH8QOLNHFRQYHQWLRQDOSRZGHUFDWDO\VWVÀDWVXUIDFHVLVDGYDQWDJHRXVLQWKDWLWVVXUIDFHVWUXFWXUHFDQEHSUHFLVHO\GHVLJQHG:HSUHSDUHGSUHFLVHO\GHVLJQHG
6E296E26LFDWDO\VWVFRQWDLQLQJ6E2ULEERQVZLWK¿QHO\FRQWUROOHGZLGWKDQGVHSDUDWLRQE\HOHFWURQOLWKRJUDSK\  :HGHPRQVWUDWHGWKDWWKHDFUROHLQJHQHUDWLRQUDWHRQWKHFDWDO\VWVZDVUHODWHGWRWKHZLGWKDQG
VHSDUDWLRQRIWKH6E2 ULEERQV7KLVZRUNVKRZVWKHSRVVLELOLW\WRUHJXODWHFDWDO\VLVE\LQKRPRJHQHLW\RIWKH
VXUIDFHVWUXFWXUHDWWKHPHVRVFRSLFOHYHO,QWURGXFWLRQ

0RWLYDWLRQ([SHULPHQWDOPP[PP PP

+DUDJXFKL<:DGD72PLQDPL<
0DWVXGDLUD1$ULJD+7DNDNXVDJL
6 $VDNXUD.
Hyomen Kagaku    s^ďKϰZĞŵŽƚĞŽŶƚƌŽůDĞĐŚĂŶŝƐŵ

ϭ

DͲ^ďϮKϰϰĞůŵŽŶ͕͖͘&ƌŽŵĞŶƚ͕'͘&͘ĂƚĂů͘ZĞǀ͘ϭϵϵϲ͕ϯϴ͕ϲϵ͘

;5'

;36

^ĂŵƉůĞ

DͲ^ďϮKϰ ůŝŶĞǁŝĚƚŚǭ
䡉͕䐟 ͬPŵs^ďKϰ ƐĞƉĂƌĂƚŝŽŶ
Ŷ͕䐠ͬPŵ
ϭ

ϭPŵ

Ϭ͘Ϯϱ

ϮPŵ

Ϭ͘ϱ

ϰPŵ

ϭ

ϭϲPŵ

ϰ

ϭϲ

ϯϮPŵ

ϴ

ϯϮ

Oxygen poor region(a)Oxygenconcentration
based on normal
latticeϭϮϰOxygen rich region(d))LJXUH3URSRVHGUHDFWLRQPHFKDQLVPEDVHGRQWKHVXUIDFHGLIIXVLRQPRGHOLQZKLFKVHSDUDWLRQLVODUJHUWKDQWKHGLIIXVLRQGLVWDQFH7KHZKLWHOLQHVUHSUHVHQWSURSRVHGR[\JHQFRQFHQWUDWLRQ

ܰ ൌ

஼௅

௠ ା௡

ൌ

஼௅

ହ௠

Q P

‫ܰ כ ݀ כ ܽ ן ݎ‬‫ ܰכ݀כܽן ݎ‬ൌܽ‫כ݀כ‬஼௅

a<m䚸d<nହ௠௠஼௅‫ ܰ כ ݀ כ‬ൌ ݀ ‫ כ‬a>m
ଶ
ଵ଴
௠ ௡
஼௅
‫ ܰכ כ ן ݎ‬ൌ݊‫כ‬
d>n
ଶ ଶ
ଶ଴

‫ןݎ‬

,QWKLVZRUNZHGHPRQVWUDWHGWKHIHDVLELOLW\RIFRQWUROOLQJDQGWXQLQJWKHUHDFWLRQSURSHUWLHVRIĮ6E296E26LVDPSOHV
E\DGMXVWLQJWKH6E2 ULEERQZLGWKDQGVHSDUDWLRQRQWKHPHVRVFRSLFVFDOH/LWKRJUDSK\LVDQDWWUDFWLYHPHWKRGWRIDEULFDWHFDWDO\VWVZLWKSUHFLVHO\GHVLJQHGPHVRVFRSLFVWUXFWXUHDQGLWZLOOOHDGWRDQHZFDWDO\VWSUHSDUDWLRQPHWKRGVWKDWLQYROYHFRPSXWHUFRQWUROOHGGHVLJQDQGPDQXIDFWXUH
7KLVZRUNKDVEHHQVXSSRUWHGE\&5(67-67³5HVROXWLRQ&DWDO\VW´
5HIHUHQFH䠗+XDQJ++:DGD7$ULJD+7DNDNXVDJL6$VDNXUD.,ZDVDZD<Chem. Phys.Lett. 2017, 683, 18.

81)LUVW3ULQFLSOHV6LPXODWLRQVRI&DWDO\WLF5HDFWLRQVDWWKH
:DWHU&H2  ,QWHUIDFH+\GUDWLRQRI&\DQRS\ULGLQH$NLUD1DND\DPD 0DVD]XPL7DPXUD.HQLFKL6KLPL]XDQG-XQ\D+DVHJDZD
1Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan

2JST PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan
Applied Chemistry, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan

3Department of

HPDLOQDND\DPD#FDWKRNXGDLDFMS
Computational details

Introduction
Catalysis of CeO2-based Materials

+
5

+

&H

2í

1

&H

2
&H

&H

Lewis acid-base site

Cerium(IV) Oxide(fluorite structure)

CeO2 has unique ..







2

+
+
2í

 DFT calculations&&&
Lewis acid Lewis base

2
2

2

2í

&H

&H

&H

Mars-van Krevelen mechanism(redox mechanism) Redox properties Oxygen storage capacity
 Acid-base properties

Periodic boundary DFT+U: (PBE functional, U = 7.0 eV)
DZVP (MOLOPT type basis set) and GTH pseudopotentials
Energy cutoff of 400 Ry for auxiliary plane wave expansion
ī-point only in the k-point sampling
CP2K program package

 Simulation cell (CeO2(111) surface) p(3㽢3) and 3 O-Ce-O tri-layers (27 CeO2 unit) a = b = 11.56, c = 25.0 Å and Į = ȕ = 90, Ȗ = 60 degrees

 NVT ensemble (T=330 K)
 Time step of 1.0 fs (the mass of a hydrogen is replaced with that of deuterium) Blue moon ensemble and metadynamics approach for free energy calculations

 MD simulations

Results and Discussions

Hydration of 2-cyanopyridine over metal-oxide catalysis

Adsorption structure of 2-cyanopyridine on CeO2(111)2-cyanopyridine (reactive)

Substrate Specificity

4-cyanopyridine (unreactive)

Free energy profile (metadynamics simulation)
M. Tamura, H. Wakasugi, K. Shimizu, and A. Satsuma, Chem. Eur. J. 17, 11428 (2011).

5

Proposed mechanism

&
1
&H

&

+

5

&H

+
2í

2
2

D

5

&H

1
&H

2-cyanopyridine

4-cyanopyridine

&H

&

+
2

+
2

&H

E

5

Unique adsorption structure of 2-cyanopyridine on CeO2(111)

+

+

1

2

&
1
&H

+
+
2

2
&H

Lattice oxygen mechanism in hydration of 2-cyanopyridine

Water/ZrO2 interface

Adsorption energy of water molecule:(molecularly or dissociative) aíH9
Surface hydroxylation increases with water
adsorption energy
Lewis acid site is not available for adsorption of nitriles

Free energy profiles
Self-assembled hybrid metal-oxide based catalysis

Catalytic reactions with hybrid catalysis

M. Tamura, R. Kishi, A. Nakayama, Y. Nakagawa, J. Hasegawa, and K. Tomishige, J. Am. Chem. Soc. 139, 11857 (2017).

82

Theoretical Study on Rhodium-Catalyzed Hydrosilylationof C=C and C=O Double Bonds
Liming Zhao,1 Naoki Nakatani,2 Yusuke Sunada 3, Hideo Nagashima 3, Jun-ya Hasegawa2
1Graduate School of Chemical Science and Engineering, Hokkaido University
2Institute for Catalysis, Hokkaido University, Sapporo, Japan
3Institute for Materials Chemistry and Engineering, Kyushu University, Japan

Introduction

Newly proposed mechanisms

Hydrosilylation describes the reaction that unsaturated bond insertion into Si-H bond under acertain catalyst. It’s an important way to produce organosilicon products. Using Rh as the catalyst,
very mild reaction conditions can be achieved.

Alternative Chalk-Harrod (aCH) mechanism+
From an analogy to Rh-catalyzed hydrosilylation of alkenes,[1] it
was assumed that the Rh-catalyzed hydrosilylation of carbonylgroup occurs through modified Chalk-Harrod (MCH) mechanism,
although there is no evidence. Our recent work that the Ptcatalyzed hydrosilylation of carbonyl group can occur via ChalkHarrod (CH) mechanism with a bifunctional hydrosilane.[2] Thus
it is worth to theoretically investigate which mechanism is takenplace in such reactions.
aCH mechanism

Method & Model
Catalyst:

Hydrosilane:

BS I



Unsaturated bonds:
Acetone / ethylene➢

Basis sets:   
BS II

Ȁ
ሺ͸ͳͳͳͳͳȀʹʹͳͳͳȀͶͳͳሻ൅
͸Ǧ͵ͳ*
͸Ǧ͵ͳ൅ȗ   

Ȁ
ሺ͸ͳͳͳͳͳȀʹʹͳͳͳȀͶͳͳሻ൅൅
͸Ǧ͵ͳͳȗȗ͸Ǧ͵ͳͳ൅ȗȗFree energy profiles for acetone hydrosilylation inmCH cycle (upper) and CH cycle (bottom)

Important transition
states:

Method: Density Functional Theory(ωͻ͹ )Existing Mechanisms



➢
➢

Free energy profile of acetone hydrosilylation inaCH cycle.

In acetone case, the rate-determining step in aCH mechanism is acetone
insertion into Rh-H bond taking 21.5 kcal/mol energy.
In ethylene case, the rate-determining step is Si-C reductive elimination
reaction with the energy barrier of 24.1 kcal/mol.
CH and aCH mechanism have the same rate-determining step and similarenergy barriers in both C=C and C=O double bond hydrosilylation. As theconsequence, in other cases (such as using Pt as the catalyst) when CH
mechanism is applicable, we should consider the possibility of aCH mechanism.

Double-hydride (DH) mechanism

CH & mCH mechanism
Path APath BDH mechanism

➢

ts1
➢

Free energy profile of acetone hydrosilylation in
DH cycle.

In acetone case, the rate-determining step in DH mechanism is also acetone
insertion into Rh-H bond and the energy barrier is 13.6 kcal/mol. This value ismuch smaller than in other catalytic cycle, which makes it become the mostpossible mechanism in acetone hydrosilylation.
In ethylene case, the rate-determining step is Si-C reductive elimination
reaction with the energy barrier of 12.7 kcal/mol. This value is just 1.5
kcal/mol higher than the largest energy barrier in mCH cycle. Thus DH andmCH mechanism are two most favorable mechanisms in ethylenehydrosilylation.

More discussions

ts2➢ For the Rh-catalyzed hydroilylation of acetone, much higher energy barrier in
mCH mechanism (43.4 kcal/mol) makes it less possible to take place.
➢ The energy different between CH and mCH mechanism is well explained by the
structures of transition states.

4e’_E➢ In Rh-catalyzed hydrosilylation of ethylene, mCH mechanism is most favorable
mechanism for the backdonation interaction in precursor complex.

➢ Incompletely broken C=O double bond and agostic interaction make the energy
barrier to be low in DH mechanism path A.
➢ π antibonding is found to have no interaction with Rh d orbital in the precursor
complex 4e’_E before ethylene insertion into Rh-Si bond. Thus Path B takes much
more energy than mCH mechanism and consequently being excluded.

Conclusions➢ Two new mechanisms were proposed, alternative Chalk-Harrod mechanism and double hydride mechanism.
➢ For ethylene, mCH mechanism is the most favorable mechanism. At the same time, DH mechanism is competitive to the mCH mechanism.
➢ For acetone, DH mechanism is the most favorable mechanism.
[1] S. Sakaki, M. Sumimoto, M. Fukuhara, M. Sugimoto, H. Fujimoto and S. Matsuzaki, Organometallics 2002, 21, 3788-3802.
[2] N. Nakatani, J. Hasegawa, Y. Sunada, and H. Nagashima, Dalton Trans. 2015, 44, 19344-19356.

83

Reaction Mechanism of DMC Formation from CO2 and Methanol
over CeO2 : A DFT Study‫ۑ‬Toshiyuki Sugiyama, Akira Nakayama, and Jun-ya Hasegawa
Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan

Background

Computational details

CeO2

CO2 + 2CH3OH

DMC

CeO2 or ZrO2 catalyst

CO2

CH3OH
Biomass resources

CO2
Monodentate• Intermediate of polycarbonates• Electrolytes for lithium ion batteries• Alkylating and carbonylating reagents

A green and sustainable process to replace the conventional methods

O2−

O2−

Ce4+

O2−

Ce4+

Ce4+

STEP1

+

STEP2

+

CH3OC(O)OH
DB1

Lewis acidCeO2(111)

Ref : Tomishige
Tomishige, K.;
K ; Sakaihori
Sakaihori, T
T.;; Ikeda
Ikeda, Y
Y.;; Fujimoto
Fujimoto, K
K. Catal
Catal. Letters 1999
1999, 58
58, 225
225–229.
229
Yoshida, Y.; Arai, Y.; Kado, S.; Kunimori, K.; Tomishige, K. Catal. Today 2006, 115, 95–101.

EB = −113.7kJ/mol

EB = −58.4kJ/mol

Path A

STEP1
Proton shift Attack of methoxy species
(TS2)
(TS1)
Int2’→ Int3

-40.0

Int4’→ Int5-100.0Ea = 27.5(−147.8)
Ea = 34.0(−150.5)TS1

Ea = 28.7(−100.6)
TS2

Ea = 33.4(−99.4)TS5

Ea = 2.8(−112.7)
TS3

-25.0

Ea = 66.0(−57.2)
TS6

Rectant-60.0 → Int1

-80.0

0.0

Potential Energy / kJ㺃mol−1

Potential Energy / kJ㺃mol−1

Potential energy profile of Path B

CeO2(slab) + CO2(g) + 2CH3OH(g)-20.0(−72.8)
Product

Ea = 11.8(−110.0)(−136.9)(−115.5)(−117.3)
Product
TS4
Int2’
Int5
(Most Stable)(−129.3) (−122.4)(−132.8)-140.0Int1’
Int2(−142.0) Int4’
Product(−148.7)Int4-160.0 Bidentate (−148.5)
Int3(−175.3) (−152.5)
Attack of methoxy species
Int1-180.0(TS5)Reactant
Int1’→ Int2DMC desorption
OH− desorption (TS3)-200.0 (−184.5)-120.0H2O formation (TS4)

Monodentate

EB = −66.1 kJ/mol EB = −60.0 kJ/molz Adsorption structures of CO2
䕾 Surface carbonate species
䠉 Monodentate / Bidentate → MC1
䕾 Molecular adsorption
䠉 Linear → DB1
z Adsorption structures of CH3OH
䕾 Dissociated adsorption
䕾 Molecular adsorption→ Both structures exhibit similar EB.

Analysis of reaction mechanism : Potential energy
Potential energy profile of Path A

Mol

Dis

+

MC1

In this work
We investigate reaction mechanisms of DMC formation
over CeO2 and clarify the role of the acid-base sites.

0.0

CH3OH

LinearBidentate

Lewis base
Ce4+x

EB = −54.1kJ/mol EB = −32.9kJ/mol EB = −16.9 kJ/mol• Acid-base sites (Lewis acid-base pairs)• Redox properties

CeO2 catalystyCeO2(111)

Adsorption structures of the reactants(CH3O)2CO

COCl2(Toxicity)z

Method 䠖 Periodic boundary DFT + U(PBE functional)
Unit cell 䠖 p(4㽢4) with 2 O-Ce-O tri-layers(32 CeO2 units)15.42 㽢 15.42 㽢 25.0 Å3

+ H2O

-50.0

STEP1

Reactant → Int1

-125.0(−122.1)
Int2

Ea = 35.4(−181.4)
TS1-150.0-175.0(−216.8)
Reactant

Path BEa = 27.6(−89.5)TS4(−117.1)
Int3(−123.0)
Product

Int2 → Int3(−185.2)(−196.1) Int1’Int1-200.0Ea = 34.2(−87.9)TS3

Ea = 64.5(−120.7)
TS2-100.0-250.0Int3 → ProductInt1’→Int2

Attack of methoxy species
(TS1)

-75.0

-225.0(TS6)

CeO2(slab) + CO2(g) + 3CH3OH(g)(−176.1)
Product(Most Stable)

Attack of methoxy species(TS3)
H2O formation(TS4)

Product

Proton shift
(TS2)

STEP2

STEP2

Analysis of reaction mechanism : Free energy
Int1 → Int2

Problems of the calculations based on the potential energy profilezNumerous local minima on the potential energy surface.
zConformation change between substrate and solvent molecules.
zThermal fluctuation of solvent molecules.

Blue moon ensemble approach

Integration of the mean force obtained by MD
simulation leads to the free energy profile of achemical reaction along a specified reaction
coordinate.
ࣈ
i

࢘࢏࢐

ࢃ ࣈ ൌන

ࣈ૙

j

૚

ࣔࢃ ǡ
ࢊࣈ
ࣔࣈǡ

ܹ ߦ ‫ ׷‬Free energyడௐǣ Mean forceడక ǡߦ ൌ ‫ݎ‬௜௝ ൌሺ࢘࢏ െ ࢘࢐ ሻଶ

Method䠖 DFT-based molecular dynamics
䠄NVT ensemble, T=360K䠅
DFT䠖 Periodic boundary DFT(PBE) + U
Unit cell䠖 p(3㽢3) with 3 O-Ce-O tri-layers(27 CeO2 units)11.56 㽢 11.56 㽢 25.0 Å3
CO2 㽢 1CH3OH 㽢 8

40.0

Free Energy / kJ·mol−1

Free energy profile in solution at finite temperature
was obtained by first principle MD simulation.

Int1 → Int2

30.0

∆A = 19.8(19.8)
TS1

20.0

Reactant → Int1

10.0
0.0
-10.0
-20.0

(0.0)
Reactant∆A = 31.8(10.0)
TS2(−21.8) Int1
-30.0

Int1

Conclusion∆A = 10.8(41.0)
TS3

Int2 → Int3

(4.6)
Int2

Attack of surface O(TS2)

Attack of methoxy species(TS1)

z The reaction mechanisms of DMC formation over CeO2 were theoretically investigated.
z The role of the acid-base sites on CeO2 was clarified.

84

Int2 → Product

Red䠖Path A
50.0 Blue:Path B∆A = 62.1(40.2)
TS2(30.2)
Int2∆A = 27.6∆A = 6.8 Int3 → Int4
(25.3)(11.4)TS5
TS3∆A = 26.1(−2.3)(5.2) Int4
TS4

C
O

(8.6)

Product(−0.8) Int3 → ProductAttack of methoxy species(TS4) (TS2)

H2O formation(TS3)(−20.9) Int3
Int3

H2O formation (TS3)
DMC desorption (TS5)CO

Adsorption and Catalytic Hydrolysis of Cellulosic Moleculesby Microporous Materials
Mizuho Yabushita,1,2 Hirokazu Kobayashi,1 Omar K. Farha,3 Alexander Katz,2 Atsushi Fukuoka1
1Institute for Catalysis, Hokkaido University, Japan (m.yabushita@cat.hokudai.ac.jp)

2Department of Chemical and Biomolecular Engineering, University of California, Berkeley, USA
3Department of Chemistry, Northwestern University, USA

Undesiredside-reaction

Hydrolysis

Objectives
Cellulose

Most abundant, renewable biomass

GlucoseKey compound

Zeolite-Templated Carbon (ZTC)¾ Consisted of warped-graphene¾ High surface area (≥ 3000 m2 g-1)
→ Suitable for organics adsorption¾ Highly active catalysts for cellulose
hydrolysis are required.
¾ For 2nd-generation bioethanol
5-Hydroxymethylproduction, by-products such as
furfural (HMF)
aromatics need to be devised.
Highly-toxic for biocatalysts

Metal–Organic Framework (MOF) NU-1000
Hexagonal
mesopore(2.7 nm)

P.-W. Chung et al., Langmuir 2012, 28, 15222;
M. Yabushita et al., ChemSucChem 2014, 7, 1443.

¾ Micropororous structure (1.1 nm)→ Ideal size for E-glucan guests→ E-Glucan was taken in the pore
within 2 min.
H. Nishihara et al., Carbon 2009, 47, 1220.

M. Yabushita et al., ACS Catal. 2015, 5, 6422.

¾ Consisted of pyrene units¾ High surface area (2320 m2 g-1)
→ Suitable for organics adsorption

Triangularmicropore(1.1 nm)
O. K. Farha et al., J. Am. Chem. Soc.
2013, 135, 10294.

¾ Well-ordered micropororous
structure (1.1 nm)

Biomass-Derived Toxins for Biocatalysts

H2O2 Treatment
Properties of parent and H2O2-treated ZTCs

Acid site Amicropore/mmol g-1 /m2 g-1
ZTC
1.05
3480
Z-H(5)
1.81
3700
Z-H(15)
2.10
3360
Z-H(30)2.32
3400
Z-H(60)2.48
3050

MaterialVpore/cm3 g-1
1.91
1.90
1.81
1.82
1.61

¾ Acid sites are successfully introduced by H2O2 treatment,with minimal change to microporous structure.

Competitive-Mode Adsorption

Adsorption and Hydrolysis of E-Glucans
1. Adsorption
2 g L-1 E-glucan solution (40 mL),
20 mg ZTC, 277 K, 10 min

E-Glucan(3,600 g mol-1)

2. Hydrolysis
ca. 25 mg E-glucan/ZTC,
1 mL H2O, 453 K, 3 h

Glucose¾ NU-1000 discriminates furanics from monomeric sugars intheir aqueous mixtures.

Adsorption uptake of E-glucans by ZTCs

Material
ZTC
Z-H(5)
Z-H(15)
Z-H(30)Z-H(60)E-Glucan uptake/mgGlc-unit g-1
306
390
315
328
315

¾ All ZTC materials exhibit similar E-glucan uptake regardless ofthe H2O2-treatment.
¾ The catalytic hydrolysis activity of ZTC directly increases uponincreasing acid-site density.

Conclusions¾ Only NU-1000 can selectively remove aromatics
from aqueous soluitons.

¾ H2O2-modified ZTCs, which have high acid-site density and surface area as well as ideally sized
micropores, show good performance in both E-glucan adsorption and subsequent hydrolysis.

M. Yabushita et al., ACS Sustainable Chem. Eng. 2016, 4, 6844.

¾ NU-1000 adsorbs aromatic compounds from aqueous solutions containing glucose co-solute,with an outstanding degree of selectivity comparable to biomolecules.

M. Yabushita et al., Chem. Commun. 2016, 52, 7094; Chem. Commn. 2016, 52, 11791; Langmuir 2017, 33, 4129.

85

Stereoselective isomerization of eugenol to trans-isoeugenol catalyzed by Ni(0) phosphines:
experimental and theoretical studies
Y. Permana,1 Arifin,2 L. Saputra,1 N. Gustini,1 S. Irle,2 A. Patah,1 M. A. Martoprawiro1
1Chemistry Department, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Bandung, Indonesia
2Institute of Transformative Bio-Molecules, Nagoya University, Nagoya, JapanI Conversion of natural products

II Catalyst design
Ru Rh Pd

Isomerization

Eugenol(US$ 19 /kg)
72-97% of clove oil

Os

Vanillin(US$ 70 /kg)trans-Isoeugenol(US$ 37 /kg)

Sharma et al. 2006. J. Mol. Catal. A Chem., 245, 200-209

Catalysts:(1) KOH : 150 °C, 10 h, Conv. 60%, excess base
Cerveny et al. 1987. React. Kinet. Catal. Lett. 33, 471-476.
(2) NiAl-HT : 200 °C, 6 h, Conv. 77%, Select. 84%
Jinesh et al. 2010. Catal. Lett. 134, 337-342.
(3) RuCl2(PPh3)3 : 78 °C, 3 h, Conv. 99%, Select. 96%
Sharma et al. 2010. J. Mol. Catal. 245, 200-209.

Ir

Late transition
metal:
Rich electron
Low oxidation
state

trans-Isosafrole

www.alibaba.com (Sept., 2015)

III This work

Fe Co NiClove oil
(US$ 5 /kg)

Hassam et al. 2015. Chem. Rev. 115, 5462–5569.

Pt
Ligands:
Good σ donor(for example
phospineligand)Conv. 94%, Select. 92%[1] Gogsig et al., 2012, J. Am. Chem. Soc., 134, 443-452; [2] Kuntz et al., 2007, Oil Gas Sci. Technol., 62, 781-785

In situ generated
Ni(0) Phosphine catalyst
Eugenoltrans-isoeugenol

Computational details

Program package: Gaussian 09 version D.01
Method: PBE0-D3
Basis sets:
Ni: Stuttgart RSC 1997 with ECP
N, O, P: 6-31+G(d)C in alkene and acetonitrile: 6-31G(d)C in alkene and acetonitrile: 6-31G(d,p)
All other atoms: 6-31G

High conversion and selectivity of trans- product can beachieved by the expensive ruthenium complex as the catalyst.

Ni(0) is an important species for the oxidative addition step.

We evaluated the performance of catalysts and elucidate thereaction mechanisms.

IV Ni source effects

V Ligand effects

VI Solvent effects (1)Reaction conditions: 0.05 mmol NiCl2·6H2O, 5 mmol eugenol, 0.5 mmol ligands, 0.5mmol Zn, 3 mL of CH3CN, 80 °C, 1 h, stirring at 400 rpm, 1 atm N2.

µµReac%on	  condi%ons:	
  0.05	
  mmol	  of	
  Ni(II),	
  5	
  mmol	  of	
  eugenol,	
  0.5	
  mmol	  of	
  Zn,	
  0.5	
  mmol	  of	
  PPh3,	
  3	
  mL	
  of	
  
MeCN,	
  353	
  K,	
  1	
  h,	
  N2	
  atmosphere.	
  a	
  No	
  addiCon	
  of	
  Zn	
  or	
  excess	
  of	
  PPh3.	
  b	
  Substrate:	
  30	
  mmol	  of	
  eugenol.	
  Ni(PPh3)3Ni(P(OPh)3)3

Reaction conditions: 0.05 mmol NiCl2(PPh3)2, 5 mmol eugenol, 0.5 mmol Zn, 0.5mmol PPh3, 3 mL solvent, 80 °C, 1 h, stirring at 400 rpm, 1 atm N2. a Using 1 mL of
4-Chlorobutyronitrile.

High activity can be achieve with NiCl2(PPh3) as the precursor.

A strong sigma donative ligand may increaseelectron density at Ni(0).

MeCN is the best solvent to achieve the best catalytic activity.

VII Solvent effects (2)VIII Time Profile of MeCN addition

VIII Proposed mechanism
MeC
N
Ni(0)L2
A

Reaction conditions: 0.05 mmol of NiCl2(PPh3)2, 30 mmol ofeugenol, 0.5 mmol of Zn, 0.5 mmol of PPh3, 3 mL of MeCN, 353 K, N2
atmosphere.
	
  

100

N C
B

A

R

C o n v .	
  (% )

	
  

B

0

10

20

30

40

R eac tio n 	
  tim e	  (m in )50

R

MeCN activation
R

H
L
Ni
L
NCH2C
H

J

60

How does MeCN increase the catalytic activity?

IX Free energy profiles

elimination

R
L
Ni
L
CH2CN
I

R

Olefin insertion

There are three important steps.

X Summary¥ Trans-isomerization of eugenol with high conversion andselectivity is successfully catalyzed by simple Ni(0) complex.
¥ The importance of MeCN in the reaction mechanisms is clearly
elucidated.

Without MeCN

Rotation from N2 to
N3 is required and
it is the RDS of thereaction without
MeCN.

Ni(0) can activate MeCN through the C-H activation reaction.

86

H
L Ni L
CH2CN

K

H
L
Ni
L
NCH2C

+ MeC N 	
  after	
  30	
  m inβ-hydride

With MeCN

Me+ MeC N 	
  fro m 	  th e	
  b eg in n in g

40
20

A small amount of MeCN dramatically increased
the catalytic activity.

OCH3

E

60

0

OH

Ni(0)L2

80

Reaction conditions: 0.05 mmol NiCl2(PPh3)2, 5 mmol eugenol, 0.5 mmol Zn, 0.5 mmol PPh3, 80°C, 1 h, stirring at 400 rpm, 1 atm N2. a Using 0.005 mL of 4-Chlorobutyronitrile besides acetonitrile.

L = P(Ph)3
R=

Acknowledgement
Financial support by:
Dispatching Young Researchers Abroad Program at theGraduate School of Science, Nagoya University, Japan

Theoretical Investigation on Photo-activation Process of Diaryl Pyrido Cyanine
A. Sarinastiti1, AriÞn1, R. Shimizu2, K. Suda2, K. Uno2, Y. Sato1, D. Yokogawa1,2
1Institute of Transformative Bio-Molecules (WPI-ITbM), Japan

2Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya, JapanI Cyanine Properties to Applications
N

N

n

R

The most investigated family ofsynthetic pigments.

R

III Photo properties of cyanine
derivatives

II Chlorinated Cyanine
In general, however, cyanine dyes has a poor chemicaland photochemical stability.
Chlorinated cyanine is one of intermediate molecules
for further derivatization to improve water solubility,
prevent aggregation, etc.

Example:cyanine dyes as pHresponsive probes todetect cancer cells.

N

Hilderbrand, S. A. et al., Bioconjugate Chem., 2008, 19, 1635.

N

Ph

B

Dost, T. L. et al., Analytical Chemistry Insights, 2017, 12, 1.

How is the photo property of cyanine derivatives?

The properties of cyanine dyes depend on its
substituent.

V Computational Details

VI Proposed Mechanism

Excited state calculation : TD-CAM-B3LYP/aug-ccpVDZ

hν = 561 nm

N

COOH

Ground state calculation : CAM-B3LYP/aug-ccpVDZ

Cl

Ph

N

HOOC

Molecule Molar Absorptivity (M-1cm-1) Stokes Shift (nm)A
60,70022
B32,20018

IV Chlorinated Diaryl Pyrido Cyanine
Symmetrical cyanine with 4 double bonds for longwavelength absorption

N
Cl

COOH

A

Ptaszek, M. et al., Progress in Molecular Biology and Translational Science,
2013, 113, 59.

Cyanine dyes have great potential applications.

N
H

HOOC

Ph

N

N

DCl

Ph

DH
Uno, K. Doctoral Dissertation, Nagoya University, 2017

Solvation Theory : RISM-SCF-SEDD
Solvent : Water
Temperature : 300 K

How is the mechanism of substitution of chlorine atomby photo-activation of DCl in water?

Program Package : GAMESS 2012 and Gaussian 16

VII Energy Diagram

VIII Model Comparison

There are three steps: excitation process, insertion of
proton, and Cl dissociation.

VIII Excitation Process
Kohn-Sham Orbital

DCl

M1-Cl

M2-Cl

HOMO

LUMO

What is the important factor for
Cl substitution process?

In DCl, low excitation energy and Cl-dissociation
barrier are important for Cl substitution reaction.

Delocalized HOMO ease the electron transfer during
excitation.

IX Proton Insertion Process

XI Summary

Acknowledgement

DCl(S0)T-DCl(S1)¥ The mechanism of photo-activation of diaryl pyrido
cyanine dyes has been studied.
¥ Delocalized HOMO is important to lowering
excitation energy.
¥ The twisted state of DCl is important for proton
insertion step.

Financial support by
Grant-in-Aid for Young Scientist B(No.2473C015) and ScientiÞc Research (C) (No.
15K05385)

Table of charge changes
Atom

DCl (S0)Cl

T-DCl (S1)

Cl

-0.05

0.10

C2

-0.09

-0.13

hν
Ph

Proton insertion becomes easier because the charge of C2
is more negative, which increases nucleophilicity of C2.

N

N

DCl

Ph

Ph

N

N

Ph

DH

87

88

Perparation, characterization, and catalytic performances ofPt nanocluster – polymer – carbon nanotube composites
䚽Kentaro ICHIHASHI1, Shota MIYAMOTO1, Kana SAKAMOTO1,
Satoshi MURATSUGU1, Mizuki TADA1, 2, 3

Dept. of Chemistry1, RCMS2 and IRCCS3,
Nagoya University

Introduction and Purpose

Anodic reaction of fuel cells:
O2 + 4H+ + 4e- Pt/C 2H2O Oxygen reduction reaction (ORR)

Catalyst Design
Strategy: Preparing Pt nanoclusters and polymer matrix in one step by co-polymerization
Pt complex

Pt/C: Carbon-supported platinum catalyst

Nanoclusters Isolated on Support Surfaces

Issues on Pt/C catalysts

䞉Large particle size distribution (> 3 nm)

Stacking conductive polymer
matrix overlayers
and reduction

Since there are few active sites,
ORR activity and electromotive force decrease.

The active sites are further reduced,
resulting in a large degradation of Pt/C.
ADT(17.5 k)

20 nm

20 nm

2

䞉Co-polymerize with
Pt4-Pyrrole complex
䞉Electrically conductive

Polypyrrole(PPy)

Catalyst Preparation and Characterization

2 16%1)  573 K, 2 h
Evacuated

4) APS2, 0.27 mmol
5) Stir 24 h, 274.5 K
6) H2O, MeOH (Wash)

NT
MWCNT

2)

20 nm

2) Et2O (Wash)

161 m2 g-1

174 m2 g-1
XRF

Particle Size Distribution
B

1 89%

A

B

2:APS = Ammonium peroxisulfate

BET

H2, 40 kPa
573 K, 1 h

20 nm

1:SDS = Sodium dodecyl sulfate

1) Acetonitrile
Acetone1H NMR (600 MHz, DMF-d )7

Polymer matrix

Pyrrole unit

TEM1) SDS1 aq.
2) Pyrrole, 8.8 mmol3) 1/MeCN, 23 mmol

8 eq.

䞉High conductivity andelectrochemical
resistance䞉Large specific surface
area

Multi-walledcarbon nanotube(MWCNT)䞉Co-polymerize with pyrrole monomer

Reflux
393 K

The fourth series of Experimental Chemistry, Vol. 17, p. 452.

Carbon support

Yamaguchi, T. et al Chem. Eur. J. 2001, 7, 5409.
Tanaka, S. et al Inorg. Chem. 2011, 50, 11384.

Preparation of size regulated andhighly stable Pt nanoclusters
with high Pt loading

Synthesize of Pt4-Pyrrole
K2PtCl4
CH3COOH
CH3COOAg

Nanoclusterization

Copolymerization

䞉In-plane acetate ligand is replaceable.
䞉Polymerization unit can be introduced.

Langmuir, 2017, 33, 10271.

PurposeH2
reduction

Pt4 core cluster(1) Size-regulated Pt nanoclusters(2) Stability enhancement as catalyst(3) Low Pt loading (< 4 wt%)

Degradated

Fresh

Carbon supports

Pt4-Pyrrole complex

Pt nanocluster
Polypyrrole (PPy) matrix

䞉Aggregation of Pt nanocluster

Size-regurated Pt nanocluster

Polymer matrix

Monomer

12.6 wt%

Pt LIII-edge
edge XANES

1.6 f 0.2 nm

163 m2 g-1
12.6 wt%
TGA 1st Differential

PtII

 = 11.4 (s, 4H), 7.66 (dd, 4H), 6.92 (dd, 4H), 6.72 (dd, 4H),
2.02 (s, 12H)

Pt0
PPy matrix

13C NMR (150 MHz, DMF-d )7A = 194.2, 180.1, 124.8, 119.5, 116.7, 110.2, 21.1

Pt foilPt(acac)2B
A

1.6 f 0.3 nm

Elemental Analysis
Calcd. for C28H28N4O6Pt4·C3H6O : C: 24.6, H: 2.26, N: 3.70
Found : C: 25.1, H: 2.44, N: 3.39

B
A

Acetatoligand

MWCNT(1) A Pt nanocluster catalyst with narrow size distribution (from TEM) was prepared in A.
(2) Sufficient amounts of Pt loading (12.6 wt%) on A was confirmed by XRF.
(3) Pt species in A was reduced to almost zero valence from Pt LIII-edge XANES.
(4) The presence of PPy was confirmed by TGA.

ESI-TOF MS
m/z 1479.05 [M+Na]+ (Calcd. for C28H28N4O6Pt4Na)

ORR Activity and Durability of the Prepared Pt Catalyst
Rotating disk electrode (RDE) method

Cyclic Voltammogramsgand Electrochemical Surface Area (ECSA)

Measurement Conditions

H2 desorption
peak area (SH)Set up of measuring system

Measuring system of RDE method

WE: GC-RDE, CE: Pt plate, RE: RHE
Electrolyte: 0.1 M HClO4 aq., 293K
Preparation of working electrode䞉Suspension of catalyst was dropped on RDE.
䞉Nafion soln. (5 L) was then dropped on RDE.
䞉Pt surface density (D-Pt): 8.8 g-Pt cm-2

A
Commercial Pt/C catalyst

Measurement Procedure
Evaluation of catalytic active site

Electrocatalytic surface area (ECSA)

Calculated by H2 desorption peak area (SH)in cyclic voltammogram.
Evaluation of ORR activity

h1.2

ECSA (m2 g-1) =Analysis Conditions
Electrolyte: 0.1 M N2-satulated HClO4 aq., 293K
Scanning rate (): 50 mV s−1

ORR Polarization Curves at 1600 rpm and Mass Specific Activity (MSA)
A

Commercial Pt/C catalyst

Mass specific activity (MSA)

Measured by ORR polarization curve(Rotating speed: 400, 900, 1600, 2500 rpm).

Accelerated durability test (ADT)
Conducted by Square wave potential cycles(3 s, 0.6 VRHE−3 s, 1.0 VRHE, 6000 cycles).
Evaluation of catalytic durability
Evaluated by decrease ratio of MSA after the ADTfrom that of before the ADT.

SH (C V s−1 m-2)
2.10 (C m-2) h (V s−1) hD−Pt (g−Pt m-2)

A

Pt/C

Koutecky-Levich equation:

j-1 = jk−1 + jL−1 = jk−1 + (B1/2)−1

j: measured current density
jk: kinetic current density
jL: diffusion-limiting current density
B: Levich constant, : angular velocity

10%

A
Pt/C

h1.5

MSA = jk/D-Pt

Small shift

Large shift

Analysis Conditions
Electrolyte:
0.1 M O2-satulated HClO4 aq., 293K
Scanning rate: 10 mV s−1(1) A exhibited 1.2 times larger ECSA value than commercial Pt/C catalyst, which suggests that A has more ORR active site per Pt weight than commercial Pt/C.
(2) The initial mass specific activity (MSA) of A was 1.5 times larger than that of commercial Pt/C catalyst, and the durability of A on the accelerated durability test (ADT) was improved by about 10%.

Conclusions
䞉We succeeded in synthesizing the new Pt4 complex (1) with pyrrole unit by the ligand exchange reaction of in-plane acetate ligands.
䞉A high loading Pt0 nanocluster catalyst (A) with narrow size distribution was successfully prepared by the copolymerization method of 1 and pyrrole on MWCNT.
䞉The mass specific activity for ORR and catalyst durability on A was improved compared to a commercial Pt/C catalyst.

89Non-Equilibrium Supramolecular Polymerization of
Fluorescent Dye in Aqueous Media(1Grad. Sch. Sci., Nagoya Univ.; 2WPI-ITBM, Nagoya Univ.) ○Natsumi Fukaya1, Soichiro Ogi1 and Shigehiro Yamaguchi1,2

1. Introduction

Fibril formation in living system

Biomimetic supramolecular polymerization insolvents of low polarity

Cooperative
growthConformational
conversion

AFM height image
Initiator

Nucleation

Prion

=

=

Normal prion
proteinHydrogenbondingElongation

Abnormal prion
protein SonicationRef.) F. Würthner et al., J. Am. Chem. Soc. 2015, 137, 3300.
AFM height image

Autocatalytic
replicationRef.) Aguzzi, A. & Calella, A. M.
Physiol. Rev. 2009, 89, 1105.
http://www.s-graphics.co.jp/
tankentai/news/prion.htm

Ref.) D. Miyajima, T. Aida et al. Science. 2015, 347, 6222.

Kinetically trapped state

Hydrogenbonding

CyclicampliÞcation

Seeds

Seeds

H

Amyloid Þbril
(Aggregate)

Normal prion
protein

2. Molecular design in this work
Diketopyrrolopyrrole
Highly ßuorescent molecule
Planar π-system
π−π stacking interaction

S
H
N

RO

Triethylene glycohol group
High solubility to water

O O
N

N

O O

OR

O

R=

Working hypothesis
Intramolecular hydrogenbonding

3

Intermolecular hydrogenbonding

Intramolecularhydrogen bonding(H-O distance: 2.0 Å)

Monomeric state
Kineticallytrapped state

Aggregated state

3. Temperature-dependent self-assembly

4. Time-dependent self-assembly

Solvent:
MeOH/H2O (1:1, v/v)
Concentration: 5 μM

Heating

UV-vis absorption spectral change upon heating

Aggregated state
20 °C

Absorbance at 601 nm

500
Wavelength / nm300

! heating! cooling

0.02

0.04

Tc = 46 °C

Tc’ = 27 °C
20

700

30

40
50
Temperature / °C

100
Time / min

6. Seeded polymerization

Effect of H-bonding on trapping 1H MNR spectrum in THF-d8/D2O = 1:1 (v/v)

N

O
N

RO
OR

H

Reference 1

OR

HA, 7.85 ppm

O

N

O

S

R=

HB

A

OHN
O

HD

HE HF, 5.24 ppm

OR

9.0

8.0

7.0

6.0

O

O
N
HF

N
HF

O

O

H

H

5.0

Effect of H-bonding on assembly UV-vis absorption spectrum in MeOH/H2O = 1:1 (v/v) at 20 °C
RO

O
RO
OR

O O
N

O O

N
S

Reference 3

OR
O

R=

O

3

AbsorbanceS

seeds solution
300 μLfast coolingto 30 °C

0.1

O O
N

N
H
O O
N

0.05

0.08

N
H

O O

700

N

O

The amide hydrogens are hydrogen-bonded intramolecularly in the monomeric stateand intermolecularly in the aggregated state.

J-Aggregate! No seeds! Seeds 300 μL

0.1

AFM height image
20 μm × 20 μm

0.06

0.04

Increase inpolymerization rate

0.02

300

Non hydrogenbonding acceptor
500
Wavelength / nm

—Seeds 300 μL

Intermolecularhydrogen bonding—compound 1—reference 3

300

90

AFM height image
5 μm × 5 μm

0.12 —No seeds

Downfeild shift

Reference 2

Reference 2

Monomeric state
60 °C, 3 mLsonicationfor 10 min
in water bath

Absorbance change at 601 nm

6

HE

HD
O
N
HF

HC

N
O

Reference 1
RO

Intramolecularhydrogen bonding

Absorbance at 30 min

HB
A

OHN

S

200

A fast cooling to a certain temperature between Tc’ and Tc resulted in a spontaneous
formation of J-aggregate with a lag time, where monomers are kinetically trapped.

5. Effect of H-bonding on trapping and assemblyHC! 22 °C! 29 °C! 32 °C

Lag time
060

A thermal hysteresis with Tc’ (27 °C) from Tc (46 °C) was observed in a cycle offormation and disassembly of J-aggregates.

RO

AFM height image The sample fast
3.5 μm × 3.5 μm cooled to 30 °C

0.06

Tc : critical temperature

0.08

Solvent:
MeOH/H2O (1:1, v/v)
Concentration: 5 μM

J-Aggregate

22, 29, 32 °C

Absorbance change at 601 nm

Absorbance at 601 nm

Absorbance

60 °C
0.05

0.1

Absorbance change at 601 nm
0.12

20 °C

0.1

Monomeric state
60 °C

Absorbance at 601 nm

Monomeric state
60 °C

Trapped state?

1 K min–1

Spontaneous
self-assembly

fastcooling

Coolingsity of ESIPT emission

Aggregated state
Intermolecularhydrogen bonding(H-O distance: 1.9 Å)

Amide group
Intra- and intermolecularhydrogen-bonding

N
H

S

1

OR

EnergyOptimized structure
Trapped state

RO

Design of kinetically trapped state in water

500
Wavelength / nm

700

0

20

Additionof seeds

40
60
Time / min

80

100

The growth of J-aggregate could be initiated by the addition of seeds in a lag time.

7. Summary
J-aggregate formation of amphiphilic DPP in solvent of high polarity
Thermal hysteresis in a cycle of the assembly and disassembly
Monomers trapped kinetically between Tc and Tc’
Seeded polymerization of J-aggregate nanorods

Rapid Access to Fused Aromatics by Palladium-catalyzed
Annulative Dimerization of Aryl (Pseudo)halides
Taito Hiraga,1 Yoshito Koga,1 Yutaro Saito,1 Kei Murakami1, 3 and Kenichiro Itami1, 2, 3
1Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
2JST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University
3Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya UniversityH

annulative
dimerization

H

OTf

Herein, we develop a one-step palladium-catalyzed annulative
dimerization of aryl triflates. This reaction allows the synthesis ofvarious π-conjugated molecules from o-hydroxybiphenyl-based starting
materials, which can be easily prepared by hydrogenation ofdibenzofuran derivatives.

Pd cat.

TfO

aryl triflates

ITAMI GROUPRGANIC CHEMISTRY

fused aromatics

Discussion
Concept

Possible Mechanism(a) Study concept

Classical dimerization

Ar
Ar

X

H

Ar

–2X

'ortho' C–H
activation

Annulative dimerization

X

+

H

Ar

– 2 HX

X = (pseudo)halogen

biarylsAr

1

PdX(L)

oxidative
addition

L = PnBu'bay' C–H
activation

HA

K2CO3

Pd0L

– HB X

HB

Cl

Cl

C
‘intermolecular’
C–H activation[O]

Ph
Koga, Y.; Kaneda, T.; Saito, Y.; Murakami, K.; Itami, K. Science 2018, in press.

Cl

OTf

This work

aryl halides

OTf¥ naturally abundant¥ low toxicity¥ less expensiveoxidative
addition
1

B

L

K2CO3

intramolecularC–H activation

insertion

Pd
X

Ph

Ph

Pd
L X

Pd
L

F

E

G

Path (ii) 'bay' C–H activation pathway
PdCl2 (5.0 mol%)
P ligand (10 mol%)
K2CO3 (3.0 eq.)
PivOH (1.0 eq.)

oxidative
addition
1

C

OTf

reductive
elimination

MeO

H

iPr

CyBrettPhos
trace

PCy3·HBF4
72%

HBF4

PCy2

iPr

P

P

P

PnBu3·HBF4
quant. (88%)(98%)adcype
trace
a 0.5 eq. of PivOH

R

Br

86%

37%a

Br

R

R

Ph

28%

Ph
94%

NaOtButoluene120 °C

OH

Ph

Ph
43%

PdCl2
PnBu3·HBF4
K2CO3
PivOH

OTf

Ph
60% (2 : 1)a,bR

Ni(cod)2
SIPr·HCl
Et3SiHPh

CH2Cl2

a absence of PivOH b PdCl

R

O

toluene/EtOH/H2O
80 °C

Tf2O
2,6-lutidine

CF3

annulative
dimerization

2-hydroxybiphenyl
derivatives

OMe

F3C

Isolated yield.

Ph

G

TfO

53%

F3C

CF3

intramolecularC–H activationHO

PhB(OH)2
PdCl2(PPh3)2
K2CO3

O
OMe

MeO

98%

J

dimer

R
dibenzofuran
derivatives

MeO

Me

Ph

2

Ph

Ni-catalyzed
reductive ring-opening

O

Me
Me

K

Application

F

Pd0L

TfO

CPME, 140 °C

Meoxidative
additionP

PdCl2 (5.0 mol%)
PnBu3·HBF4 (10 mol%)
K2CO3 (3.0 eq.)
PivOH (0.5 eq.)
OTf

I

reductive
elimination

D

Result in parentheses represent the isolated yield.

Substrate ScopeL
Pd

intramolecularC–H activation

L

Path (iii) ‘intermolecular’ C–H activation pathway

OMe

HBF4

Pd

L X Ph2 (NMR yield)

Me

X

Pd

K2CO3

CPME (0.5 M)
140 °C, 20 h

1

46%

Ph

D

Path (i) 'ortho' C–H activation pathway

phenol derivatives

Condition Screening

PnBu(Ad)2
Cs2CO3 : N.D.
K2CO3 : 33%

Path (iii)

TfO

HC

chlorophenylenes

P

L

Pd

1
– HCX

H

(c) This work

Path (ii)PdLA

X = OTf or CO3K
Pd cat.

Path (i)

B

OTf

Ar

edge-sharing
fused aromatics(b) Previous work

HPdL

– H AXCPME
140 °C68%n
2 (15 mol%), P Bu3·HBF4 (30 mol%)91

Rapid N-Alkylation of Amines by Alcohols Using a
Copper–Gold Photocatalyst◯ Lyu-Ming Wang1, Yuna Morioka1, Kellie Binder2, Andrew E. H. Wheatley2, Susumu Saito1, and Hiroshi Naka1
1Graduate School of Science and Research Center for Materials Science, Nagoya University
2Department of Chemistry, University of Cambridge

H
N

H

hν

CH3
N

Cu/TiO2 x Au/TiO2+ CH3OH

room temperature

O

CH3

N

O

Abstract: Late-stage functionalization of amino groups in complex organic compounds is
one of the most important key technologies in modern organic synthesis towards bio-active
molecules and pharmaceuticals. We report here the Þrst late-stage N-alkylation ofpharmaceutically relevant amines with alcohols at ambient temperature. The mixed
photocatalytic system enabled the rapid N-alkylation of pharmaceutically relevant molecules,
the selective mono- and di-alkylation of primary amines, and the non-symmetrical dialkylationof primary amines to hetero-substituted tertiary amines.

CH3

Rivastigmine

Introduction

N-Alkylamines in Pharmaceuticals
CH3
N

O

N

H3CO
N

CH3

N

HO

CH3

Imipramine

CH3– H 2O(depression)

Results and Discussion
N

O

NH2

O

hν (λ = 300–470 nm)
photocat (M/TiO2 22 mg)

N

N

CH3

CH3

N

CH3

[ ]9

H

N

CH3

[ ]9

89%, 3 h

CH3
N

none
<1%

O

OCH3

Boc N

hν

hν

Cu/TiO2
NH2

CH3

O

O

NH2

H

N

87%, 50 min, (43)CH3O

CH3OH (5 mL), Ar, 50 °C

73%, 8 hCD3N85%, 2.5 h
NHAc
O

90%, 3 hn-hexane (10 mL), Ar, 25 °C, 50 min

N

CH3

CH3

87%, 10 h

O

N

easy
work-up[ ]9 NH
82% isolated yield

N
H

O CH3

CH3

N

N

CH3

CH3

[ ]7

80
60
40

Cl

20

C 2H 575%

NH84%, 20 h, (3)result with (rac)-rivastigmine
100

R1

R2

3

N
H

(d) Catalyst recycling

hν
R2OH

O CH3

neat, 71%, 16 h, (130)86%, 20 h, (4)389%, (50 °C), 13 h, (2)R1OH, CPME

N

N
H

95%, 1.5 h, (33)067%

2 3 4 5 6 7 8
Number of times recycled
82% isolated yield in 9th run

1

Cl

N

CD3

CD3

N

N

CD3

N

CH3

N CH3

C 2H 5

N

92

CH3

CH3

H3CO

CH3

Cl

N

83%, 18 hhν, Cu/TiO2, Au/TiO2NHhνCu/TiO2, Au/TiO2

NH2

O

HO

1.0 g

CH3

N

CH3

CH3

N

CH3

CH3

96%, 55 min, (33)Cl

97% isolated yield

CD3

91% (89%D), 16 h
Rivastigmine-d6

O

O

N

(c) Non-Symmetrical Dialkylation

hard to promote(+ 2H+, 2e–)

12 min

N

N

N

N
H

[ ]7

Au/TiO2CH3(43 equiv)

79%, 16 h, (2)hνhν (λ = 300–470 nm)
Au/TiO2 22 mg
Cu/TiO2 22 mg

NH2 + C2H5OH

[ ]9

H3CO
O

[ ]9

N

H3CO

92%, 4 h

5. Synthesis of Bioactive Compounds
CH3

Au/TiO2

Cu/TiO2

91% isolated yield (S:R = 96:4)

89%, 5 h

N
H

N
H
H
N

H
H 2O

50 µmmolR1

in n-hexane (10 mL), 0.2 mmol scale

3. Rapid Synthesis of (rac)-Rivastigmine
N

N

CH3

in CPME (10 mL), 1 mmol scaleH

fast(– H+, e–)

CH3

R

CH3OH (10 mL), Ar, 25 °C, 5 h

N

H3CO

[ ]9

91% (4 h)isolated yield
Cu + Au

efficient(+ 2H+, 2e–)N

Au/TiO2R(b) Monoalkylation of Amines by Solvent Control

Cu/TiO2HN
R1OHhν, Cu/TiO2, Au/TiO2

N

CH3

2. Synergistic Effect in Cu–Au Mixed Photocatalytic SystemhνCu/TiO2 x Au/TiO2

t = 0.2–20 h

R

R

hν

83%, 4 hNmajor side product

Cu
Cu
Cu
Cu
Cu
Cu
Cu
+ > + > + > + > (double) > Cu > +
+
Pt
Pd
M
Au
Au
Ag
Yield 70% 59% 50%
42%40%
21% (<< 1%)
1%(dark)

CH3OHhν

Non-symmetrical
dialkylation

NH2

88%, 5 h

O

+

ROH

CH3

major intermediate

Pt >
1%

hν

neat conditions (alcohols 10 mL), 1 mmol

3. mixed Cu/TiO2 & Au/TiO2 showed best
result in increasing reaction rate in 2 hmoderate(– H+, e–)

H
N▶︎︎ Applicable to pharmaceutical synthesis (up to 1 g)

O

H

N

1. Au/TiO2 showed highest Conv. in 1 h
MAu > Pt > Pd > Cu > Ag
Conv. 93%
75%
74%
60%
54%

>

NH2

hetergeneous catalysts
e.g. Metal(OH)x/Al2O3, Metal/Al2O3
Metal/TiO2, et al.
– selectivity/recyclable catalyst– harsh reaction conditions(typically > 110 °C)
or high pressure (5 atm)(a) Dialkylation of AminesOO

M/TiO2 ( 5 wt %, Cu, Pd, Au,
Pt, or 4 wt %, Ag )2. Cu/TiO2 gave highest yield in 7 h
MCu > Pd > Ag > Au
Yield 92%
65%
68%
5%

R

4. Substrate Scope

CH3

CH3OH (10 mL), Ar, 25 °C

1 mmolN– limited scope of both simple amines and simple alcohols– large excess (> 140 equiv) of alcohols– long reaction time (> 4 h for completion of 0.2-mmol scale)

1. Optimization Study for Rapid Reaction
CH3

R

Selective
monoalkylation(solvent control)Rorphotocatalysts
Pt/TiO2 (Ohtani, Kagiya, 1986), Pd/TiO2 (Shiraishi, 2013; Shi, 2015)
Au/TiO2 (Sá, 2013), Ag/TiO2 (Saito, 2015), Cu-Mo/TiO2 (Shi, 2015)

CH3

Venlafaxine(depression)

H
N

Review: Yu et al. Chem. Soc. Rev. 2015, 44, 2305.

(gastropathy)(dementia)

catalyst

homogeneous catalysts
transition metal complexes(e.g. Ru, Ir, Fe, Co, Mn)– broad substrate scope– high temperature requested(typically > 80 °C)

Alverine

Rivastigmine

N

+ ROH

C 2H 5

CH3

O

NH2

N

CH3

This Work

N-Alkylation of Amines with Alcohols

Yield (%)

hν

72% (> 95%D), 50 °C, 10 h
Venlafaxine-d6

94% (> 95%D), 5 hImipramine-d3

88%, 50 °C, 17 h
Me-Desloratadine

90%, 3.5 h
Alverine

BnO
HO
BnO

O
H 3C

O

N CH3

OCH3

75%, 50 °C, 12 h
Glucosamine derivative

93

Catalytic Oxidation of Small Gaseous Alkanesby P450BM3 with Decoy Molecules

Shinya Ariyasu,1,2 Zhiqi Cong,1,2 Osami Shoji,1,2 Yuichiro Aiba,1,2 Chie Kasai,1,2 Hiroki Onoda,1 Kazuto Suzuki,1 Hiroshi
Sugimoto, 2,3 Yoshitsugu Shiro,3 Takashi Kamachi,2,4 Kazunari Yoshizawa,2,4 Yoshihito Watanabe,5
1Department of Chemistry, Graduate School of Science, Nagoya University. 2JST-CREST. 3RIKEN SPring-8 Center, Harima Institute. 4Institute for Materials Chemistry and Engineering, Kyushu

University. 5Research Center for Materials Science, Nagoya University.

94

1HZ,QVLJKWLQWRGV'1$,QYDVLRQE\1/631$V
૓*HUDUGR8UELQD<XLFKLUR $LED2VDPL 6KRML<RVKLKLWR :DWDQDEH
'HSDUWPHQWRI&KHPLVWU\*UDGXDWH6FKRRORI6FLHQFH1DJR\D8QLYHUVLW\5HVHDUFK&HQWHUIRU0DWHULDO6FLHQFH1DJR\D8QLYHUVLW\,QWURGXFWLRQ
3HSWLGH 1XFOHLF$FLG 31$,PSURYLQJ,QYDVLRQ(IILFLHQF\
1/6FRQMXJDWHG31$ 1/631$'RXEOH'XSOH[ ,QYDVLRQ

1XFOHDU/RFDOL]DWLRQ6LJQDO1/6

1 $PLQRHWK\O JO\FLQH
EDFNERQHнн

6LQFH LW FDQ UHFRJQL]H GV'1$ GLUHFWO\ DQG VHTXHQFH
VSHFLILFDOO\31$LV DJRRG FDQGLGDWH DVDWRRO LQPROHFXODUELRORJ\ DQGLQWKH GHYHORSPHQW RIQXFOHLFDFLGPHGLFLQHV

GV'1$EHFRPHVVWDEOHXQGHUKLJKVDOWFRQFHQWUDWLRQVUHVXOWLQJLQDORZLQYDVLRQHIILFLHQF\

31$'1$GXSOH[ LV PRUHVWDEOH WKDQ GRXEOHVWUDQGHG '1$‫ܒ‬$PRUHVWDEOHLQYDVLRQFRPSOH[LVQHFHVVDU\нн+RZHYHU
31$SRVVHVVHVDQHOHFWURVWDWLFDOO\QHXWUDO EDFNERQH
1RUHSXOVLRQEHWZHHQ31$DQGWKHSKRVSKDWHJURXSVRI'1$

㻼㻺㻭

н

н

7ZR31$ VWUDQGVFDQ
‫ܢ‬LQYDGH‫ܣ‬GV'1$

н

䠇

䠇

䠇

䠇

н

E>^ͲWEE

(OHFWURVWDWLFLQWHUDFWLRQEHWZHHQ1/6DQG'1$
߮+LJKHULQYDVLRQHIILFLHQF\
ŝďĂ͕ĞƚĂů͘ŚĞŵ͘Ƶƌ͘:͘Ϯϭ͗ϰϬϮϭʹϰϬϮϲ͘

2EMHFWLYHV

0HWKRGV$PHU31$ VKRUWHUWKDQWKRVH
XVHGLQSUHYLRXVZRUNVZDVXVHG'HYHORSPHQWRIDQ1/631$WKDWVKRZVKLJKLQYDVLRQHIILFLHQF\XQGHUSK\VLRORJLFDOFRQGLWLRQV KLJKVDOWFRQFHQWUDWLRQ E\VWXG\LQJ
࢘

7KHHIIHFWRIWKHORFDWLRQRIWKH1/6⁅& RU1WHUPLQXV RQLQYDVLRQHIILFLHQF\࢙

7KHGHSHQGHQFHRILQYDVLRQHIILFLHQF\RQVDOWFRQFHQWUDWLRQ࢚

7KHHIIHFWRIDFKDQJHLQWKH1/6FRPSRVLWLRQ(5’)...ATCATCAGTAACCC...(3’)||||||||||
c-GUDGUCDUUG-nn-CDUCDGUDDC-c||||||||||(3’)...TAGTAGTCATTGGG...(5’)$ES '1$IURPWKHS%5
SODVPLGZDVXVHGDVDWDUJHW,QRUGHUWR

831$ XQPRGLILHG31$
c-KK-GUDGUCDUUG-K-nn-K-CDUCDGUDDC-KK-cϴϬ&31$ &WHUPLQDO1/6
c-VKRKKKP-GUDGUCDUUG-K-nn-K-CDUCDGUDDC-PKKKRKV-cϲϬϰϬ131$ 1WHUPLQDO1/6
c-KK-GUDGUCDUUG-VKRKKKP-nn-PKKKRKV-CDUCDGUDDC-KK-c

ϮϬ

Ϭ

ϮϬ

ϰϬ

ϲϬ

EĂůŽŶĐĞŶƚƌĂƚŝŽŶ;ŵDͿ

ϴϬ

ϭϬϬ

hͲWE

&O\V31$ $UJ ߕ/\V
c-VKKKKKP-GUDGUCDUUG-K-nn-K-CDUCDGUDDC-PKKKKKV-c

831$VKRZVDKLJKLQYDVLRQHIILFLHQF\DWILUVWEXWDPDUNHGGHFUHDVHLVREVHUYHGDWKLJKHUVDOWFRQFHQWUDWLRQV

6\QWKHVL]HGE\VROLGSKDVHSHSWLGHV\QWKHVLV

7KLVLVQRWHQRXJKIRULQYLYRDSSOLFDWLRQV࢙ &31$ VKRZVDKLJKLQYDVLRQHIILFLHQF\
HYHQDWKLJKVDOWFRQFHQWUDWLRQ,QYDVLRQ(IILFLHQF\7UHQGVї<їEĂů;ŵDͿ͗ϬϬϰϬϬϰϬϬϰϬ

131$VKRZHGDORZLQYDVLRQHIILFLHQF\
HVSHFLDOO\DWKLJKVDOWFRQFHQWUDWLRQ/ŶǀĂƐŝŽŶĨĨŝĐŝĞŶĐǇ;йͿ&RPSDULVRQEHWZHHQ131$831$&/\V31$
E
EͲWE Ͳ>ǇƐͲWE
hͲWE
KŶůǇ
ϭ Ϯϯϰϱϲϳ
ϴ

࢚ 7KHFRPSRVLWLRQRIWKH1/6DIIHFWVERWKHIILFLHQF\DQGVSHFLILFLW\&31$ DQG&/\V31$ FRPSDULVRQ ZLWK1D&OϭϬϬ

Ͳ>ǇƐͲWE
E
ͲWE
ŽŶůǇ
ϭϮϯϰϱϲϳϴϵϭϬϭϭ

ϴϬ
ϲϬ
ϰϬ

ї

ϮϬ

ї

Ϭ

Ϭ

ϮϬ

ϰϬ

ϲϬ

EĂůŽŶĐĞŶƚƌĂƚŝŽŶ;ŵDͿ
ͲWE

hͲWE

ϴϬ

ϭϬϬ

&31$ VKRZVDKLJKLQYDVLRQHIILFLHQF\DWVDOWFRQFHQWUDWLRQVDERYHP0

1/631$VFDQLQYDGHGV'1$HYHQXQGHUKLJKVDOWFRQFHQWUDWLRQV
7KHHIIHFWRIWKH1/6PRGLILFDWLRQYDULHVGUDPDWLFDOO\GHSHQGLQJRQZKLFKVLGHRIWKH31$LVPRGLILHG,QSDUWLFXODUD&WHUPLQDOPRGLILFDWLRQZDVH[WUHPHO\EHQHILFLDO
7KHGHFUHDVHLQLQYDVLRQHIILFLHQF\ZLWKKLJKHUVDOWFRQFHQWUDWLRQVZDVOHVVPDUNHGIRU&31$
,QRUGHUWRREWDLQDKLJKHULQYDVLRQHIILFLHQF\MXVWDSRVLWLYHFKDUJHLVQRWHQRXJK7KHHIILFLHQF\DQGVSHFLILFLW\YDU\GHSHQGLQJRQWKHDPLQRDFLGFRPSRVLWLRQRIWKH1/6

‫ܒ‬:LWKWKHRSWLPDOFRPSRVLWLRQDQHYHQKLJKHULQYDVLRQPLJKWEHREWDLQHG
8VLQJVXFK1/631$VDEURDGHUUDQJHRI31$DSSOLFDWLRQVLVSRVVLEOHEĂů;ŵDͿ͗ϬϭϬϮϬϯϬϰϬϬϭϬϮϬϯϬϰϬ
1RQVSHFLILF
LQYDVLRQEͲWE

&RQFOXVLRQV,QYDVLRQHIILFLHQF\ZDVHYDOXDWHGE\DVKLIWLQHOHFWURSKRUHWLFPRELOLW\

31$VXVHGLQWKLVUHVHDUFKϬ࢘ 7KH1WHUPLQDO1/6PRGLILFDWLRQLVGHWULPHQWDOIRULQYDVLRQHIILFLHQF\,QYDVLRQFRPSOH[

5HODWLRQEHWZHHQLQYDVLRQHIILFLHQF\DQGVDOWFRQFHQWUDWLRQIRU831$
E
hͲWE
ϭϬϬ
KŶůǇ

,QYDVLRQ&RQGLWLRQV
>'1$@ Q0>31$V@ Q0 HT
>+(3(6 S+ @ P0
R&IRUK

 ES '1$

5HVXOWVDQG'LVFXVVLRQ/ŶǀĂƐŝŽŶĨĨŝĐŝĞŶĐǇ;йͿ

2SWLPL]HWKH1/6PRGLILFDWLRQ
IRULQYLYRDQGLQFHOODSSOLFDWLRQVRI31$LQYDVLRQ

31$
  &31$DQG&/\V31$FRPSDULVRQ ZR1D&O⁆
E
ŽŶůǇ

ͲWE

Ͳ>ǇƐͲWEϭϮϯϰϱϲϳϴϵїїWE;ĞƋ͘Ϳ͗ϬϮϯϰϱϮϯϰϱ

,QWKHFDVHRI&/\V31$QRQVSHFLILFEDQGVDSSHDUHGZKHQWKHLQYDVLRQHIILFLHQF\ZDVKLJK

95

Improvement of Catalytic Activity of Self-sufficient Cytochrome P450
by Enzymatic Ligation○Keita Omura1, Shinya Ariyasu1, Yuichiro Aiba1, Osami Shoji1,2, Hiroshi Sugimoto2,3,
Yoshitsugu Shiro4, Yoshihito Watanabe1（ 1Nagoya Univ., 2JST-CREST, 3RIKEN SPring-8, 4Univ. of Hyogo）

NAGOYA UNIVERSITY

Aim

Introduction

 P450BM3（BM3）from Bacillus megaterium Development of metal-substituted BM3 to catalyzedifficult reactions

 Hydroxylation of fatty acids（→ C-H activation）

 Self-sufficient cytochrome P450 fused with its redox partner

2e�

Reductase domain

metalcomplex

 Enabling hydroxylation of various small organic substrates, which is not usually
recognized as substrate (benzene, cyclohexane, propane, etc.)

Cultivation,
Harvesting• O. Shoji. et al. Angew. Chem. Int. Ed. 52, 6606-6610 (2013), Z. Cong. et al. ACS Catalysis, 5, 150–156 (2015).
Decoy molecule

Non-native substrates

＝

＝

＝

Native substrate

PFC9-Trp

Strategy Reconstitution of full-length Fe-BM3

 We investigated the effect of ligation between the reductase domain andthe heme domain containing heme as cofactor

FAD
domainFMN
domainFAD
domainmetal
complexmetal
complex

BM3
1

Heme-substituted BM3

FMN
domainH2N-GG Incorporation of Mn-PPIX was confirmed by UV-vis spectra,
ICP-OES, and X-ray crystallography.

Ligation condition
heme domain
reductase domain
SortaseA
25°C for 1 h

FMNdomain

HO

Fe

N

N

N

N

O O

HO

OH

heme

Mn

propane

N

O O

OH

Mn-PPIX[metal] / µM

Abs.

[Mn]

1.0

[Fe]

0

1

wavelength / nm2

Crystal structure of Mn-substituted heme domain.

3[protein] / µM

The anomalous scattering different from Fe was observed.

 Reconstitution of Mn-substituted full-length BM3
 Catalytic activity of Mn-BM3 was
confirmed by pNCA assay.

 Ligation was confirmed by SDS-PAGE.
after

purification

Ligation condition
heme domain
reductase domain
SortaseA
4°C for 15 h

10 µM,
30 µM,
10 µM

0.40

66 kDaReductase domain(66 kDa)

45 kDaHeme domain(55 kDa)

Mn

Abs. at 410 nm

Full-length BM3(120 kDa)

0.30

Fe-BM3

0.25
0.20
0.15
0.10

Mn-BM3

0.05
Mn

0.00
0

0.5

1

1.5

2

2.5

reaction time / min

Reaction condition;
10 µL of SortaseA reaction solution, 10 µL of 10 mM pNCA, 100 µL of 1.0 mM NADPH
in O2 sat. Tris-HCl buffer (pH 8.2) at 25°C for 3 min Full-length BM3 containing Mn-PPIX (Mn-BM3) was successfully reconstituted.
 Mn-BM3 exhibited catalytic activity for pNCA

96

1

1.5

2

2.5

0

3

0.5

1

1.5

2

2.5

3

3

reaction time (min)Reaction condition;
0.1 µM of BM3, 0.05 mM of pNCA, 0.1 mM of NADPH in O2 sat. Tris-HCl buffer (pH 8.2)
at 25°C for 3 min

 BM3 did not exhibit catalytic activity
without connection between domains

 High catalytic activity of BM3
was maintained after ligation

BM3, PFC9-Trp

200

2-propanol

1-propanol

H-CH(CH3)2 : BDE = 411 kJ/mol
H-CH2C2H5 : BDE = 422 kJ/mol

50

Mn

0

 In contrast, TOF decreased.

Reaction condition;
0.5µM of BM3, 100µM of PFC9-Trp, 5mM of NADPH
in propane sat. Tris-HCl buffer at 25° for 10 min(BDE = 439 kJ/mol) extremely high C-H bond dissociation energy

High pressure reactor was developed(methane gas pressure : 0.1 MPa → 10 MPa)

4.8%

95.2%

100

 Selectivity for 1-propanol was improved.

 low solubility in water

1-propanol

2-propanol

Fe

150

Fe-BM3

Mn-BM3

17.5%

82.5%

4.8% → 17.5%
Fe

Mn

8
7
6
5
4
3
2
1
0
Fe-BM3

Fe-BM3

Mn-BM3

Mn-BM30.1MPa10MPa0.1MPa10MPa

Reaction condition;
0.5µM of BM3, 100µM of PFC9-Trp, 1mM of NADP+, 100mM glucose,
1U glucose dehydrogenase, in Tris-HCl buffer at 25°C for 10 min
under 10MPa of methane.

 TOF for methane was improved

Conclusion

0.35

200 kDa116 kDa

0.5

methane oxidation is challenging because of;y = -0.0145x + 0.0255

700

Ligated BM30

Reaction condition;
10 µL of SortaseA reaction solution, 10 µL of 10 mM pNCA, 100 µL of 1.0 mM NADPH
in O2 sat. Tris-HCl buffer (pH 8.2) at 25°C for 3 min

O2, 2e-, 2H+

0.0

600

10 µM,
10 µM,
10 µM

BM3, PFC9-Trp

Mn-BM30

WT BM30.15
0.1

 Methane oxidationy = 1.3018x - 0.3968

Fe-BM30.2

0.05

O2, 2e-, 2H+
N

ICP-OES

0.2

0.3
0.25

Result 3 | Catalytic properties of Mn-BM3

3.0

0.4

+

0

 Propane oxidation

1.2
2.0

Fe

0.1

initiation

0.35

-0.1

TON (10 min reaction)N Mn-PPIX was introduced into heme pocket.

Kawakami, N. et al. (2012).

initiation

0.2

TOF [min⁻¹]

 Apo heme domain was expressed in Fe-limiting culture.

N

0.4

0.3

reaction time / min

Result 2 | Preparation of Mn-BM3

before

0.5
0.45

Fe

0.4

0

 Introduction of Mn-protoporphyrin IX (Mn-PPIX)
into heme domain

1Reductase domain(65 kDa)
Heme domain(52 kDa)

45 kDaFAD
domainLPATGG

UV-vis spectra

Full-length BM3(117 kDa)

66 kDaSortaseA

SortaseA
PDB : 1T2P

ligation

7

pNCA

Abs. at 410 nm

LPATGG-COOH

 Sortase A recognizes the
specific peptide sequenceand catalyzes formation of
new peptide bond

PM

+

NADPH

7

1 protein marker
2 before ligation
3 after ligation

Abs. at 410 nm

116 kDa Isolated from
Staphylococcus aureus

500

3

FAD
domainSortase A recognition sequence A type of transpeptidase

400

2

200 kDa

0.5

 SortaseA300

 Catalytic activity was measured by pNCA assay (UV absorbance at 410 nm)

FMN
domainLigation with reductase domain
Heme-substituted heme domain

0.6holo heme domain

Result 1 | Effect of ligation by Sortase A Ligating heme-substituted heme domain with
reductase domain

Introduction of metal complex

apo heme domain
E. coliFe-limited culture New method for reconstitution was required

＝

＝

O

metal
complexmetal
complex

Sonication• Kawakami, N. et al. ChemBioChem 13, 2045–7 (2012).

― Fe ―

n = 8 - 16

0.8

metal-substituted heme
M = Mn, Co, Rh, etc.

 The heme domain (not full-length BM3) can be reconstituted with an artificial metal
complex (but catalytic activity is lost).

 Altering the substrate specificity by using natural substrate analog

1.4

OH

heme

 BM3 is denatured by conventional reconstitution method using acid/organic solvent.

PDB : 1BVY, 4DQK

apo heme domain

N

O O Structural complexity prevents BM3 from being reconstituted in its full-length form.
BM3 : 120 kDa (e.g. myoglobin : 18 kDa)

 Decoy system

ON No reports for heme substitution of full-length BM3

FMN domain― Fe ―

HOFe

Problem

NADPH
FAD domain

PDB : 1BVYN Oxidation of substrates which are difficult to be oxidized
like methane ( CH4
CH3OH )

Catalytic Cycle of P450s

Heme domainN Improvement of catalytic activity of hemoprotein
by substitution of central metal ( Fe
Mn, Co,..) Very high catalytic activity among P450s (16400 min-1, arachidonic acid) It was found that this reconstitution method was useful for
preparing the BM3 containing artificial metal complexes.
 Therefore, this method have potential for expanding the reaction
scope of BM3.
 Mn-BM3 exhibited catalytic activity for C-H hydroxylation.

Design of Whole-cell Biocatalyst for Aromatic Hydroxylation Utilizing
P450BM3 and Decoy Molecules
Masayuki Karasawa,1 Sota Yanagisawa,1 Osami Shoji,1,2 Yoshihito Watanabe,3
1 Dept. of Chem., Grad. Sch. of Sci., Nagoya Univ., 2 CREST, Japan Science and Technology Agency, 3 Research Center for Materials Science, Nagoya Univ.

Introduction
Cytochrome P450BM3 (P450BM3)

Substrate binding
turn the enzyme
switch “on”.

FAD

2e-

O2, 2H+

Substrate Misrecognition System

NADPH
NADP+

Decoy molecule canturn the enzyme
switch “on”.

FMN
Reductase domain
fused to the heme domain

H2O

Arg47

PDB: 1FAG

H2O

FeIII

Fatty acid• P450BM3 is a self-sufficient monooxygenase that catalyzes thehydroxylation of long-chain fatty acids at the sub-terminus.

H

H

FeIII

P450BM3O
FeIV
OH

Research Aim
Decoy
Molecule

O2, 2H+, 2e

NADPH

PFC9
1st generation• Efficient whole-cell biocatalyst for aromatic hydroxylation has been developed.

Extration with
CH2Cl2

100 mM Phosphate Buffer (pH 7.4)
Total amount 1 mL

 Whole-cell Benzene Hydroxylation
40

GC Chromatogram

30

Internal Standard(Indane)25
20
15

S-Ibu-Phe
C10-Phe
PFC9

50
40
30
20
10
0

0 10

100

200

Concentration of Decoy Molecules (µM)

without Decoy moleculewith C7-Pro-Phe

35

Phenol GC-yield (%)

GC analysis

 Time Course Experiment
C7-Pro-Phe
R-Ibu-Phe
Z-Pro-Phe

0 1

5

100

40

80

30

60

20

10

Decoy Concentration (µM)––

40
Benzene
10 mM
C7-Pro-Phe 100 µM

100

0 1 2 3 4 5 6 7 8 9 10 11 12

20
0Reaction time (h) Fluorescence Microscopy after Reaction
C7-Pro-Phe
Benzene

50

Remaining Benzene (%)

6 mL Vial

40 mM
100 µM
10 mM
1.5%

50
45
40
35
30
25
20
15
10
5
0

Phenol GC-yield (%)

pBR322 ori

E. coliBL21(DE3)

 Concentration Dependence

Reaction at
25 ºC, 200 rpm for 5 h

E. coli BL21(DE3) OD600 6.3(25 g/L Wet Cell Weight)

KanR

C7-Pro-Phe
4th generation• Decoy molecules permeates into the cell and thus activates P450BM3 expressed in the cell.

Phenol GC-yield (%)

pET28a(+)

C9-Phe
3rd generation

Heme

Summary

Results and Discussion

lacI

Tyr51

Substrate misrecognition system is a promising platform for the hydroxylation of small organic molecules.

BenzeneWhole-cell benzene hydroxylation

Glucose
Decoy Molecule
Substrate
DMSO

PDB: 3WSP

PFC9-Trp

O. Shoji et al., Angew. Chem. 2017

PFC9-Leu
2nd generation

GC-yield (%)

Can decoy molecules function as a activatorof the intracellular enzyme?

Gln73

Ala74

TOF: 259 min-1
Decoy: C7-Pro-Phe

Decoy Molecule

PhenolE. coli

Arg47

Z. Cong et al., ACS Catal. 2015

CO2

P450BM3

Crystal Structure with Decoy

Hydroxylation of non-native substrates

Reaction does not proceed without decoy molecules.

 This unique reaction system would be a potential
green alternative for current high energy-consuming
process to produce phenol.

EcoRI

·+

Active species

TOF: 256 min-1
Decoy: PFC9-Leu

NADPH: 20,000,000 yen/mol
Glucose:20 yen/mol

BamHI

FeIV

Decoy molecules
are not oxidized.

Active species

GlucoseNADP+ Hydroxylation by P450BM3 is supported with
the intracellular production of NADPH cofactor
via glucose metabolism.

Wild-type P450BM3O·+ Inert dummy substrates are misrecongnized by P450BM3 and thus control thecatalytic activities of the enzyme.

Developing the Whole-cell
Biocatalyst using Substrate
Misrecognition System

 Experimental Procedure

NADPH, O2, 2H+(2e )Substrate
Misrecognition
SystemResting state
H
H
O

P450BM3

Heme• P450BM3 shows the high substrate specificity that imposes the limitationon the practicality of the enzyme.

NADP+, H2O

FeIII

Tyr51

• P450BM3 possesses one of the highest catalytic activities among P450s.

O

FeIII

H2O NADP+, H O
2Native Reaction

Resting state

Palmitoleic acid

Decoy Molecule

NADPH, O2, 2H+
(2e )

–
+

+
–

+
+

Green:
Living Cells
Red:
Dead Cells

105

without Decoy
GC yield: 0.4%

0with C7-Pro-Phe
GC yield: 38%

P450BM3:
Expressed

scale bar: 3 µm

• Time course experiment revealed that the reaction rate of the whole-cell biotransformation of benzene isrelatively high, reaching a phenol yield of 18% after 1 h reaction.

• C7-Pro-Phe activate intracellular P450BM3 even at a low concentration of 0.5 µM.
• C7-Pro-Phe has not shown serious toxicity towards E. coli, even though it is taken into the cell.

GC yield:

PFC9(0.6%)

PFC9-PheGC yield: (1.9%)<

C9/ C10 /C11-Phe(7.9% /9.2%/ 4.4%)

Non-fluorinateddecoy molecules
were superior to
PFC series.

<

Some of decoy
moecules drasticallyenhanced the benzenehydroxylation.

Z-Pro-Phe(3.0%)(S/ R)-Ibu-Phe(38%/ 20%)

 Hydroxylation of Mono-substituted Benzenes
GC Chromatogram (Anisole)

C7-Pro-Phe(38%)• We presume that decoy molecules are selectively taken into a microbial cell depending upon the structures,

affecting the effective concentration of decoy molecules present in the cell.

Substrate(10 mM)

Product
GC-yield(%)

ortho
Selectivity(%)

Toluene (Ph-CH3)

26

97

Anisole (Ph-OCH3)

63

90

OH

without Decoy moleculewith C7-Pro-Phe
OCH3

Internal Standard We demonstrated that decoy molecules can permeate into the cell and thus
activate intracellular P450BM3.

Fluorobenzene (Ph-F)

25

64

Chlorobenzene (Ph-Cl)

1389 We succeeded in developing the efficient whole-cell biocatalyst for benzenehydroxylation, reaching a phenol yield of 38%.

 The ortho position of Mono-substituted benzenes was selectively hydroxylated by P450BM3.

In the presence of 25 mM α-cyclodextrin as a solubilizer

Without Decoy Molecule
GC yield: 15%

With C7-Pro-Phe
GC yield: 63%

97

Studies on the Heme Uptake Proteins (PhuUV-T)
from Pseudomonas aeruginosa‫( ٳ‬ULND
D6DNDNLEDUD
D ¢ ‫<؞‬XPD
D6KLVDND
D ¢‫ ؞‬2VDPLL 6KRMLL ¢ ‫؞‬+LURVKL6XJLPRWR
R ‫<؞‬RVKLKLWR:DWDQDEH
ǢŃŧƈƓƄƕƗƐƈƑƗŃƒƉŃŦƋƈƐƌƖƗƕƜŏŃŪƕƄƇƘƄƗƈŃŶƆƋƒƒƏŃƒƉŃŶƆƌƈƑƆƈŏŃűƄƊƒƜƄŃŸƑƌƙƈƕƖƌƗƜŞŃ
Ɠ
Ɯŏ
ŏ
Ɗ Ɯ
ƜŞ
ǟŃŵŬŮŨűŃŶųƕƌƑƊƊŐś ŦƈƑƗƈƕŞŞ ǠŃŵƈƖƈƄƕƆƋŃŦƈƑƗƈƕŃƉƒƕŃŰƄƗƈƕƌƄƏƖŃŶƆƌƈƑƆƈŏŃűƄƊƒƜƄŃŸƑƌƙƈƕƖƌƗƜ

,QWURGXFWLRQ

6WUDWHJ\ $LP

 ųƖƈƘƇƒƐƒƑƄƖŃƄƈƕƘƊƌƑƒƖƄ
ųƖƈƘƇƒƐƒƑƄƖ

 &U\VWDOVWUXFWXUHRI3KX7&U\VWDO VWUXFWXUH‫؞‬2SSRUWXQLVWLFEDFWHULD‫؞‬$SSHDUDQFHRIPXOWLGUXJUHVLVWDQWųőŃƄƈƕƘƊƌƑƒƖƄ
LVDFULWLFDOLVVXH‫؞‬,URQLVQHFHVVDU\IRUWKHVXUYLYDO

 +HPH DFTXLVLWLRQ

+DV$

3KX5

0HPEUDQH

$UJ
J 

,URQVRXUFHV+HPH([WUDFHOOXODU

7\U

+DV5+HPH ELQGLQJVLWH

3'%5

+HPH XSWDNHLQWRSHULSODVP
E\+DVRU3KX V\VWHP
DSR3KX7

3HULSODVP

3KX7

0HPEUDQH

3KX8&\WRSODVP+HPHV\QWKHWLFPHWDOFRPSOH[



3KX8
3KX9

7UDQVSRUWDWLRQWRF\WRSODVP
YLD3KX89 FRPSOH[

3KX8
3KX9
W
1RWUDQVSRUW

6XPPDU\%KX7%‫ق‬3%3‫ك‬
‫ق‬
3
%KX8
%
‫ق‬70'‫ك‬
‫ق‬7
%
%KX9
‫ق‬1
‫ق‬1%'‫ك‬<1DRHƈƗŃƄƏőűƄƗőŃŦƒƐƐƘƑőŃŚ

3KX7

3KX8
3KX9
1RLQWHUDFWLRQ

7UDQVSRUW

3KX98QIRUWXQDWHO\WKHPHFKDQLVPRIKHPH WUDQVSRUWKDVQRW EHHQ HOXFLGDWHG

 

3KX7&ROOHFWLRQRIIXUWKHULQIRUPDWLRQDERXWWKHKHPHWUDQVSRUWPHFKDQLVPXVLQJ3KX7 FRQWDLQLQJV\QWKHWLFPHWDOFRPSOH[HVPhuUV complex is the sole passage of heme from periplasm to cytoplasm

7KHFU\VWDOVWUXFWXUHRIDKHPH WUDQVSRUWHURUWKRORJ %KX897FRPSOH[ KDVEHHQUHSRUWHG

‫ء‬

3KX7

,QFRUSRUDWLRQLQWR3KX7

 3UHYLRXVVWXG\RQKHPH WUDQVSRUWHU

7KLVVXJJHVWVWKDWWKHKHPH LQ3KX7
FDQEHUHSODFHGZLWKDV\QWKHWLF
PHWDOFRPSOH[

 $QDO\VLVRIWKHLQWHUDFWLRQEHWZHHQ3KX7 DQG3KX89

KROR3KX7
DSR3KX77KHKHPH ELQGLQJVLWHLVH[SRVHG
WRWKHRXWVLGHRI3KX7

z :HGHYHORSHGDUHFRQVWUXFWLRQPHWKRGRI3KX7 DQGVXFFHHGHGLQLQWURGXFLQJV\QWKHWLFPHWDOFRPSOH[HV2UDQJH ‫؟‬+ROR3KX7&\DQ ‫؟‬0HVRKHPH3KX7

z 7KHVWUXFWXUHRI0HVRKHPH3KX7 ZDVGHWHUPLQHGE\;UD\FU\VWDOVWUXFWXUHDQDO\VLVƒƏƌz :HFRQVWUXFWHGWKHH[SUHVVLRQV\VWHPRI3KX9 XVLQJŨőŃƆƒƏƌ

3'%%
%%([SHULPHQW 5HVXOW 3UHSDUDWLRQRIDSR3KX7
3UHSDUDWLRQ RI DSR 3KX

 &U\VWDOVWUXFWXUHDQDO\VLV
 $IWHUWKHUHPRYDORIKHPH
DSR3KX7 ZDVREWDLQHGE\GLDO\VLV

Heme
1

2

holo-PhuT

apo-PhuT+ hemin

apo-PhuT$EV&'VSHFWURVFRS\

0Z +HPH ‫ ؟‬

DSR3KX7
holo-PhuT
holo-PhuT
apo-PhuT
apo-PhuT
apo-PhuT +hemin
hemin
apo-PhuT+

0HVRKHPH3KX7

+HPH ZDVDGGHGWRWKHVROXWLRQRIDSR3KX7(6,72)06

899LVVSHFWURVFRS\

5HVROXWLRQ‫؟‬Å



7KHDQJOHRIPHVRKHPH ZDVGLIIHUHQWIURPWKDWRIKHPH

KROR3KX7
KROR3KX7
DSR3KX7KHPLQ
DSR3KX7 KHPLQ
















:DYHOHQJWKQP

















63ULQJ%/%

:DYHOHQJWKQP

P] 3KX89 ([SUHVVLRQ&ROXPQFKDUW

0HWKRG3ODVPLGGHVLJQ

UV
1_280
Absorption
derived from protein (280 nm)$GGLWLRQRIFRPSOH[WRDSR3KX7,QVHUW

UV
2_400
Absorption
derived from complex (400 nm)

S8&3

apo-PhuT

3XULILFDWLRQE\ DQLRQH[FKDQJHFROXPQ$PS5,QVHUWTime

0HVRKHPH)H3F

ٙ 5LERVRPDOELQGLQJVLWH UEVŨőŃƆƒƏƌ
& '(Collected as Mesoheme-PhuT,QWHQVLW\'LDO\VLVRIWKHPL[WXUHWRUHPRYH'062

7KHGLIIHUHQFHRIWKHDQJOHPD\KDYH
DQHIIHFWRQKHPH WUDQVSRUW:HVXFFHHGHGLQWKHFU\VWDOVWUXFWXUHDQDO\VLVRI0HVRKHPH3KX7+HPH ZDVVXFFHVVIXOO\LQFRUSRUDWHGLQWRWKHSUHSDUHGDSR3KX7

 ,QWURGXFWLRQRIV\QWKHWLFPHWDOFRPSOH[+HPH GL20H

RULųőŃƄƈƕƘƊƌƑƒƖƄ
3$2

7KUHHSODVPLGVZHUHWUDQVIHUUHG
LQWRŨőŃƆƒƏƌ DQGųőŃƄƈƕƘƊƌƑƒƖƄ

)H733,QŨőŃƆƒƏƌ:KROHFHOO
N'D 0  

899LVVSHFWUD

399 nm

390 nm



$EV

$EV


































:DYHOHQJWKQP:DYHOHQJWKQP























:DYHOHQJWKQP:DYHOHQJWKQP(6,72)06
0Z

0Z







0Z







P]





0Z







P]









P]









P]

:HVXFFHHGHGLQWKHLQWURGXFWLRQRIV\QWKHWLFPHWDOFRPSOH[HV

98

ƓƋƘŹ

ƓƋƘŸ

ƓƋƘŹ

,QVHUW
ƓƋƘŶ

ƓƋƘŷ

ƓƋƘŸ

ƓƋƘŹ

0HPEUDQH 

LQVHUW,QųőŃƄƈƕƘƊƌƑƒƖƄ
0HPEUDQH  LQVHUW:KROHFHOO
N'D 0  









ƓƋƘŸ

,QVHUW





$EV





673 nm,QVHUW

$EV



2UDQJH‫؟‬+ROR3KX7 3'%‫؟‬5
&\DQ ‫؟‬0HVRKHPH3KX7





3KX7
N'D
3KX9
N'D



3KX7
N'D



7KHH[SUHVVLRQRI3KX9 ZDVREVHUYHGXVLQJŨőŃƆƒƏƌ DVWKHKRVWFHOO,QWKHIXWXUHZHZLOOSHUIRUPLPPXQREORWWLQJDVVD\WRVSHFLILFDOO\GHWHFW3KX8

Covalent Organic Frameworks for Electrochemical Energy Storage
Yang WU, Zhongyue ZHANG, and Kunio AWAGA*
Department of Chemistry & Integrated Research Consortium
on Chemical Sciences (IRCCS), Nagoya University
Covalent Organic Frameworks (COFs)
A class of porous crystalline polymers with periodic structures

Large Surface Area: Thousands m2/g
Designed Pore Size: Micropore (< 2 nm)
Mesopore (> 2 nm)
Lightweight Elements: C, H, B, O, N
Strong Covalent Bonds

I. Covalent Organic Framework-graft-polysulÞde (COF-graft-PS)
Synthesis

Characterization
TGA

Powder XRD

S8Δ

N2 sorption

CV

FT-IR

mp-COF

mp-COF-graft-PS

Battery tests

1 Separator 2 Gasket
3 Cathode (70 wt% COF-graft-PS, 20 wt%
carbon black and 10 wt% PVDF)
4 Positive pole (cell can)5 Anode (Lithium) 6 Negative pole

Galvanostatic discharge and chargeproÞles at a rate of 250 mA g-1

Discharge capacity values at a rate of
250 mA g-1 & 2500 mA g-1 for 15 cycles

Electrolyte: 1 M LiTFSI in DOL/DME(1:1, v/v)
with 0.2 M of LiNO3

Cycling performance at a rate of 2500 mA g-1 for 500 cycles.

II. Poly(3,4-ethylenedioxythiophene)@Covalent Organic Framework (PEDOT@COF)
Strategy

Characterization
FeCl3

PEDOT

FeCl3

EDOT

Intensity (a.u.)

EDOTTransmittance (a.u.)

Powder XRD

FT-IR

FeCl3@PI-COF

N

N

O

O

O

Li

N

O

Li

O

Synthesis

3100

O

N

TAPB

TAPB

N

N

N

O

O

O

O

O

O

N

O

O

O

O

N

O

O

FeCl3

N

N

N

N

O

O

O

O

O
O

O

O
O

O
OO

PMDA

O
O

PMDA

O

N

O

N

O

O
O

O

N

N

O

O

PI-COF

N

N

O

O

O

O
S

EDOT

O

N

O

O

N

O

O
O

O

N

N

O

O

PEDOT@PI-COF

N

N

O

-1

2800

O

20

0

0.2

30

2Theta (û)

40

50

60

200
150
100
50
N2 sorption

0
0.4

P/P0

0.6

0.8

1.0

100

O
C

700

10

250

2700

O

O

O

2900

Wavenumber (cm )

FT-IR
N

O

S

O

OO

O

N

O

+

3000

O

Weight loss (%)

O

NH2

NH2

2

O

O

Transmittance (a.u.)

O

NH2

+

H H
H
C C
O
O

H

S

NH2

H 2N H N

1000

-1

FT-IR

O

N

-2Li+,-2eCharge

PEDOT@PI-COF

2000

Wavenumber (cm )Transmittance (a.u.)

PI-COF
Electrochemical redox reaction
Discharge
OO+2Li+,+2e-

3000

Quantity Adsorbed (cm3 g-1, STP)

4000

680

660

640

-1

Wavenumber (cm )

620

O
S

80
60
40
20

C

600

0

TGA

100

200
300
400
Temperature (°C)

500

99

Impurity doping to molecule-based honeycomb
lattices of organic radicals〇1Ryo Ushiroguchi, 1Yoshiaki Shuku, 2Byeong-Kwan An, 3Ji Eon Kwon, 3Soo Young Park, 1Kunio Awaga(1Department of Chemistry, Nagoya Univ. 2Department of Chemistry, The Catholic University of Korea, 3Department of Materials Science and Engineering, Seoul National University)

Introduction

Electrochemistry of TTQPrevious work
K4 lattice by Rb3NDI - Δ

Carbon allotropes

p-BQ

p-BQ, TTQ: 1 mM
TBAClO4: 0.1 M
in MeCNp-benzoquinone (p-BQ)

replace
Graphenesp2 2D
conductor

TTQ

K4 Carbon
sp2 3D
Metallic

Diamondsp3 3D
insulator

・Electron acceptor
・Air-stable radical

A. Mizuno, Y. Shuku, R. Suizu, M.M. Matsushita, M. Tsuchiizu, D. Reta Maneru, F. Illas, V. Robert, K. Awaga, J. Am. Chem. Soc.
2015, 137, 7612-7616

Band structure, Magnetic property …

A. Mizuno, Y. Shuku, M.M. Matsushita, M. Tsuchiizu, Y Hara, N. Wada, Y. Shimizu, K. Awaga, Phys. Rev. Lett. 2017, 119, 057201.

This work① Construction of honeycomb structure
by organic radical molecularreplace

Quinones

impurity molecular

Impurity molecular

・Substitution available
・Variable functional
group

・TTQ
・TTQ : TDQ = 1:1(TDQ 50% fed)
・TTQ : TMQ = 1:1(TMQ 50% fed)

MeCN

Crystal structure?
Magnetic property?

RbClO4TMQ

TDQ

Electrochemical method
Pt wire② Find property change by doping

doping
TTQ

Sample preparation

Objective

Crystallize

・Hard to doping by atom
substitution
・Chemical modification
is not available(Trypticene Triquinone)

Radical anion of NDI - Δ Crystal structure
sp2 Carbon
K4 was successfully obtained by replacing sp2 carbon with NDI - Δ

Our interest

sp2 Carbon

π-π interaction between radicals
induce dimerization

TTQ(calculation)

M. Itoh, Phys. Rev. Lett,
2009, 102, 055703.

(Trypticene Diquinone) (Trypticene Monoquinone)

Result and discussion
Crystal structure of anion radical salt

Band calculation

High temperature EPR measurement

Honeycomb structure c

Layered structurea

TMQ 50% fed

TDQ 50% fed

TTQ
400K

400K

Increase

400K
350K

Similar

350K
300K

b

300K

TMQ 50% fed

Oor
O Benzene moiety
Quinone moietycThese moieties are randomly exist in crystal structure
Occupancy

TTQ(reference)

TDQ 50% fed

TMQ 50% fed

Quinone

0.98
0.02

0.82
0.18

0.88
0.12

Occupancy of benzene increased→ Impurities molecular seem to be introduced

100

-1

Hexagonal, P6/m(#175)
a = b = 11.65100, c = 8.67300 Å
V = 1019.59188 Å3
R1 (I > 2s(I)) = 0.0656, wR2 (all) = 0.1745, GOF = 1.227
Residual electron density in pore was removed by SQUEEZE
T = 123 K

0.7

0.6

0.5

pure TTQTMQ 50%
TDQ 50%0.4

・Extension along c axis

・Occupancy of quinone moiety

Conclusion

Graphene

Extension

Rb3TTQTDQ 50%fed

8.6575(14)8.7595(6)0%1.178%

TMQ 50%fed

8.67300

0.179%

7

pure TTQTMQ 50%
TDQ 50%

6
5
4
3
2
1
0

0.3

c axis(Å)

Intensity ∝ 1/T→(Intensity * T) = const.

Signal intensity was increased
by increasing temperature.
Relative molar intensity [TTQ(300K) = 1] / mol

Hexagonal, P6/m(#175)
Hexagonal, P6/m(#175)
a = b = 11.6708(6), c = 8.7595(6) Åa = b = 11.6406(19), c = 8.6575(14) ÅV = 1033.26(10) Å3
V = 1016.0(3) Å3
R1 (I > 2s(I)) = 0.1161, wR2 (all) = 0.3136, GOF = 1.168
R1 (I > 2s(I)) = 0.0249, wR2 (all) = 0.0621, GOF = 1.119
Residual electron density in pore was removed by SQUEEZE Residual electron density in pore was removed by SQUEEZE
T = 123 K
T = 123 K

Line width / mT

TDQ 50% fed

317.0 318.0 319.0 320.0 321.0 322.0
H / mT

317.0 318.0 319.0 320.0 321.0 322.0
H / mT

317.0 318.0 319.0 320.0 321.0 322.0
H / mT

Ideal honeycomb structure with 1D pore
Even though impurity was doped, honeycomb structure was retained.
Impurity molecules were disordered in crystal.

Benzene

350K

300K

1D poreTTQ

From curie’s law
Intensity ∝ 1/T

Rb3TTQ

300

310

320

330

340

350 360
T /K

370

380

390

300

400

Line width change→ spin environment change
Impurity added

310

320

330

360

370

380

390

400

Radical spinon quinone
Benzene ring which
work as impurity

Extension

Quinones
Inter layer force: Rb-O bondImpurity doping → Rb-O bond decrease→ c axis extension

350

T /K

Pure TTQ

Quinones
Rb

340

Molar (EPR intensity * T) increased→Number of isolated spin increased→Thermal activation

1.
2.

Isolated spin generated by addition of impurity
Weak interaction make thermal activation easier・Honeycomb lattice by TTQ and impurity molecules were prepared by electrochemical method.
・Occupancy change of quinone and benzene moiety in mixed crystal was observed
・Extension of c axis around 1% was observed in crystal structure of TDQ 50% fed.
・Thermal excitation phenomena was observed at doped crystals.
・Determination of actual ratio of TTQ and TDQ or TMQ was failed. → Future workThree-dimensional photoelectron momentum imaging of D2
in circularly polarized intense laser fields○T. Nakamura1, M. Yamamoto1, M. Fushitani1, A. Hishikawa1, 2

1Department of Chemistry, Nagoya University, 2Reserch Center of Materials Science, Nagoya University

Introduction

Results and Discussion

Chemical reaction ; Frontier orbital (FO) theory"frontier electron plays a decisive role in chemical reaction"
Nitration of naphthalene

Molecular frame three-dimensional photoelectron
momentum images

Fukui et al., J. Chem. Phys. 20, 722 (1952)

Highest occupied molecular orbital (HOMO)
More large electron density: NO2+ attacks C1 site

NO2+

D2 → D+ + D + ee-

low

All carbons havesame electron density
This selectivity can't be explained byelectronic theory

Imaging of molecular orbitals by tunneling ionization

Concentric torus-like distributions

Intense laser fields Tunneling Ionization refers to the shape of molecular orbital (MO)~1014 W/cm2
Ionization rate
Fragmented ion
large

ε
ε

xy

yz

Ground state Alnaser et al., Phys. Rev. Lett. 93, 163002 (2004).
Excited state Endo et al., Phys. Rev. Lett. 116, 163002 (2016).

low

NO → N+ + O + e-

NO 2pπe-xz

Red dashed line :p0= 0.56 a.u.

MFPAD: integral over TMD

Photoelectron transverse momentum
distribution (TMD)

Photoelectron image normal to pol. axis
two dimensional MO information

Three-dimensional photoelectron imaging !

Molecular frame photoelectron angular distribution

HOMO Staudte et al., Phys Rev. Lett. 102, 033004 (2009).
HOMO-1 Akagi et al., Science 325, 1364 (2009).

Electron momentum spectrum
Photon energy
discrete peaks

Probing 3D shape of MO by measuring TMD➢ More direct understanding of chemical reaction

This
work

p0=F/ω=0.56 a.u. for tunneling model(position and velocity =0 at tunneling)p0

Probing electron dynamics by measuring 4π str photoelectron momentum

・Construction of electron-ion three dimensional momentum imaging system
・Performance test with D2 in intense circularly polarized UV laser fields

MFPAD

Circularly polarized intense laser fields
Avoiding recollision process→conservation of initial information
Convenient rotation sweep of laser electric fields

D

Experiment

Position Sensitive Detector (PSD)
Ion side

Laboratory frame𝑥𝑥

Electrode

𝑋𝑋

𝑍𝑍

𝑒𝑒 −
D+

𝑧𝑧

𝑦𝑦

Flighttube

SQ
Windowe-

𝑌𝑌Electron-ion coincidence imaging(1)D2 → D2+ + e-(2)D2 → D+ + D + e-

Quarterwave
plate(3)D2 → D+ + D+ +2e-( )=T ( )
px
py
pz

pX
pY
pZ

β-BBO
crystal𝜃𝜃

Kinetic energy release spectrum
D+

D2+

Ellipticity
ε=0.98𝑧𝑧

PSDelectron side

Tolstikhin et al., PRA 84, 053423 (2011).

Ion momentum image

Concavemirror(f = 75 mm)

Molecular
beam D2

Elliptical distribution
NIR laser fields
tunneling regime

Molecular frameT
pX=mX/tRotation
pY=mY/tpZ=qF(t-t0) matrix

Position: ( X, Y )Time of flight: tD++

σ=0.217(2) a.u.
WFAT tunneling theory2/F)p(p⊥)∝exp(-κ p⊥→σ=0.235 a.u.
κ= 2I0
F: laser electric fields

Staudte et al., PRL 102, 033004 (2009).

Electron-ion three dimensional momentum imaging system

Flighttube

Transverse momentum spectrum

Circular distribution
UV laser fields
multiphoton regime
D

Above threshold ionization
Non-perturbative response
cf. Γ(n)=σ(n)In(2)

HP TDC (25 ps/bin)
HP timing trigger(NIM jitter~120 ps)

KER=Σ

pi 2
2mi

(3)

𝑥𝑥

800 nm,
1 kHz, 50 fs

(2)

(3)

Labeling photoelectron

Summary✓ Construction of three-dimensional momentum imaging system✓ Observation of molecular frame photoelectron tori
D2

401 nm, 70 fs
2.6×1014 W/cm2
circ. pol.

(1) D2+ + e-

(2) D+ + D + e-

(Parent ion)

(Dissociative ionization)(3) D+ + D+ + 2e- (Coulomb explosion)

Outlook：molecular orbital imaging

101

102

103

104

Synthesis of Doped Reduced Graphene Oxide
and application to batteries

Tsukasa Inoue, Haruka Omachi1, Hirofumi Yoshikawa2, Ryo Kitaura1, Yusuke Nakanishi1 and Hisanori Shinohara1
1Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya, 464-8602, Japan
2School of Science and technology, Kwansei Gakuin University, Sanda, 669-1337, Japan

Background

Doped GO
Graphene oxide (GO)Liu et al., J. Mater. Chem. C, (2013)

Kume et al., J. Mater. Chem. A. (2014)

Lawesson’s Reagent can reduce GO and dope hetero atoms into

Polyoxometalate(POM) and graphene (reduced graphene oxide ; rGO)

graphene from GO

performs as energy storage

Graphene is for coordination materialGraphene is battery active material

My work

 Measuring performance of POM/Doped GO hybrid material
 Determine how to synthesize the best Doped GO for an energy storage

Experience
doped GO synthesis

POM/GO nanohybrid materials preparation
Wash with DMF
and MeOH

THF
Under N2

*TBA3[PMo12O40] (POM)

GO

Doped GO+
Stirring
Lawesson’s Reagent Reflux

Acetonitrile
Sonication

TolueneDry*TBA : Tetrabutyl ammonium

GO

Filtering
Dry

Stirring

GO analysis

Nanohybrid Material observation

X-ray photoelectron spectroscopyO

TEM imageC

GO
Doped GOC
74
79

Atomic conc. / %
O
P
26
16
2

S
3

P

S

POM model

 GO was reduced
 Sulfur and phosphorus doped GO
was synthesized

Cycle performance measurement
PVDF 20wt%

260
66
60

CB 50wt%(mAhg-1)

GO 20wt%
POM 10wt%

Comparison of Doped GO and rGO

CapacitymAhg-1
Capacity /(mAh/g)

400

400

Capacity (mAh/g)

350

dGO/POM
rGO/POM

350

Initial capacity
After 100 cycle

300
250
200
150

Doped GO
dGO/POM
rGO
rGO/POM

100

300

50

250

0
0

10

20

30

40

50

60

Cyclenumber
numberCycle

200

EDX analysis

Battery coin cell preparation

POM
rGO
Doped GO

70

80

90

100

1 nm in diameter

1.054 nm

Doped GO/POM rGO/POM
326
368
289
242

(mAhg-1)

 Stable battery capacity was gainedby S and P doped GO/POM
nanohybrid material

C
Intensity

Initial capacity

POM/GO nanohybrid material

Mo

Cu

Energy / keV

 POM molecules were on the surface of doped GO

Future planOptimize battery performance by how synthesize Doped
GO another way

150
100
50
0
0

10

20

30

40 50 60
Cycle number

70

80

90

100

105

Semiconducting Carbon Nanotubes Extraction by Aqueous-Two Phase (ATP)System and Thin-Film-Transistor Application
Kazuki Ueno1, Haruka Omachi1,2, Tomohiko Komuro1, Jun Hirotani3, Yutaka Ohno3,4, and Hisanori Shinohara1,5
1 Graduate School of Science, 2 Research Center for Materials Science, 3 Graduate School of Engineering,

4 Institute of Materials and Systems for Sustainability, and 5Institute for Advanced Research, Nagoya University, Nagoya Japan

E-mail: omachi@chem.nagoya-u.ac.jp, noris@nagoya-u.jp

BackgroundPEG removal treatment

Single-Wall Carbon Nanotubes (SWCNTs)
CH2Cl2✓ Durable and ßexible ✓ High carrier mobility

s-SWCNT dispersion
PEG

Promising materials for electric devices
Metallic(m-) and Semiconducting(s-) due to chirality

s-SWCNT thin Þlm transistor (s-SWCNT TFT)

mixingcentrifuge

CH2Cl2s-SWCNT dispersion

1HNMR spectra (CD CN)
3

PEG-CH2Cl2 interaction

PEG peakPEG

imidazole(standard)solvent

Form emulsion

Rapid precipitation

A. M. Fréon et al., Eur. J. Pharm. Biopharm,, 73, 66-73 (2009).

Aqueous-Two Phase (ATP) System>99% of PEG was removed

TFT fabrication

MethodFabrication StepsAPTES coated Si/SiO2 substrate

s-SWCNT dispersion

s-SWCNT thin Þlm

UV spectra✓ High purity
High reproducibility

AFM observation

APTES : 3-Aminopropyl-triethoxysilane

EB deposition

CNT patterning

Source / Drain fabrication O2 plasma✓ Easy to scale up
Large scale extraction✓ Fast process

s-SWCNT thin Þlm
AFM imageHeight proÞle

15.00 nm15.00
nm

Accomplish within 30 min

5

Z[nm]

Z / nm4

Separated s-SWCNT thin Þlm

3
2
1

2.0µm

0

0

2

00.00
nmnm

Uniform 1Ð2 thin layer ÞlmPEG
surfactant

TFT characterization

channel length = 100 µm

channel length = 100 µm

2 10

Vds = -5 V

-6

-6

C-O

Vds = -0.5 V

1.5 10
D

1 10

-6

5 10

-7

0

0

1

2

3

-V

Normally on

10-I / AXPS spectra

8

-5.0V
-4.5V
-4.0V
-3.5V
-3.0V
-2.5V
-2.0V
-1.5V
-1.0V
-0.5V
0V

-6

Transfer characteristics

6

Output characteristics

Transfer characteristics
2.5 10

TFT performance with separated s-SWCNT

4

XX[µm]
/ nm

DS

4

/V

High on/off ratio >105 with normally-off state

SummaryHigh performance, but normally-on state due to p-type doping by PEG

High purity s-SWCNT was obtained by ATP system
Rapid and efÞcient removal of PEG was demonstrated

TFT performance will be improved by elimination of PEG

106

High performance with normally-off state was achieved

5

107

Synthesis and Properties of Endohedral C70 Co-Encapsulating HF and H2O Molecules
Rui Zhang, Michihisa Murata, Atsushi Wakamiya, Yasujiro Murata

Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011
Introduction

Previous Work

Doubly Encapsulating Fullerene C70

Inner Space of C60 and C70

unpublishedSaunders, M. et al., Murata, Y.; Komatsu, K. et al.,J. Am. Chem. Soc.
J. Am. Chem. Soc.
1998, 120, 6380.
2008, 130, 158000.



Murata, Y. et al.,Nat. Commun.
2013, 4, 1554/1.
Zhang, R.; Murata, Y. et al.,Nat. Chem.
2016, 8, 435.

Zhang, R.; Murata, Y. et al.,J. Am. Chem. Soc.
2014, 136, 8193.

Synthesis of Endohedralfullerene ~Molecular Surgery Methods~

This Work
Creating an
opeing

Closing an
opeing

H2@C70Komatsu, K. et al.,Science
2005, 307, 238.

H2O@C70
Murata, Y. et al.,Science2011, 333, 613.

HF@C70+

Whitby, R. J. et al.,Nat. Chem.
(doi: 10.1038/nchem.2563)

Results and Discussion

HF & H2O Insertion+

X-Ray Structure of (H2O-HF)@C70
Encapsulated H2O-HF Complex (X-ray)

0.2% expansion

refined1.39(4) Å

fixed

1.05(4) Å

2.438(2) Åsmaller

Free H2O-HF Complex (calculated)

MP2/6-311++G(3df, 3pd)

1.705 ÅX= ~0.4

0.934 Å1H NMR (500 MHz, CDCl /CS )32

2.495 Å–173 ºC, Triclinic, P-1
R1 = 0.0370, wR2 = 0.1015

NMR Measurements of HF@C70 & H2O@C70 & (H2O-HF)@C70
1

H2O: 27.1 ppm

H NMR (500 MHz, CDCl3/CS2)

HF@C70 & H2O@C70 (1:1)

HF: 25.0 ppm(JHF = 507 Hz)

Insertion Mechanism of HF & H2O (Push-and-Pull Strategy)–10“Push”“Pull” from outsideGan, L. B. et al.,Chem. Eur. J.
2015, 21, 13539.

1

–12

–14

–16

H NMR (500 MHz, CDCl3/CS2)

–18

–20
(ppm)

–22

–24

HF: 17.5 ppm(JHF = 457 Hz)+7.5 ppm(H2O-HF)@C70
No proton exchange !

–26

–28

–30

–28

–30

H2O:
25.3 ppm+1.8 ppm

effect of hydrogen bond !
–10

–12

–14

–16

–18

–20
(ppm)

–22

–24

–26

“Push”“Pull”
from inside

5 signals

9 signals !

Restoration of an Opening

Free translation and rotation

No positional exchange !

Summary
Estimated ratioa

Encapsulation ratioa

Estimated ratiob

1. Push-and-Pull strategy resulted in the formation of (H2O-HF)@C70 in high yield.

Empty C70 : 34%

Empty C70 : 31%

Empty C70 : 43%

2. HF@C70 and H2O@C70 were also obtained.

HF@C70 : 32%

HF@C70 : 34%

HF@C70H2O@C70 : 25%

H2O@C70 : 27%

H2O@C70(H2O-HF)@C70 : 9%

(H2O-HF)@C70 : 8%

(H2O-HF)@C70 : 6%a) estimated by 1H NMR.

108b) estimated by HPLC.

51% (mixture)

3. Single hydrogen bond is formed between HF and H2O in the C70 cage without
Almost no escape !

proton transfer even at 140 ºC.
4. The position of encapsulated H2O-HF complex is fixed in the C70.

Fabrication of Sn-Based Perovskite Solar Cells
Using Solvent-Coordinated SnX2 Complexes as Key Precursors(1Institute for Chemical Research, Kyoto University, 2Department of Applied Chemistry, Graduate School of Engineering, Osaka University)○Masashi Ozaki,1 Jiewei Liu,1 Yukie Katsuki,1 Taketo Handa,1 Ryosuke Nishikubo,2 Shinya Yakumaru,1 Yoshifumi Hashikawa,1
Yasujiro Murata,1 Takashi Saito,1 Yuichi Shimakawa,1 Yoshihiko Kanemitsu,1 Akinori Saeki,2 Atsushi Wakamiya1,*

Introduction

 Purification of SnI2

 Pb-Based Perovskite Solar Cells (Pb-PSCs)

CH3NH3PbI3 (MAPbI3)

0

50

Sn

Tin
MASnI3Lead
MAPbI322.7%: Pb-based PSCs
: Sn-based PSCs

25
20
15

・・

10

 Environmentally friendly✕ Low efficiency (~9.0%)✕ Low stability (Sn2+ → Sn4+)

3.8%
・

5

–529.1absence of SnI4

0

-2000

-500
-1000
-1500
Chemical shift (ppm)

8.1% PCE
in inverted structure

-2000

・・
・

Z. Liu and Z. Bian et al., Adv. Sci. 2017, 1700204.

This work Further Purification of SnI2 by Complexation

9.0%

 Examination of Inherent Electronic Structures of MASnI3 and FASnI3

・02008 2010 2012 2014 2016 2018
Year

H. J. Snaith, et al., Energy Environ. Sci. 2014, 7, 3061.
M. A. Loi et al., Adv. Energy Mater. 2017, 1702019.

SnI2

SnI2

-500
-1000
-1500
Chemical shift (ppm)

119Sn MAS NMR

M. Ozaki, Y. Murata, A. Wakamiya, et al., ACS Omega 2017, 2, 7016.

30

PCE (%)

replacePbsublimation

SnI4

SnI2

 Sn-Based Perovskite Solar Cells (Sn-PSCs)
82

SnI2

–387.7

T. Miyasaka. et al., J. Am. Chem. Soc. 2009, 131, 6050.
M. Grätzel, N. G. Park, et al., Sci. Rep. 2012, 2, 591.
H. J. Snaith, et al. Science 2012, 338, 643.
E. K. Kim, J. H. Noh, S. I. Seok, et al. Science 2017, 356, 1376.

sublimed SnI2

119Sn MAS NMR–1742.8:I–389.3: Pb–527.2

 Wide range absorption
 Solution processability
 High efficiency (~22.7%)✕ High toxicity: MA

 High PCE Sn-PSCs

commercially available SnI2
(99.9%, trace metals basis) Optimization of Fabrication Method for Sn-PSCs

Results and Discussion
 Isolation of [SnX2(S)n] Complexes (S = DMF and DMSO)

 Energy Level Diagram

Single-crystal X-ray Structures
MAPbI3

typical ETM

Energy levels (eV)
:C
:O
:N
: Sn
:I

:C
:O
:S
: Sn
:I

Monoclinic, P21/c,
R1 = 0.0183
wR2 = 0.0344[SnI2(dmf)]–4.17a–4.0

C60–4.55c

1.28

–4.5

–5.0

–4.75b
–5.45

–6.0

VB:

–3.76

–3.74

–3.90

TiO2

CB:

–3.3d

–3.49b

–4.0

Monoclinic, P21/c,
R1 = 0.0164
wR2 = 0.0379

FASnI3

MASnI3

–3.0

1.40

–4.7d
–5.02

PEDOT:
PSS

spiroOMeTAD

PTAA–5.96ca Y. Yan, et al., RSC Adv. 2016, 6, 90248. b M. G. Kanatzidis, et al., J. Phys. Chem. Lett. 2016, 7, 776.

c N. Mathews, et al., J. Mater. Chem. A 2015, 3, 14996. d M. G. Kanatzidis, et al., J. Am. Chem. Soc. 2016, 138, 14998.

[SnI2(dmso)]

–5.0

–5.1

–5.2

–5.16

–5.47atypical HTM

VBs of MASnI3 and FASnI3 are significantly higher than those of MAPbI3 or typical HTM.

 Verification of the Reported Method ref.) Z. Liu and Z. Bian et al., Adv. Sci. 2017, 1700204.
Precursor
solution
Monoclinic, P21/c
R1 = 0.0198
wR2 = 0.0486

Orthorhombic, Pnma
R1 = 0.0145
wR2 = 0.0278[Sn3I6(dmf)2][SnI2(dmso)2]

Top-view SEM

Ph-Cl dropping

Orthorhombic, P212121
R1 = 0.0343
wR2 = 0.0622[SnCl2(dmf)]
spinning

spinning

annealing

1 µm

FA0.75MA0.25SnI3

Poor coverage and low PCE by the reported method
Orthorhombic, Aba2
R1 = 0.0152
wR2 = 0.0314

Monoclinic, P21/c
R1 = 0.0176
wR2 = 0.0358[SnBr2(dmf)]

Triclinic, P-1
R1 = 0.0144
wR2 = 0.0368

 Impact of Ph-Cl Temperature[Sn2F4(dmso)2][SnBr2(dmso)2]

PCE ~3%Top-View SEM Images
65 °C

45 °C

rt

85 °C

100 °CA series of [SnX2(S)n] were developed as purified materials.

Crystalline powder
prepared from[SnI2(dmf)]
100

200
111

5

210

10

220
221

15
2 θ (°)

simulated*
222
311 320

410
400

20

25

1 µm

200
111

5

10

210

220
221

15
2 θ (°)

20––: rt––: 45 °C––: 65 °C––: 85 °C––: 100 °C

10

410
400

25

Promising material as MASnI3 and FASnI3 precursor

0.0

0.1

0.2

* M. G. Kanatzidis, et al., Inorg. Chem. 2013, 52, 9019.

1.0･: FASnI3––: MASnI3––: FASnI3
FASnI3––:
with SnF2

0.8

0.06

~1.6 eV

0.6

0.04
0.02
0.00

0.2

5.16 eV
4.0

4.5

5.0 5.5 6.0 6.5
Photon energy (eV)7.0

Summary

0.0

1.0

1.2

 Development of [SnX2(S)n] Complexes
as Purified Tin Halide Materials

1.2
1.0
0.8

~1.4 eV

0.6~1.3 eV

0.4

5.02 eV

1.4

FWHM

0.4

110 meV
160 meV
110 meV

0.2

1.4
1.6
1.8
Photon energy (eV)2.0

Current density (mA·cm-2)●: MASnI3

1.40 eV
1.28 eV
1.44 eV

Optical density

1.2
PL intensity (normalized)(Yield)1/3

0.08

PL and absorption spectra

PYS spectra

0.10

JSC
(mA·cm-2)

VOC
(V)

FF

PCE
(%)

19.04
18.80
18.77

0.47
0.49
0.51

0.62
0.59
0.69

5.50
5.40
6.62

85 °C

19.68

0.46

0.45

4.10

100 °C

16.85

0.39

0.36

0.3
0.4
Voltage (V)

0.5

2.35

0.6

 Best Performance PYS, PL and Absorption Spectra of MASnI3 and FASnI3

J–V Curves

20
15

JSC 18.9 mA·cm-2
VOC 0.53 V
FF 0.71
PCE 7.09%

10
5
0
-5

-10
-15

0

0.1

0.2

0.3

––– Forward - - - dark_F––– Reverse - - - dark_R

Voltage (V)

1 µm

rt
45 °C
65 °C

5
0

1 µm

Photovoltaic Parameters

15

simulated*
222
311 320

1 µm

J–V Curves

20

Crystalline powder
prepared from[SnI2(dmf)]
100

1 µm

FASnI3

0.4

0.5

0.6

IQE, EQE, Reflectance (%)

X-Ray Diffraction Patterns

Current density (mA·cm-2)

MASnI3

Intensity (normalized)

Intensity (normalized)

 Fabrication of MASnI3 and FASnI3 with [SnI2(dmf)]

80
70
60
50
40
30
20
10
0

IQE, EQE, Reflectance Spectra––: IQE––: EQE––: ReflectanceIntegrated JSC
18.3 mA·cm-2

300

400

500

600

700

800

Wavelength (nm)

900

1000

Cross-sectional SEM

0.0

500 nmglass-ITO / PEDOT:PSS (20 nm) / perovskite (120–200 nm) / C60 (50 nm) / BCP (8 nm) / Ag (100 nm)

 Improvement of Coverage with Hot
Ph-Cl Dropping
reported method

optimized method

1 µm

1 µm

Acknowledgement
・ SEM Images (Kyoto Univ.) by Prof. Toshiharu Teranishi, Prof.
Masanori Sakamoto, Dr. Ryota Sato, and Dr. Tokuhisa Kawawaki
・Partially Supported by ALCA

[SnI2(dmf)][SnI2(dmso)]~3% PCE

7.1% PCE

109Naphthalene Diimide-Based Electron-Transporting Layer
for Planer Perovskite Solar Cells(Institute for Chemical Research, Kyoto Univ.)◯Tomoya Nakamura, Nobutaka Shioya, Takafumi Shimoaka, Takeshi Hasegawa, Yasujiro Murata, Atsushi Wakamiya

Introduction
Molecular Orientation in Organic Electronics
OFETs

OLEDs

Electron Transport Layer for Perovskite Solar Cells
Solar cells

Previous work: TiOx as electron transport layer✕ Need of sintering at high temperature (500 °C)
unsuitable for mass production and film application

Au
Hole transport layer

ref. Wakamiya, A.; Saeki, A.; Scott, L. T. et al.
J. Am. Chem. Soc. 2015, 137, 15656.

Metal electrode
Electron transport layer
Drain

SourceSemiconductor

Emission layer

Light absorption layer

Hole transport layer

Electron transport layer
ITO
Glass

Insulator
Glass

This work: Naphthalene diimide (NDI)-based
electron transport layer

Metal electrodeHole transport layer

ITO
Glass

e–

OFETs













Perovskite

glass/ITO

NDI-C6 (R = alkyl)

NDI-H (R = H)

Edge-on orientationFace-on orientation ??
Sheet-like structure:
Intermolecular N–H···O hydrogen bonds

In-plane mobility (OFET) = 0.7 cm2 V–1 s–1

OLEDs and solar cells+

Electron transport layer✓ High electron-accepting ability✓ Transparency (absorption < 400 nm)

Molecular orientation required for good charge transport
Organic molecule–

Out-of-plane mobility (OLED & solar cells)
R = alkyl  H



e–
??


Edge-on orientationFace-on orientationref. Shukla, D. et al. Chem. Mater. 2008, 20, 7486–7491.

Results and Discussion
Molecular Orientation Analysis

p-Polarized multiple-angle incidence resolution spectrometry (pMAIRS)
NDI-H (R = H) on Si

1248

850

800

0.02

889

1084

(C–H)769 = 31°Si(100)

0.025
0.015
0.005

0.04

769

1350

0.01

1377

1581

1454

0.02

900

2AIP
AOP

(C–H)

(C–H)‐0.005

850

800

750

700

769

0.06

950

0.035

875

0

0.08

0.045

812

0.001

-0.001

0.03

IP
OP

a(C=O)

out-of-plane
direction

1099

Si(100)s(C=O)

0.1

1265

(C–H)

 = 69°short-axis
direction

1346

1659

IP (in-plane)
0.003
OP (out-of-plane)
0.002
0.004

long-axis
direction

1447

(C–H)

0800

1800 1700 1600 1500 1400 1300 1200 1100 1000

edge-on700

Two-dimensional grazing incidence X-ray diffraction (2D-GIXD)

NDI-C6 on ITO/PEIE

lamella(edge-on)
1.5

vapor
deposition

PEIE

1.0

1.0
0.5

0.5
0.0 0.5 1.0 1.5 2.0
qxy [Å–1]

NDI on ITO/PEIE

1.5qz = 2.0 Å–1d = 3.2 Å

1.0
0.5
0.0

face-on

2.0

2.0

1.5

1.5

1.0

annealing(100 °C)

0.5
0.0

0.0 0.5 1.0 1.5 2.0
qxy [Å–1]

0.0 0.5 1.0 1.5 2.0
qxy [Å–1]

HOMO & LUMO Energy levels
Experimental

 stacking(face-on)

2.0

0.0

0.0
ITO substrate

700

NDI-H on ITO/PEIE

NDI-H on Si

qz [Å–1]PEIE

qz [Å–1]

spincoatingqz [Å–1]

NDI on Si(100)lamella(edge-on)
1.5
2.0

2.0
Si(100) substrate

800

Dr. T. Koganezawa (JASRI, Spring-8 BL19B2)

NDI-C6 on Si

vapor
deposition

900

Wavenumber [cm–1]

qz [Å–1]

900

Wavenumber [cm–1]qz

01800 1700 1600 1500 1400 1300 1200 1100 1000

[Å–1]

0.04

0.005

a(C=O)

(C–H) 

1374

Absorbance (a.u.)

0.05

1709

s(C=O)

out-of-plane
direction
889

0.06

short-axis
direction  tan –1

1677

long-axis
direction

2AIP
AOP

1581

  tan –1

Absorbance (a.u.)change indipole moment

1698

NDI-C6 (R = alkyl) on Si�� stacking(face-on)

1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0
qxy [Å–1]

0.0 0.5 1.0 1.5 2.0
qxy [Å–1]

Applications to Perovskite Solar Cells
SEM imageCalculations

Au
Spiro-OMeTAD (200 nm)
MAPbI3 (460 nm)

LUMO–4.04 eV

(R = alkyl)

NDI-R
KS-LUMO–3.41 eV

NDI-H

KS-LUMO

Energy–0.15 eVblocking
VB–5.45 eV+
MAPbI3–3.56 eVHOMO

KS-HOMO

KS-HOMO–0.16 eV–7.04 eV
–7.20 eV

110

1 m

Spiro-OMeTAD

J-V characteristics
Current density [mA cm–2]

injectionCB–3.90 eV–

NDI-R

NDI-H (40 nm)
ITO

25

Au

20
15

Spiro-OMeTAD

JSC = 18.9 mA cm–2
VOC = 0.88 V
FF = 0.64
PCE = 10.7 %

10
5

+
–

0
-5

0

0.2

0.4

0.6

Voltage [V]Acknowledgement

0.8

1

MAPbI3
NDI-H
PEIE
glass/ITOThis work was partially supported by the Center of Innovation Program (COI) and Advanced Low
Carbon Technology Research and Development Program (ALCA) from Japan Science andTechnology Agency (JST).

111

112

The Role of Chloride Additives on Tin Halide Perovskite
Solar Cells and Thin Films
7RPRNR $KDUHQ 7DNHWR +DQGD $WVXVKL :DNDPL\D DQG <RVKLKLNR .DQHPLWVX,QVWLWXWH IRU &KHPLFDO 5HVHDUFK .\RWR 8QLYHUVLW\,QWURGXFWLRQ/HDG 3E EDVHGSHURYVNLWH VRODUFHOO• ,QFUHGLEOHSHUIRUPDQFHRYHUDVSRO\FU\VWDOOLQHWKLQILOPVRODUFHOO KWWSVHQHUJ\JRYHHUHVXQVKRWGRZQORDGVUHVHDUFKFHOOHIILFLHQF\UHFRUGV• +LJKHQYLURQPHQWDOLPSDFWLVDPDMRUGUDZEDFN*URXS

0DWHULDO3UHSDUDWLRQ
DQG&KDUDFWHUL]DWLRQAu

7LQ 6Q EDVHG SHURYVNLWH VRODUFHOO DVSULPDU\VXEVWLWXWLRQ• 6LPLODUFKHPLVWU\ VDPHIDPLO\ZLWK3E• ,QVWDELOLW\RI6Q ,, LVDPDMRUGUDZEDFN• $GGLWLYHUHTXLUHG8VXDOO\Spiro OMeTAD
Perovskitec-/m- TiO2
FTO




'HYLFH$UFKLWHFWXUH
VWDQGDUGFHOO.H\WRPDNH6QEDVHGVRODUFHOOVZRUNDEOHWRGDWH
6Q ,, H[FHVVDQGVRPHUHGXFLQJFRQGLWLRQ

0+.XPDUHWDO$GY0DWHU–   7]H%LQ6RQJHWDO$&6(QHUJ\/HWW
897−903 (2017)



6RIDU6Q) KDVEHHQGHPRQVWUDWHGDVHIILFLHQWDGGLWLYHEXWVWLOOJLYHVVRPHSUREOHPV DJJORPHUDWLRQHWF&RPSDFW7L2
VSUD\S\URO\VLVRQSDWWHUQHG)72
7L&O WUHDWPHQWDQGDQQHDOHGDW&0HVRSRURXV 7L2VSLQFRDWLQJ DGLOXWHG7L2 QDQRSDUWLFOH
SDVWHRQF7L2 DQGDQQHDOHG
3HURYVNLWH )$6Q,
VSLQFRDWLQJ 0SHURYVNLWH SUHFXUVRUVROXWLRQ 6Q&O DGGLWLYHLQFOXGHG DQG
DQQHDOHG
6SLUR20H7$'
VSLQFRDWLQJ6SLUR20H7$' ZLWKDGGLWLYHVLQFKORUREHQ]HQH$X– 7KHUPDOHYDSRUDWLRQ)RUFU\VWDOTXDOLW\&KORULGH &O LQFOXVLRQZRUNVIRULPSURYHPHQWRQRSWLFDOSURSHUWLHVDQGFU\VWDOOLQLW\ IRU/HDGEDVHG
VRODUFHOOV =KDQJ:HWDO1DWXUH&RPPXQ  7LGKDU<HWDO-$P&KHP6RF

)72
$X

–  :LOOLDPV67HWDO$&61DQR–  0RRUH'7HWDO-$P
&KHP6RF– → &RXOGLWEHDSSOLFDEOHIRU6Q DQDORJXHV"

6Q&O DOVRPHHWVH[FHVV6Q DQGPRGHUDWHUHGXFLQJFRQGLWLRQ
DQGRIIHUVFRPELQDWLRQZLWKSRWHQWLDOIRULPSURYHPHQWLQFU\VWDOTXDOLW\

2SWLFDO3URSHUWLHV

3/HQHUJ\IRUWKLQILOPVZLWKYDULRXV6Q&O 
UDWLR• %OXHVKLIWLQ3/HQHUJ\
IRUDOO6Q&O DGGLWLRQV→ 6OLJKW&O LQFOXVLRQFRQWULEXWLRQ "• 3DUWLFXODUO\VDPSOHV
PRUHWKDQPRO 
6Q&O DGGHGVKRZJUHDWHUEOXHVKLIWVDQG
WKHGHYLFHVEDVHGRQ
VXFKFRPSRVLWLRQ
DUHZRUNDEOH

3;5'SDWWHUQVIRU6Q) DGGHG EOXH
DQG6Q&O DGGHG UHG )$6Q, ILOPVDUHHTXLYDOHQW1RDGGLWLRQDOSKDVHVREVHUYHG

3;5'SDWWHUQVIRU6Q&O PRODGGHG
EOXH DQG6Q&O PRODGGHG UHG
1RDGGLWLRQDOSKDVHVREVHUYHG'HYLFH3HUIRUPDQFH
DQGFKDUDFWHUL]DWLRQ'HYLFHSHUIRUPDQFHZLWK'062SUHFXUVRUVROXWLRQ-VF P$FP

9RF 9

))

3&(

&O









&O









&O









&O









&O









9RF LQFUHDVHVDV&O DGGLWLRQLQFUHDVHV'HYLFHSHUIRUPDQFHZLWK'0)'062SUHFXUVRUVROXWLRQIDEULFDWHGZLWKWROXHQHGULSSLQJ%HWWHU9RF NHSWZLWKKLJKHU6Q&O DGGLWLRQ

3/OLIHWLPHIRUWKLQILOPVZLWKYDULRXV6Q&O
UDWLR
6DPSOH/LIHWLPH
QV

)



&O



&O



&O



&O



&O



/RQJHU OLIHWLPH
WKDQ6Q) DGGLWLYH

6XUIDFH6(0LPDJHV
Cl 50

1R72/GULSSLQJ

Poor coverage/DUJHJUDLQ[[Cl 30(DMF/DMSO)

72/GULSSLQJ

F 20

6XPPDU\
6Q&O DOVRZRUNVDVHIIHFWLYHDGGLWLYHDQGWKHWUHQGZDVIRXQGLQ9RF
YV 6Q&O UDWLR2SWLFDOPHDVXUHPHQWVVKRZORQJHUOLIHWLPHZLWK6Q&O 
VXSSRUWLQJSRWHQWLDOIRUFRPSDUDEOHSHUIRUPDQFHWR6Q)  DGGLWLYHYHUVLRQ'LPLQLVKLQJWKHWUDGLQJRIIEHWZHHQ-VF DQG9RF REVHUYHGLQGHYLFHSHUIRUPDQFHVHHPVZRUNLQJE\VROYHQWHQJLQHHULQJ

72/GULSSLQJ• 1RVHYHUHDJJORPHUDWLRQ
REVHUYHGIRU&O
DGGLWLRQVXUIDFH6(0 
6XUIDFHFRYHUDJHSDUWLDOO\LPSURYHGE\FKDQJLQJVROYHQW
PL[WXUH "• /DUJHUJUDLQVL]HREWDLQHG
DJJORPHUDWLRQUHGXFLQJERXQGDU\DUHD IRU&O DGGLWLRQV$FNQRZOHGJHPHQW

&5(67DQG,5&&6IRUIXQGLQJ

6KLPDNDZD /DEIRUDFFHVVWR;5'IDFLOLW\7HUDQLVKL /DEDQG0DWVXGD/DEIRUDFFHVVWR6(0113

Synthesis and structural analysis of Ag-Bi-I for solar cells
Anucha Koedtruad, Takashi Saito, Atsushi Wakamiya, and Yuichi Shimakawa
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan

Introduction

Experiments

Solar cells

Synthesis by solid state reaction

Conduction
band

Main components:
1) Solar absorber layers
2) Hole transport layers (HTL)
3) Electron transport layers (ETL)

ETL

HTL
Absorber
ETL
Glass

Absorber

Metals: Au, Ag,

Working principle:
Photons captured by absorber materials activate
electrons in valence bands to conduction bands
producing electrons and holes. The charges thenare separated: Electrons are injected into andtransported through the ETL layer to an electrode,
while positive charge holes move to the HTL layer
and a counter electrode.

AgI

BiI3

Light

Au

HTL

Raw materials were mixed andsealed in a glass (10-4 mbar)

Valenceband

A solar cell device and a working principle

Pyrex glass tube

The key properties of solar absorbers:
suitable band gap (1.1 - 1.55 eV), strong solar absorption, high charge carrier mobilities, close bandalignment with HTL and ETL, high stability and non-toxicity

610 oC, 1 day
350 oC, 5 days

Ag-Bi-I

RT

Ag-Bi-I compounds were reported to be used as solar absorbers. The compounds are stable
and non-toxicity.
- AgBiI4 (Ag0.5Bi0.5I2) and AgBi2I7 (Ag0.29Bi0.57I2) with defect spinel structures- Ag2BiI5 (Ag0.8Bi0.4I2) and Ag3BiI6 (AgBi0.33I2) with CdCl2-type structures
Problems at the current stage:- It was difficult to obtain single phase samples.
- Actual chemical compositions for the compounds were not revealed.
- Detailed crystal structures were not clarified.

CdCl2-type structure

Ag-Bi-I compounds

Materials characterization

Aims of the research- Synthesis of single phase of Ag-Bi-I compounds- Analysis the chemical compositions and crystal structures- Evaluation of physical and chemical properties
Defect spinel structure

Reference: Chem.Commun. 2017, 53, 20 – 44.

- Phase identification by XRD- Structure analysis with synchrotron XRD data
- Measurement of Valence band energy levels by photoelectron spectroscopy- Measurement of band gap by UV-Vis spectroscopy

Results and discussion
Synchrotron X-ray diffraction and structural refinement

CdCl2-typenearlysinglephase

R3m space group

The structure analysis with synchrotron X-ray
diffraction data revealed two distinct phases: thedefect spinel structure with the Fd3m space group andthe CdCl2-type structure with the R3m space group.
Atom
Bi
Ag1
I
Ag2

Defect spinel,
Fd3m space groupnearlysinglephase

Synchrotron X-ray diffraction spectra of AgxBiyI2 (x = 0.20 – 1.00 , y = 0.33 – 0.60)

Yield0.33

CdCl2-type

5

Energy gap (Eg) measurement by UV-Vis spectroscopy0

The VB levels of the defect spinel andCdCl2-type compounds are locatedbetween -6.1 – -6.3 eV

VB = -6.23 eV

4

4.5

5

5.5

6

6.5

7

Yield0.33

Defect spinel-type
100

Eg values were calculated from Taucplot (Absorbance*hν)2 vs. hν [1]Eg values of the defect spinel and CdCl2-type
compounds were located between 1.6 – 1.8
eV

VB levels of samples

20

VB = -6.12 eV

4

4.5

5

5.5

6

6.5

Compounds
Defect spinel-type Ag0.44Bi0.52I2
Ag0.35Bi0.55I2
Ag0.29Bi0.57I2
Ag0.65Bi0.45I2
CdCl2-type
Ag0.56Bi0.48I2

VB (eV)- 6.19- 6.12- 6.13- 6.26- 6.23

7

Energy (eV)
X-ray photoelectron spectra of the samples with the defect spinel and CdCl2-type structures

Conclusions

Normalized absorbance spectra (left) and Tauc plot (right)
Eg values of samples
Compounds
Ag0.44Bi0.52I2
Defect spinel
Ag0.35Bi0.55I2
Ag0.29Bi0.57I2
Ag0.65Bi0.45I2
CdCl2-type
Ag0.56Bi0.48I2

Eg (eV)
1.61
1.68
1.66
1.70
1.74

For both the defect spinel and CdCl2–type compounds, the top of thevalence bands consist of I 5p states, and the bottom of the conduction
bands consists of Bi 6p and I 5p states. [1-2]• AgxBiyI2 (x = 0.20 – 1.00 , y = 0.33 – 0.60) compounds have been prepared by solid state reaction.
• Nearly single phase compounds were obtained for samples with x = 0.29 -0.44 and y = 0.52 – 0.57 compositions for the defect spinel-type structureand x = 0.56 -0.65 and y = 0.45 – 0.48 compositions for the CdI2-type structure.
• The VB levels of defect spinel and CdCl2-type compounds are between -6.1 – -6.3 eV.
• The Eg of the compounds are between 1.6 – 1.8 eV.

114

I

Site
16c (0 0 0) Defect spinel, Fd3m space group
16c (0 0 0) Nearly single phase compositions :32e (x x x) AgxBiyI2(x = 0.29 – 0.44, y = 0.52 – 0.57)
X = 0.25264 Impurity phase : BiI3
y = 0.25264
z = 0.25264

Examples of structural refinement of samples with defect spinel and CdCl2-type structures

Valence band level (VB) measurements by photoelectron spectroscopy
10

Atom
Bi
Ag

Site
3a (0 0 0) CdCl2-type structure, R3m space group
Nearly single phase compositions :3a (0 0 0)
AgxBiyI2 (x = 0.56 – 0.65, y = 0.45 – 0.48)
6c (0 0 z)
Impurity phase : AgIz = 0.24762
3b (0 0 1/2)

References[1] Chem.Mater. 2015, 27, 7137 – 7148.
[2] Angew.Chem.Int.Ed . 2016, 5, 9586 – 9590.

DFT and AFIR Study on the Mechanism and the Origin of Enantioselectivity
in Iron-Catalyzed Cross-Coupling Reactions
Akhilesh K. Sharma†, W. M. C. Sameera§, Masayoshi Jin#, Laksmikanta Adak‡, Chiemi Okuzono‡, Takahiro Iwamoto‡,
Masako Kato§, Keiji Morokuma†* and ○Masaharu Nakamura‡*† FIFC, Kyoto University, § Hokkaido University, # Daiichi Sankyo Co., Ltd., ‡ IRCELS, ICR, Kyoto University, Uji

Introduction

Computational Methods

h Use of Fe-catalyst in different reactions is increased recently due to its non-toxic
nature and abundance.
h Recently, first Fe-catalyzed enantioselective cross-coupling reaction is developed. 1
h Mechanism of Fe-catalyzed cross-coupling reaction is of recent debate, and notproperly understood. 2

k Recently developed Artificial Force Induced Reaction (AFIR) method (implemented in
GRRM) is useful in finding approximate TSs without initial guess.3
k AFIR is very effective for finding different conformational TSs, which is necessary
while dealing with stereoselective reactions.4

Detailed
Mechanism

MC-AFIR : GRRM Program with Gaussian 09
ONIOM(B3LYP-D3:PM6-D3)/SDD(Fe), 3-21G(all atoms except Fe)
Optimization: Gaussian 09 RevisionD.01
PCMTHF/B3LYP-D3BJ/SDD(Fe,Br); 6-31+G**(O, Mg, P, Cl); 6-31G*(H, C)
Energies: PCMTHF/B3LYP-D3BJ/SDD(Fe, Br); cc-PVTZ (H, C, O, Mg, P, Cl)
Energies are in kcal/mol at 25 ͦC temperature.

Origin of
Enantioselectivity?

Proposed Mechanism

Active Species Generation

C-Cl Activation

R = Theptyl, X = Ph or Cl, PᴖP = BenzP*
Transmetalation

Comproportionation

Activation Barriers (Gibbs freeenergy) for C-Cl activation
FeI
FeII
41
32
19.8
1.5
PhPh
Cl
52
41
25.8
5.0
PhCl
Ph
52
III
38.3
Fe
ClCl
43
50.3
PhClClC-Cl
activation

C-C Coupling C-Cl activation from FeI (41Cl) is more favorable. 5

Reductive
Elimination/
C-C Coupling

Fe-C
Coordinationk Energies of Fe(I) and Fe(II) species arealmost same. 5

C-C coupling Reaction of FeII species (2PhCl) withester radical is more feasible than withFeIII. 5
 Reaction occurs through inner-spheremechanism in quartet spin state.
 >50 TSs for C-Fe and TSs for C-C
bond formation were studied though
MC-AFIR to explore enantioselectivity.
 C-C bond formation step isenantioselectivity determining.
More deformation in TS2 is
responsible for enantioselectivity.

 C-Cl activation from FeI (41Ph) is less likely, as low concentration of
Grignard reagent is maintained during reaction.
 C-Cl activation from from FeII (as proposed) will be slow due to highactivation barrier.

Free Energy Profile for Favorable
Mechanism

C-Cl
Activation

Transmetalation

C-C
coupling

Out-of-Cage

Conformations of radical and FeII used for MC-AFIR Calculation

Fe-C
coordination

In-Cage

Enantioselectivity
Enantiomeric Ratio (er)Exp. er: 90:10
Calc. er: 95:5

Major ProductMinor Product FeI/FeII/FeIII mechanism is found to be operating in Fe-Phosphine catalyzed C-C
coupling reaction. 5

Conclusion

References

h C–Cl activation occurs from iron (I) species [FeICl(BenzP*)] and not from iron(II)species.
h Radical species (S2) formed after C-Cl activation will react with Fe(II),[FeIIPhCl(BenzP*)] leading to the formation of Fe(III) and followed by C-C coupling by
reductive elimination in quartet spin state.
h The reaction of radical species with [FeIIPh2(BenzP*)] will mainly lead to biphenyl
formation, hence, slow addition of Grignard reagent is required during the reaction
h C–C bond formation is enantioselectivity determining.

(1) Jin, M.; Adak, L.; Nakamura, M. J. Am. Chem. Soc. 2015, 137, 7128.
(2) Bedford, R. B. Acc. Chem. Res. 2015, 48, 1485.
(3) Maeda, S.; Ohno, K.; Morokuma, K. Phys. Chem. Chem. Phys. 2013, 15, 3683.
(4) Sameera, W. M. C.; Hatanaka, M.; Kitanosono, T.; Kobayashi, S.; Morokuma, K. J. Am. Chem.
Soc. 2015, 137, 11085.
(5) Sharma, A. K.; Sameera, W. M. C.; Jin, M.; Adak, L.; Okuzono, C.; Iwamoto, T.; Kato, M.;
Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 2017, 139, 16117−16125.

Acknowlegment

Research Center for Computational Science and Kyoto University for Supercomputing facility.
Prof. Satoshi Maeda for the development version of the GRRM program.

115

116

117

118

119

Asymmetric Synthesis of Highly Functionalized Silacyclopentanes
Kazunobu Igawa, Daisuke Yoshihiro, Akihiro Kuroo, Yusuke Abe, Katsuhiko Tomooka
IMCE, and IRCCS, Kyushu University, Japan
BackgroundPrevious Works

Asymmetric Synthesis of Chiral Silicon Compound

Dias tereos elec tiv e 1,4-Ar migration aXclose but not the same

O

★

Si

★

C

X
OH
Ar

Si

R 3OH
acid cat.

O

R2Ar
X = NR1, O

Chiral Silicon

R1natural chiral molecules

unnatural chiral molecules

Chemical Bond Properties of C

Chemical Bond Properties of Si

C–C: 1.53 Å (80 kcal/mol)

Si–C: 1.89 Å (88 kcal/mol)

C–H: 1.09 Å (100 kcal/mol)

Si–H: 1.48 Å (90 kcal/mol)

C–O: 1.41 Å (81 kcal/mol)

Si–O: 1.63 Å (128 kcal/mol)Electronegativity of Si χSi: 1.74

Electronegativity of Si χSi: 1.74

R2

R1
R2

Si

H

R
R
up to 86% ee2) A. Nakazaki, J. Usuki, K. Tomooka, Synlett 2008, 2064.

b K. Igawa, J. Takada. T. Shimono, K. Tomooka, J. Am. Chem. Soc. 2008, 130, 1613.
c K. Igawa., D. Yoshihiro, N. Ichikawa, N. Kokan, K. Tomooka, Angew. Chem. Int. Ed. 2012, 51, 12745.

Related Report

R1

Hb

R1

base ★

O

R2
R3
up to 84% ee

O

Carbocycle Systema

–Hb

Si

HO
O

Si

a 1) K. Tomooka, A. Nakazaki, T. Nakai, J. Am. Chem. Soc. 2000, 122, 408.

This Work

R2

R1

R 3Li / L ★

Enantios elec tiv e Hy dros ily lation c
R
RH
R1cat. M ★
Si
R2
HFirst Report of Enantio-enriched Chiral Silicon Molecule: F. S. Kipping, J. Chem. Soc. 1907, 209. !
Review: Brook, M. A. Silicon in Organic, Organometallic, and Polymer Chemistry, 2000.!

R1

O

Si

Ar
OR3

R2
Ar
>99% dr

Enantios elec tiv e Nuc leophilic Subs titution b

Chiral Carbon

Si

R2

O

Si

R2

N
Li

O

Si

OH

R1

–Ha

R2

OH

R1

Si

R2

FG1
Si

THF, rt

FG 2

FG 3

NLi

Ph
Ph

86%, 89% ee
89%, 94% ee

d

N

OH

Ph

1.5 eq.

O

Si

N
H H
(+)-trans-195AOH

Silacycle Systemc

H

Me
H

b

X = 150, DBU = 1.65 eq.
X = 20, LDA = 1.0 eq., DBU = 6.0 eq.

base ★

HaN

X mol%

DBU-THF, –78 ºC

PhSi1) mCPBA
2) RLi or RMgX
3)TBHP, KH

OH

78%, 95% ee

Si

Cl
Cl

Ph

Scope and Limitation

MgBr
THF, rttBu

Grubbs 1st cat.

Si

CH2Cl2, rt

Ph

Ph

mCPBA

Si

tBu

97%

CH2Cl2, 0 ºC

tBu

Si

O +

tBu

syn, 46%

96%

Ph

O

Si

Ph
tBu

O

Si

base* 3.0 eq.
DBU 6.0 eq.
toluene, 0 ºC

Si

tBu

tBu

X-ray analysis

28%, 33% ee ( siS, S)

N

N
Li

94%, 53% ee ( siS, S)

N
Li

quant., 38% ee ( siR, R)

R2

OH
Si

R1
R2

CO2Me

1) ClCO2MePh2) Pd2(dba)3P(o-tolyl)3
NaCH(CO2Me)2tBu
82%, >98% dr

DEAD, PPh3

Ph

CO2Me

Si

O

OH

with

Si

O
R1=Ph, R2=tBu: 81%, >98% dr
R1=tBu, R2=Ph: 78%, >98% dr
R1=Me, R2=Ph: 95%, >98% dr

Oaq. NaOH
then aq. HCl

Ph

CO2H

Si

aq. HCl

O

Ph

R1
R2

O

O

82%
93% eec

BnO

Si

OH
Si

tBu

66%
>98% eec(Ar = 3,5-Me2C6H 3)

OH
Si

70%
93% eecaAbsolute configuration was determined by X-ray Analysis.

DFT Calculation

:C

Hb

:N

Ha

tBu
87%, >98% dr

: Li

–1 a

DEa = 6.5 k c al⋅ mol

:O
: Si

N

Ph

N2H4·H2O

Si
O
tBu
65%, >98% drwith HNO

RhCl(PPh3)3
DABCO

Ph

OH

then aq. HCl

tBu

Si
HO

OH

tBu

OH

Ph

61%, >98% dr
IC50: 6.4 µMa

Ph

Si

Si
tBu
93%, >98% dr

HO

OH

Ph

OH

Me

64%, >98% dr

IC50: >100 µMa

SiHO

TS1 for (SiS,S)-2b

NH2

OH
OH

51%, >98% dr

IC50: >100 µMa

a Binding inhibition activity for the specific binding of 5-HT with lysergic acid diethylamide
2B

120

quant.
93% eec

OH

tBuO

O

OH
Si

Ar

CO2H

Si

BF3·OEt2
OH

tBu

Si

Ph

83%
95% ee ( SiS,S)aquant., 91% ee ( siS, S)

quant.
87% ee ( SiS,S)a(Ar = 3,5-Me2C6H 3)

OH

Me

Ph

Si

tBu
77%, >98% dr

O
Si

tBu
49%, >98% dr

O

O

N

OH
Si

OH
Si

O

O

mCPBA

quant., 88% ee ( siS, S)

N
Li

tBu

quant.
>98% ee ( SiS,S)a

R2

OH

Ar

Si

Me

R1

toluene–DBU, 0 ºC

bChiral amine 5 mol%, PhLi 3.0 eq.
cAbsolute configuration was assigned by analogy in the sense of stereoselectivity.

Stereoselective Transformation

R1

N

Ph

N

3.0 eq.

OH

Ph

Si

93%, 84% ee b

Ph
N

O

Si

quant.
91% ee ( SiS,S)a

OH

Ph

N
Li

OH

Ph

NLi

Ph

R2

tBu

base*
N
Li

R1

anti, 39%

Enantioselect ive b-Elimination

PhOH

b N. Holub, J. Neidhöfer, S. Blechert, Org. Lett. 2005, 7, 1227. c D. Liu, S. A. Kozmin, Angew. Chem. Int. Ed. 2001, 40, 4757. d M. J.
Södergren, P. G. Andersson, J. Am. Chem. Soc. 1998, 120, 10760.

Preparation of Substrate

PhOHa 1) M. Asami, T. Suga, K. Honda, S. Inoue, Tetrahedron Lett. 1997, 38, 6425.; 2) M. Asami, J. Synth. Org. Chem., Jpn. 1996, 54, 188.

ResultstBu

OH

R

TS2 for (SiR,R)-2b

a Zero -p o in t v ib ratio n al en erg y calcu lated

at B3 LYP/6 -3 1 1 +G(d ,p ) lev el o f th eo ry .

Summary
R1
R2

Si

O

N
Li

N

R1
R2

OH
Si

up to >98% eestereoselective
transformation

R1

OH
Si

R2
OH
HO
bioactive Si★ molecule

K. Igawa, D. Yoshihiro, Y. Abe, K. Tomooka, Angew. Chem. Int. Ed. 2016, 55, 5814.
K. Igawa, A. Kuroo, D. Yoshihiro, Y. Yamanaka, K. Tomooka, Synlett 2017, 28, 2445.

9

N

N

EfÞcient Synthesis of Multi-Functionalized DACN
and Its Application

Mol2

Yuuya Kawasaki,1 Shin Aoyama,2 Takeru Kashiwagi,1 Kazunobu Igawa1,2 and Katsuhiko Tomooka1,2
1Institute for Materials Chemistry and Engineering, 2Department of Molecular and Material Sciences, Kyushu University

Background
Click Chemistrya

Evolution of Click Reaction DeviceÒClick Chemistry: Diverse Chemical Function from a Few Good ReactionsÓ

1st generation: terminal alkyne

+

Mol1

click reaction

Mol2

N3

Mol2

Mol1

Mol1

N3
8

Huisgen Reaction b+

N3[Cu] catalyst c

Mol2

N

N

Mol1

Mol2

N

Mol1

Huisgen, G. Szeimies, L. Möbius, Chem. Ber, 1967, 100, 2494.
Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67, 3057.
2) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596.

9

N Mol2

Mol2

N

Mol2

× × ○ ○ ○8

cyclooctyneNN○ △ △ △ ×Mol1

3rd generation: 4,8-diazacyclononynes (DACN)

c 1) C. W. R.

N

N

Mol2

N3

N

N
Mol1

[Cu] free

Mol1

b

Mol2

2nd generation: cyclooctyne

wide in scope, high yield, generate only inoffensive byproducts,
simple reaction condition, rapid completion, high selectivity, etc.

Mol1

Problems[Cu] catalysta H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2001.

[C
u]
ca
Bio taly
st
or
th
og
Fu
on
nc
ali
tio
ty
n
Sy
nth al D
ive
es
rs
is
Sta
ity
bil
ity

Mol1

Mol3

Mol3

N

9

N

Mol1

[Cu] freeNNN○ ○ ○ ○ ○Mol2

a R. Ni, N. Mitsuda, T. Kashiwagi, K. Igawa, K. Tomooka, Angew. Chem. Int. Ed. 2015, 54, 1190.

DACN

ResultSynthesis of DACN

Reactivity and Stability of DACN

(OC)3Co

Co(CO)3BF3·OEt2

Co2(CO)8

3 stepsynthesis

HO(OC)3Co
+

OH

X NH

Co(CO)3+(OC)3Co

Co(CO)3

X N

N Y

+
HN Y

CAN

double Nicholas reaction
HO

X N

OH
X NH

Co2(CO)8

HN Y

CAN

Ts N

N Ts

Ts N

83% (up to 3.1 g)

N Ns Ns N

a N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc. 2004, 126, 15046.

36%

b H. Stöckmann, A. A. Neves, S. Stairs, H. Ireland-Zecchini, K. M. Brindle, F. J. Leeper, Chem. Sci. 2011, 2, 932.
c R. van Geel, G. J. M. Pruijn, F. L. van Delft, W. C. Boelens, Bioconjugate Chem. 2012, 23, 392.

a K. Igawa, S. Aoyama, Y. Kawasaki, T. Kashiwagi, Y. Seto, R. Ni, N. Mitsuda, K. Tomooka, Synlett 2017, 28, 2110.

Synthesis and Reaction of DACN Peptide

HO

N
O

N
HO

O

H
N

HOOC

N FmocCollaboration with Tanaka Group in Nagoya Univ.

N3

N

Mol1

N

O

O

N
HN

O

N

N

BnN3 (1.0 eq)
MeOH (10 mM)
25 °C, 15 h

HN
HO

O

O

O

X N
N

+

O

O
S

N

prfODN1OP S– Cl
OH

Ts

N
O
OH N
O 2
O

N

N

NH

O
O
O O
O
NH

HN

N

N
N

N

O
NH2 OO
O O

O

N

N N
N

O
O
O O NH2 O N
Ts
O
O
O O

N Ts

HN

Cover Picture:
K. Tanaka et al.
Oxygen Reduction to Water by a Cofacial Dimer of Iron(III)–Porphyrin
and Iron(III)–Phthalocyanine Linked through a Highly Flexible Fourfold Rotaxane

Supported byOÒnovel electrochemical catalystÓ
N. Mihara, Y. Yamada, H. Takaya, Y. Kitagawa, S. Aoyama, K. Igawa, K. Tomooka, K. Tanaka, Chem. Eur. J. 2017, 23, 7508.

a Observed by MALDI/TOFMS.

Summary

N

N
N Ts

RNA2

RNA1

Mol1

N

9

N

Mol2

DACN
High Synthetic Efficiency
One-pot synthesis with double Nicholas approach was achieved.

O
N
H

N N
N
N

N3

N Ts

N

NH

N

RNA2

N Ts
N

N

www.chemeurj.org

O
O

O

N3
+

N

S
HN

N

N

2017-23/31

O

N

RNA1

Ts N

Ts

N

O O
O H N O
2
O
O
O O

Ts

Collaboration with Nagatsugi Group in Tohoku Univ.

N Ts

N N

NH

H
N

O

N

N

Ts N

a

O

N

H
N

O

NH2

N X

N3

N3

NH2

O

HN

N
H

O

N

NH2

N
H

N Bn
N

O

N

N

N

O

O

43% from 3

N

O

HO

O

N

H
N

HOOC

NH2

solid-phase
peptide synthesis

N Fmoc2.40 x 10 –3 M–1s–1

N Fmoc79% (up to 6.3 g)

Mol1

OR

no reaction

Tolerance for Thiolc
Tol-SH (1.0 eq, 10 mM)
25 °C in toluene
for 2 weeks

double Nicholas reaction

a

cf.

N Ts

Ts N

Thermal Stabilityb
80 °C in toluene
for 2 weeks

pyridine

BF3·OEt2

N Bn

5.50 x 10 –3 M–1s–1

N Ts

Ts N

N

8

CD3CN, 25 ºC
5 mM

N Y
DACN

one-pot
synthesisN

N3–Bn (1.0 eq)

prfODN2High Thermal Stability
No reaction was observed at 80 °C for 2 weeks.
High Bioorthogonality
No reaction was observed with thiol at 25 °C for 2 weeks.

RNAwith DBCO; K. Onizuka, F. Nagatsugi, Y. Ito, H. Abe, J. Am. Chem. Soc. 2014, 136, 7201.

High Functional Diversity
A variety of functional units were introduced to endocyclic nitrogens.

121Formation of Pseudo-symmetric Functional Molecules and Crystals by Using Chirality(IMCE, Kyushu Univ.)Shinji Kanegawa and Osamu SatoE-mail: kanegawa@cm.kyushu-u.ac.jp

Introductions

Valence Tautomerism of Homometallic [CoCo]

Electron transfer in homometallic [CoCo]O. Sato et al, J. Am. Chem. Soc. 2006,1790-179.

Symmetric vs. Asymmetric

Strategy

Based on [CoCo] complex; [(Co(rac-cth)) 2(dhbq)](PF6)3

Enantiopure Monometallic Complexes

Ref. A. Dei et al, Angew. Chem. Int. Ed.,2004, 43, 3136-3138.

Crystal Structure of [CrCo]

Identification of [CrCo]

Magnetic Properties of [CrCo]

Temperature-dependent Spectra

Homometallic [CoCo] vs. Heterometallic [CrCo]

Several Heterometallic Complexes

Magnetic Properties of [FeCo]

Summary

Ligand Substitution Effect

Magnetic Properties of [CrFe]

122

123

2EVHUYDWLRQRI+\SHUEUDQFKHG 3RO\PHU0HWDO1DQRSDUWLFOH
&RPSRVLWH0DWHULDOV
.DWVXPL&KLNDPD.HLVXNH.RMLPD<XGDL0RULPRWR
+LGHR1DJDVKLPD

1LVVDQ&KHPLFDO,QGXVWULHV/7' .\XVKX8QLYHUVLW\

3XUSRVH,QWURGXFWLRQ&ODVVLILFDWLRQRIEUDQFKHGSRO\PHUV‫؞‬6WDUSRO\PHU'HQGULWLFSRO\PHU+\SHUEUDQFKHG SRO\PHU‫& ٴ‬UHDWLRQ RI QHZ EXVLQHVV XVLQJ K\SHUEUDQFKHG
SRO\PHUV +%3 WKURXJK FROODERUDWLRQ ZLWK .\XVKX
8QLYHUVLW\+\SHUEUDQFKHG SRO\PHU +%3 ‫؟‬,UUHJXODUEUDQFKLQJDUFKLWHFWXUH3VHXGH VSKHULFDOSRO\PHUZLWKPDQ\IXQFWLRQDOJURXSV'LIIHUHQWSURSHUWLHVIURPOLQHDUDQGFURVVOLQNHG SRO\PHU

‫ٴ‬6WXGLHVRQIXQFWLRQDOL]DWLRQRI+%3‫ٴ‬$SSOLFDWLRQVRIIXQFWLRQDOL]HG+%3WRQHZPDWHULDOV&KDUDFWHULVWLFIHDWXUHVRIRXU+%3‫ٷ‬1DQRVL]HGSVHXGRVSKHULFDOVWUXFWXUHZLWK‫؞‬/RZYLVFRVLW\‫؞‬/LWWOHHQWDQJOHPHQWRISRO\PHUFKDLQV‫؞‬+LJKGLVSHUVLELOLW\ WRYDULRXVVROYHQWV‫؞‬+LJKPRELOLW\LQWKHVROLGPDWUL[‫[(ٷ‬LVWHQFHRIODUJHQXPEHURIWHUPLQDOIXQFWLRQDOJURXSVZKLFKFDQ
EHFKHPLFDOO\PRGLILHGZLWKHDVH
‫؞‬7KHIXQFWLRQDOJURXSPRGLILFDWLRQPDNHVSRVVLEOHFRQWURORISK\VLFDOSURSHUWLHVRI+%3HJFRPSDWLELOLW\DQGGLVSHUVLELOLW\‫&؞‬RQWUROFRPSDWLELOLW\DQGVROXELOLW\0HWDO +%3FRPSRVLWHV+LJKGLVSHUVLRQVWDELOLW\ E\+%3+LJKFDWDO\WLFUHDFWLYLW\RIPHWDOQDQRSDUWLFOHV‫(ٴ‬OXFLGDWLRQRIWKHVWUXFWXUHRI+%3DQG+%3PHWDOFRPSRVLWHV‫ٴ‬$SSOLFDWLRQV

6WDU3RO\PHU'HQGULF 3RO\PHU
B

B
B

n A

B
A

B

BA

BA

B
BA

BA

BA

BA
B

BA

BA

B

BA

B

BA

B
B
BA

B

B
B

B

+\SHUEUDQFKHG 3RO\PHU +%3
EDFNERUQ +%3 
SRO\VW\UHQHSRO\DFU\ODWHHWF

9LVXDOLX]DWLRQ RI+%3E\7(0$)0670DQG67(0+$$')

7(0$)0DQG670LPDJH +%367(0+$$') LPDJH PHWDO#+%3 QDQRSDUWLFOHFRPRVLWH

7(0‫؟‬7UDQVPLVVLRQ(OHFWURQ0LFURVFRSH$)0‫؟‬$WRPLF)RUFH0LFURVFRSH
670‫؟‬6FDQQLQJ7XQQHOLQJ0LFURVFRSH

67(0+$$')
6FDQQLQJ7UDQVPLVVLRQ(OHFWURQ0LFURVFRSH+LJK$QJOH$QQXODU'DUN)LHOG‫؞‬+HDY\HOHPHQWVDUHGDUNLQWKH67(0LPDJHEULJKWLQWKH67(0+$$')LPDJH‫&ڀ‬RQWUDVWSURSRUWLRQDOWRDWRPLFZHLJKW = LVREWDLQHG

7(0LPDJH$)0LPDJH SRO\VW\UHQHW\SH+%3+%3

SRO\VW\UHQHW\SH+%3

+%3

QP

VHFWLRQDQDO\VLV
0.5Pm
QP

$X

QP

$X

670LPDJH SRO\VW\UHQHW\SH+%3
SRO\DFU\ODWH W\SH+%3

QP

H[SDQVLRQ

6HFWLRQDQDO\VLV

QP

+%3

3G

QP

+%3
7(0 LPDJH+‫ق‬+,7$&+,N9[
6DPSOHV‫؞‬SRO\VW\UHQHW\SH+%3‫؞‬SRO\DFU\ODWH W\SH+%3+%3 0Zf 
VHYHUDO‫ع‬QP SVHXGRVSKHULFDOVKDSH$)0670LPDJHQDQRVFRSH ,9 9HHFR ,QVWUXPHQWV
SUREH6L $)0 :,Q 670
PRGHWDSSLQJ
6DPSOHSRO\VW\UHQHW\SH+%3
6XEVWUDWH
PLFD

3G

67(0+$$')LPDJH-(0) -(2/N9 )(VDPSOHV$XRU3G#+%3 SRO\VW\UHQHW\SH $SSOLFDWLRQRI+%3PHWDOFRPSRVLWH+%3PHWDOFRPSRVLWHV PHWDO 3W5X3GHWF DUHDSSOLFDEOHWRFDWDO\VWVIRURUJDQLFUHDFWLRQVDQGHOHFWUROHVV SODWLQJ'HYHORSPHQWRI3G#+%3 LQNXVHIXOIRULQNMHWIOH[RDQGRWKHUSULQWLQJWHFKQLTXHV(OHFWUROHVV SODWLQJ &XSDWWHUQSODWLQJ&KHPLFDOUHDFWLRQFDWDO\VW +\GURJHQHUDWLRQ UHDFWLRQHWF
HWFᶇᶌᶉᶈᶃᶒᴾᶎᶐᶇᶌᶒᶇᶌᶅ
ᶇᶌᶉᶈᶃ
ᶌᶉᶈᶃ
ᶃᶒᴾᶎᶐᶇᶌ
ᶎᶐᶇᶌ
ᶌᶒᶇᶌᶅ
ᶅ
ᵆ
ᵆᶄᶊᶃᶖᶍᶍ ᶃᶒᶁᶒᶁᵇᶂᶐᶗᶇᶌᶅ

ᶃᶊᶃᶁᶒᶐᶍᶊᶃᶑ
ᶃᶊᶃᶁᶒᶐᶍᶊᶃᶑᶑ
ᶍᶊᶃᶑᶑᶑᶑ ᶎᶎᶊᵿᶒᶇᶌᶅ
ᶎᶊᵿ
ᵆᵡᶓᵊᴾᵬᶇᴾᵬᶇ ᶃᶒᶁ
ᵬᶇᴾᶒᶁᶁᵇ1&,SURFHVV

6XPPDU\+%3 LV SRO\PHUV ZLWK XQLTXH SK\VLFDO SURSHUWLHV RI ZKLFK IHDWXUHV DUH GLIIHUHQW IURP OLQHDU SRO\PHUV
+%3 ZHOO GLVSHUVHV YDULRXV PHWDO QDQRSDUWLFOHV DQG WKH FRPSRVLWHV DUH VWDEOH HQRXJK WR LQGXVWULDO DSSOLFDWLRQV
7KH UHVXOWLQJ +%3PHWDO QDQRSDUWLFOH FRPSRVLWH PDWHULDOV FDQ EH XVHG DV WKH FDWDO\VWV IRU YDULRXV RUJDQLF UHDFWLRQV
7KH\ DUH DOVR DSSOLFDEOH WR WKH FDWDO\VWV IRU HOHFWUROHVV SODWLQJ E\ XVLQJ D YDULHW\ RI SULQWLQJ PHWKRGV
7KH HOHFWUROHVV SODWLQJ WHFKQRORJ\ KDV D SURPLVLQJ IHDWXUH IRU LQGXVWULDO DSSOLFDWLRQV WR IOH[LEOH HOHFWURQLFV124ᵿᶌᶌᶃᵿᶊᶇᶌᶅ

,QN-HWSULQWKLQJ&XSODWLQJ RQ3,ILOP/6 PPPP

Efficient and Selective Hydrogenation of Nitroarenes using Platinum Nanoparticle
Catalysts Supported by Ammonium Salts of Hyperbranched Polystyrene
Hideo Nagashima, Yuma Yamamoto, Yuki Maeda, Lei Gao, Arada Chaiyanurakkul
1Institute for Materials Chemistry and Engineering ,Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580

125

Atom Transfer Radical Polymerization by Solvent-stabilized(Me3TACN)FeX2: A Practical Access to Reusable Iron (II) Catalysts
So-Ichiro Nakanishi,1 Atsushi Tahara,2 Mitsunobu Kawamura,2 Yusuke Sunada,2 Hideo Nagashima1,2,3

1Graduate School of Engineering Sciences, Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580

2Institute for Materials Chemistry and Engineering, Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580
3CREST, Japan Science and Technology Agency (JST), Gobancho 7, Chiyoda-ku, Tokyo, 102-0076

Introduction

Previous Work : ATRP catalyzed by a series of (R3TACN)FeX2

Atom Transfer Radical Polymerization (ATRP)<Molecular Structure of [(Cyclopentyl)3TACNFeX2]>a) [R = Me] S. Niibayashi, H.
Hayakawa, R.-J. Jin, H. Naga
shima, Chem. Commun., 2007,
1855.
b) [R = iPr] M. Kawamura,
Y. Sunada, H. Kai, N. Koike, A.
Hamada, H. Hayakawa, R.-H.
Jin, H. Nagashima, Adv. Synth.
Catal., 2009, 351, 2086.
c) [R = cPen] S.-I. Nakanishi,
M. Kawamura, H. Kai, R.-H. Jin,
Y. Sunada, H. Nagashima, Chem.
Eur. J., 2014, 20, 5802.

a) Matyjaszewski, K.; Xia, J. Chem. Rev. 2001,
101, 2921; b) Kamigaito, M.; Ando, T.; Sawamoto,
M. Chem. Rev. 2001, 3689; c) Matyjaszewski, K.
Macromolecules 2012, 45, 4015.

Highly-controlled ATRP shows…
䞉Narrow Molecular Weight Distribution.
䞉Functionalization by changing
Monomer / Initiator䞉Block Copolymerization.
(Late Stage Functionalization)
Problem is …
䞉Control of Radical Density.
䞉Substrate Scope䞉Efficient Removal of Metal Residue.
䞉Reusability of the Catalysts.

This Work<R = Me: sterically small>䞉Ionic Dinuclear Complex
㽢 Substrate scope was limited
㽢 Low Reactivity (120 °C, 18h)
䖂 Easy separation of metals by MeOH

Results & Discussion (1)<R = cyclopentyl: sterically medium>䞉Both Ionic and neutral Complex
䖂 Wide Substrate scope䖂 High reactivity & stable䖂 Easy separation of M by MeOH

Synthesis of Me3TACNFeX2L complexes

Strategy : Plausible Catalytic Cycle for ATRP

Stable when R = small<FeBr2><FeCl2><Molecular structure of 6 (R=Me) and 7 (R=Ph)><VT-1H NMR of 1 in CD3CN: possibility of in situ generation of 5 (R=Me)>㼚㻜㼒㼙㼑㻙㼏㼘㻙㻤㻜㻙㼛㼢㼑㼞㼚㼕㼓㼔㼠㻙㼞㻚㼠㻙㼍㼓㼍㼕㼚㻙㻝㼚㻜㼒㼙㼑㻙㼏㼘㻙㻤㻜㻙㼛㼢㼑㼞㼚㼕㼓㼔㼠㻙㻤㻜㼐㼑㼓㼞㼑㼑㻙㻠㼚㻜㼒㼙㼑㻙㼏㼘㻙㻤㻜㻙㼛㼢㼑㼞㼚㼕㼓㼔㼠㻙㻢㻜㼐㼑㼓㼞㼑㼑㻙㻝㼚㻜㼒㼙㼑㻙㼏㼘㻙㻤㻜㻙㼛㼢㼑㼞㼚㼕㼓㼔㼠㻙㻠㻜㼐㼑㼓㼞㼑㼑㻙㻝㼙㼟㼜㼑㼏㼠㼑㼙㼜㻜

Stable when R = bulky

P21/c (#14)
R1 = 0.0572
wR2 = 0.1458

Pna21 (#33)
R1 = 0.0643
wR2 = 0.1631

Results & Discussion (2)Time (h)25Υ

Spectra E

80Υ

Spectra D

60Υ

Spectra C

40Υ

Spectra B

25Υ

Spectra A

㻼㻼㻹
㻝㻡㻜

㻝㻞㻡

㻝㻜㻜

㻣㻡

㻡㻜

㻞㻡

[2] ATRP of Styrene (St), Methyl methacrylate (MMA) and Butyl acrylate (BA)[1] ATRP of Styrene catalyzed by Fe complexes

Cat.

Fe-Br(1): 2.5710(7)Fe-Br(2): 2.5678(7)Fe-N(1) : 2.183(4)Fe-N(2) : 2.233(3)Fe-N(3) : 2.277(3)Fe-N(4) : 2.292(4)Fe-N(2): 2.250(8) Fe-Br(1): 2.5424(15)Fe-N(3): 2.287(7) Fe-Br(2): 2.6024(15)Fe-N(4): 2.274(8) Fe-N(1) : 2.251(8)Stabilized by L even when R = small

Entry

䞉Highly-reactive and highly-controlled ATRP
iron catalysts were synthesized by using
commercially-available Me3TACN ligands.
䞉Substrate scope 䞉Reusability of catalysts
䞉Removal of metal residue from polymer䞉In situ generation from FeX2 / Me3TACN /CNMe.

<R = iPr: bulky>䞉Neutral Mononuclear Complex
䖂 Wide Substrate scope䕧 High reactivity (4h) but instable㽢 Impossible to separate by MeOH

Entry Monomer

Catalyst

Cat./init./monomer

Solvent b

6 (in situ)

1 / 1 / 500

Toluene (1 / 1)12

94

51,00047,0001.32

2

6 (in situ)

1 / 1 / 1,000

Toluene (1 / 1)30

9299,00092,0001.32

3

6 (in situ)

1 / 1 / 1,500

Toluene (1 / 1)30

86133,600

129,000

1.39

4

6 (in situ)

1 / 1 / 2,000

Toluene (1 / 1)30

90

157,400

180,000

1.58

5

6 (in situ)

1 / 1 / 5,000

Toluene (1/1)

30

92

175,600

460,000

1.62

1

1 / 1 / 250

Bulk

5

90

30,00022,5001.80

75 (in situ)

1 / 1 / 250

Bulk

1.3

94

30,00023,50085 (in situ)

1 / 1 / 250

MeCN (1/0.2)

1088

24,90022,0001.32

9

4

1 / 1 / 250

Bulk

8

90

24,90022,5001.65

106 (in situ)

1 / 1 / 250

Bulk

5

92

24,40023,0001.65

116 (in situ)

0.1 / 1 / 250

MeCN (1/0.2)

1092

25,00023,0001.37

12

6 (in situ)

0.05 / 1 / 250

MeCN (1/0.2)

24

92

23,60023,0001.33

13

6 (in situ)

1 / 1 / 1000

Toluene (1 / 1)

30

86

89700

86000

1.38

4

1 / 1 / 250

Bulk

20

>95

42,00025,0002.01

15

6 (in situ)

1 / 1 / 250

MeCN (1 / 1)60

74

17,80018,5001.38

16

6 (in situ)

1 / 1 / 250

MeCN ( 1 / 0.3)

48

88

24,90022,0001.32

17

6 (in situ)

0.25 / 1 / 250

MeCN ( 1 / 0.3)

50

>95

24,90025,0001.36

18

6 (in situ)

0.125 / 1 / 250

MeCN ( 1 / 0.3)

120

92

27,90023,0001.78

Conv.(%)

Mn (exp.)

Mn (Calcd.)

Mw/Mn

1

1

18aaa

>95

21,90025,0001.30

25 (in situ)

8aaa

94

23,60023,500

1.27

3

4

28aaa

93

23,90025,0001.25

4

6 (isolated)

8aaa

94

24,60023,5001.19

56 (in situ)

8aaa

>95

24,00025,0001.20

6

6

7 (isolated)

8aaa

>95

25,10025,0001.21

77 (in situ)

8aaa

92

24,00023,0001.21

In all cases, bulk polymerization experiments were performed at 120 °C with the [catalyst]/[initiator]/[monomer] ratioof 1 : 1 : 250. The initiator used was (1-chloroethyl)benzene (entries 1 and 2) or (1-bromoethyl)benzene (entries 3–5).

(a) time vs. ln([M]0/[M]) plot of 1 and 5 (X=Cl) (b) time vs. ln([M]0/[M]) plot of 4 and 6 (X=Br)(c) conv. vs. Mn plot / vs. Mw/Mn plot of 4 and 6.

1

14

St

MMA

BA

Time (h) Conv. (%) Mn (exp.) Mn (calcd.) Mw / Mn

1.90

aPolymerizations were carried out by using methyl 2-bromoisobutylate as the initiator at 90oC. bFigures in parenthesis are the ratio of the monomer to the solvent (v / v). .

[4] Block Copolymerization of St and MMA.

[3] Removal of Catalysts and its reusability<Purification of polymer by MeOH>
Before Purification (Fe: 500ppma)

MeOH
After Purification (<0.3 ppma)a Measured by ICP-MS

Entry Monomer Recycle Time(h) Conv.(%) Mn(exp.) Mn(Calcd.) Mw / Mn
1
Stb
1st
10
>95
22,50025,000
1.21
2
2nd
10
92
23,20023,000
1.26
3
3rd
10
93
26,70023,200
1.26
1st
8
>95
22,50025,000
1.36
4
MMAc
5
2nd
8
92
25,50023,000
1.35
6
3rd
8
92
28,60023,000
1.38
1st
50
90
23,30022,500
1.33
7
BAd
8
2nd
50
>95
42,50025,0003.01
aThe catalyst used was 6 (in situ) with the initiator (1-bromo-1-phenylethane) to monomer (styrene) ratio of 1 : 250. The

reaction was performed at 120oC for 8 h. bThe residual amount of iron species in the polystyrene was determined by ICP-MS.

126[5] ATRP of St and MMA by easy preparable FeBr2 / Me3TACN / MeCN
Entry Monomer Recycle Time (h) Conv. (%) Mn (exp.) Mn (Calcd.) Mw/Mn
1
Stb
1st
10
>95
24,50025,000
1.24
2
2nd
10
89
20,40023,000
1.26
3
3rd
10
89
22,70023,200
1.24
4
MMAc
1st
8
>95
23,60025,000
1.35
5
2nd
8
90
21,50023,000
1.33
6
3rd
8
92
25,50023,0001.34

Summary
9Highly-reactive and highly-controlled ATRP iron catalysts
were synthesized by using commercially-available Me3TACN
ligands.
9ATRP of Styrene, Methyl methacrylate and Butyl acrylate
was achieved by solvent-stabilized iron complex 6.
9Reusability of catalysts
9Removal of metal residue from polymer
9Block copolymerization of St. and MMA was achieved
9In situ generation from FeX2 / Me3TACN / CNMe.
Nakanishi, S.; Kawamura, M.; Suanada, Y.; Nagashima, H.
Polymm. Chem. 2016, 7, 1037-1048. [Selected as cover]aIn all cases, the ratio of
catalyst/initiator/monomer was
0.25 : 1 : 250. bBulk polymerization
was performed at 120oC by using 1bromo-1-phenylethane as theinitiator. cSolution polymerization[MMA / MeCN = 1 : 0.2 (v/v)] wascarried out at 90oC using methyl 2bromoisobutylate as the initiator.
dSolution polymerization [BA /MeCN = 1 : 0.3 (v/v)] was carriedout at 90oC using methyl 2bromoisobutylate as the initiator.

Hydrosilylation of Alkene with Hydrosiloxanes Catalyzed by Co(0) or Fe(0)Isocyanide Complexes
Atsushi SANAGAWA,1 and Hideo NAGASHIMA*,1,2

1Institute for Materials Chemistry and Engineering and 2Graduate School of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, JapanACKNOWLEDGMENTS:
This work was conducted in collaboration with Dr. Daisuke NODA and Mr. Koji SAKUTA (Shin-Etsu Chemical Co., Ltd.) and supported by CREST, JST.

Cobalt or iron catalysts for alkene hydrosilylation

Hydrosilylation of alkenes is an important reaction for…
䐟Synthetic intermediates(ex)䐠Industrial production of organosilicon compounds

applicable to Tamao-Fleming oxidation (green), alkoxysilane (red), siloxane (blue)

Previous work
Catalytic active species ?

Efficient and convenient catalyst systems

Proposed active species forhydrosilylation catalyzed by
Fe(CO)5 or Co2(CO)8Photo credit: Shin-Etsu Chemical Co., Ltd.

Most commonly used catalyst
Earth-abundant
metal catalyst(Fe, Co…)High catalytic activity
Easy to handle

Fe(CO)5; Wrighton, M. S. et al J. Organomet.
Chem. 1977, 128, 345.
Co2(CO)8; Chalk, A. J.; Harrod, J. F. J. Am.
Chem. Soc. 1967, 89, 1640.Wrighton, M. S.
et al Inorg. Chem. 1980, 19, 3858

J. Am. Chem. Soc. 2016, 138, 2480-2483.

 Up to TON = 9700 (Fe), 1840 (Co) Modification and cross-linking of silicone polymers

High and volatile price
The lack of natural resources

Iron-catalyzed hydrosilylation of styrene with PMDS

Entry

Catalyst

1

Fe(CNAd)52

Fe(CNAd)5

 Comparison with M(OPiv)2/CNR systems (M = Co, Fe) Comparison with Co2(CO)8 or Fen(CO)m

Catalyst
loading(mol% Fe
atom)
1

Substrate scope

Yield(%)a

Temp.
(ºC)

Conv.(%)

80

a

b

c

>99

81

9

10

>99

1

50

>99(95)b<1<1

 Modification of silicone ﬂuids

3

Fe(CNAd)5

1

RT

7

7

<1

<1

 Cross-linking of silicone polymers

4

Fe(CNAd)5

0.1

50

>99

97

1

5

1

RT

9

<1

5

4

Synthesis of cobalt and iron isocyanide complexes

Fe(CNMes)5

6

Fe(CO)5

1

50

46

14

17

17

7

Fe2(CO)9

1

50

>99

30

38

32

8

Fe3(CO)12

1

50

45

13

14

14

2

a NMR yield. b Isolated yield

Fe(OPiv)2/CNAd system
Modification of silicon polymers

R = AdIR(ATR):Q(CN) =1647 (bridge),
2101, 2000, 1954 (terminal)
cm-1

Catalytic activity
Fe(CNR)5 < Fe(OPiv)2/CNR

R = AdIR(ATR):Q(CN) = 2106
cm-1

Conventional method
Reductant = Na-Hg;(Co)Woodward, P. et al. J. Chem. Soc., Chem. Commun.
1977, 256. (Fe) G. A. Stone, et al. J. Chem. Soc., Chem. Commun., 1977, 853
K Naphthalenide; Cooper, N. J. et al J. Am. Chem. Soc. 1994, 116, 8566.

Cobalt-catalyzed hydrosilylation of D-methylstyrene with PMDS

Co2(CO)8 + CNR → Co2(CNR)8; Yamamoto, Y.; Yamazaki, H. J. Organomet.
Chem. 1977, 137, C31.

Na silica gel was also applicable as a reductant.

Na silica gel; J. Am. Chem. Soc. 2005, 127, 9338
Commercially available (Aldrich)

Entry
1

Catalyst

Catalyst loading Temp.
(mol% Co atom) (ºC)
RTTime (h)24

Conv.(%) Yield(%)aCo2(CNAd)8

1

>99

>99

2

Co2(CNAd)8

0.1

80

3

>99

>99 (96)b3

Co2(CNtBu)8

0.1

80

3

>99

>99

4

Co2(CNMes)8

1

RT

24

>99

>99

5

Co2(CNMes)8

0.01

RT

48

36

36

6

Co2(CO)8

1

RT

24

>99

>99

7

Co2(CO)8

0.1

80

3

88

88

Cross-linking of silicon polymers

Proposed reaction mechanism

a NMR yield. b Isolated yield

Co(OPiv)2/CNAd system

Catalytic activity
Co2(CNR)8 > Co(OPiv)2/CNR

127

Iridium-catalyzed Syntheses of -Conjugated Enamines bearing Acceptor Units
and Their Application into Donor-Acceptor Compounds
Atsushi Tahara, Ikumi Kitahara, Hideo Nagashima
1Institute for Materials Chemistry and Engineering ,Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580

Introduction●Donor-Acceptor (D-A) compounds
Red light emission dye1 Organic EL emission material2●Previous Work : Ir-catalyzed Syntheses of aldenamines●Chemoselective Hydrosilane Reduction of Amides(1) Hydrosilane reduction of N,N-dialkylcarboxamides catalyzed by Vaska’s complex(1) Charette’s work (Hantzsch Ester)Non-linear optical material3

Donor
Acceptor●Blue shift of absorb / emission(2) Hydrosilane reduction of N,N-diarylcarboxamides●Large stokes shift

Barde, G.; Charette, A. B., J. Am. Chem. Soc. 2008, 130, 18.

●solvatochromism(2) Adolfsson’s work (Mo(CO)6 & TMDS)(1) M. Shimizu, et al., Tetrahedron Lett., 2011, 52, 4084. (2) B. Z. Tang, et al., Phys. Chem. Chem. Phys., 2015, 17, 1134.
(3) W. Rettig, et al, J. Phys. Chem. A, 2007, 111, 2035.

●-Conjugated Enamines as Donors
photoreceptor

Hole transport material

Xerography●This Work

(1) Motoyama, Y.; Aoki, M.; Takaoka, N.; Aoto, R.; Nagashima, H. Chem. Commun., 2009, 1574.
(2) Tahara, A.; Miyamoto, Y.; Aoto, R.; Shigeta, K.; Une, Y.; Sunada, Y.; Motoyama, Y.; Nagashima, H. Organometallics, 2015, 34, 4895.
F. Tinnis, A. Volkov, T. Slagbrand, H. Adolfsson, Angew. Chem. Int. Ed. 2016, 55, 4562.

(2) Mashima’s & Okuda’s work (BPh3 & PhMeSiH2)

シャープ株式会社
特開 2016-184100

J. Jankauskas, et al,
Synthetic Metals, 2008, 158, 993.

京セラドキュメント
ソリューションズ
特開 2016-31474

Results

Mukherjee, D.; Shirase, S.; Mashima, K.; Okuda, J., Angew. Chem. Int. Ed. 2016, 55, 13326.

●Hydrosilane Reduction of Amides 2a-2j catalyzed by 1a or 1b●Synthese of Amides 2 having EWG●Competitive Reduction of Amides and EWGs

(1) -Arylation of zinc amide enolates (Hartwig)

Ph-FG + Amide (2a)Conv.a0%>99%

Hama, T.; Culkin, D. A.; Hartwig, J F. J. Am. Chem, Soc., 2006, 128, 4976.

(2) Acylation of p-Bromophenylacetamide

Ketone + Amide (2a)Hama, T.; Culkin, D. A.; Hartwig, J F. J. Am. Chem, Soc., 2006, 128, 4976.

(3) Cross-coupling reaction
Yielda13%

96%

Aldehyde + Amide (2a)(4) Syntheses from Phenylacetic acids

Yielda23%

90%

Chemoselective hydrosilane reduction of amides into enamines
were achieveda Determined by 1H NMR using an anisole as an internal standard.

Properties●Photochemical Property of 3i (NO2)●Photochemical Property of 3j (Benzothiadiazole)●Photochemical Property of 3f (Ketone)< UV >< FL >< UV >< FL >< FL >< UV >

3f

3f

HexanetolueneTHF

CH2Cl2

CHCl3

TolueneTHF

CH2Cl2

TolueneTHF

CH2Cl2

CHCl3

3j

3i
3f

Summary
Syntheses of carboxamides which bears

electron-withdrawing group.
Chemoelective hydrosilane reduction ofamides were achieved to form -conjugatedenanines.
Enamines 3f, 3i, 3j showed some emission,of which quantum yield is the bestcompared with the reported molecules
特願2017-039057, KAKEN (17K17944)

128

Hexane

CHCl3

DMF＜Previous Report＞

Ff = 0.11 (in Chloroform) 1●Aplication (2) : Synthesis of D-A-D Compound

Ff = 0.53 (in Nitrobenzene) 2 Ff = 0.29 (in THF) 3●Application (1) : Syntheses of D-A Compounds with NO2
3k (in Toluene)labs = 413 nm
lFL = 550 nm
Ff = 0.64

tol

3n

labs (nm) 464

THF

465

CH2Cl2 CHCl3 DMF

462

463

467

lFL (nm) 571

605

613

602

-

0.59

0.36

0.17

0.31

0.02

FFL

Theoretical Studies of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic
Complexes bearing cis- and trans-Dicarbonyl Ligands (M = Fe, Ru, Os)
Tahara, A.;1 Hoshi, K.;1 Sunada, Y.;2 Tanaka, H.;1 Shiota, Y.;1 Yoshizawa, K.;1 Nagashima, H.1
1Institute for Materials Chemistry and Engineering, Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580
2Institute of Industrial Science, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo, 153-8505

Introduction

Syntheses of complexes 1, 2

Hydrogenation of Alkenes

Hydrogenation of Alkenes catalyzed by Fe- or Ru-(CNMes)2 Complex<Fe complex>

Dalton Trans. 2013, 16687.

<Ru complex>
Angew. Chem. Int. Ed. 2002, 41, 2008.

Bull. Chem. Soc. Jpn. 2017, 90, 616.

<complex 1, 2 showed catalytic activities toward…>
䞉 Hydrosilane reduction of carbonyl compounds
䞉Hard reaction condition (pressurized H2, high temperature, irradiation) are required䞉Mechanistic studies are difficult due to the high spin state of iron complexes

Results (1)䞉Theoretical study for the property of complex 1,
2 and catalytic cycles for alkene hydrogenation

Cat. 1

Cat. 2mol%time(h)Yield(%)

TON

mol%

time(h)Yield(%)

TON

0.25

2

>99

400

1

6

>99

100

1

1

>99

100

5

6

>99

20

1

2

>99

100

5

6

>99

20

1

6

>99

20

5

6

>99

20

5

4

>99

20

5

6

>99

20

5

6

>99

20

5

4

>99

20

5

6

20

4

5

6

5

1

Angew. Chem. Int. Ed. 2007, 46, 2578.

<well-defined Fe-complexes for alkene hydrogenation><This work>

Alkenes䞉 Hydrosilylation of alkenes
䞉 Hydrogenation of alkenes (under 1atm of H2, rt)Comparison of the Structures obtained experimentally and theoretically[Fe] X-ray

Isomerization and Ligand Exchenage

䞉Estimation of Os analogues<Condition of the calculation>
䞉For Optimization: M06 / SDD, 6-31G**
䞉For Energy Calculation: M06 / SDD, 6-311+G**/
PCM (toluene)
Measured 1H NMR of 1: –10.21 (JSi-H = 13.2 Hz)<Publications>
䞉For Fe:

Measured 1H NMR of 2: –7.33 (JSi-H = 16.8 Hz)[Fe] calc.

J. Org. Chem. 2016,
81, 10900-10911.
䞉For Ru:
Bull. Chem. Soc. Jpn.
2017, 90, 616-623.
BCSJ award

Simulated 1H NMR of 1: –10.71 (JSi-H = 12.2 Hz)

Simulated 1H NMR of 2: –5.60 (JSi-H = 16.3 Hz)

Results (2)Relative Energy Diagrams ['G, kcal/mol]

Suggested catalytic Cycles for Alkene Hydrogenation by 1, 2

Optimized structures of the intermediates for Ru[step a] H-H & Ru-Si
are in coplaner[step b] C=C & Ru-H
are in coplaner[step c] Si-H & Ru-C
are in coplaner[step a] & [step b]
occurs at same time
䞉Change of thegeometry is required

Estimation of Os analogues<Comparison of the reactivity of Fe, Ru and Os complexes toward H-H bond cleavage by Mayer bond order analyses>

䞉trans-isomer
is more stable䞉Fe & Ru : H-H bond iscleaved with the formationof C-H bond (via one TS)
䞉Os : H-H bond is cleaved
followed by the formation of
C-H bond (via two TS)

129

Synthesis of Syn-Substituted Triptycenes Using Triple-Cycloadditions ofArynes to Ynolates and their Transformations‫ۑ‬Takayuki Iwata,1 Tatsuro Yoshinaga,2 Takumi Fujiwara,2 Takuto Fukami,2 Mitsuru Shindo1
1Institute for Materials Chemistry and Engineering, Kyushu University, 2Interdisciplinary Graduate School of Engineering Sciences, Kyushu University

Introduction

Triptycene

D3h symmetry
Rigid three-dimentional molecule
Firstly synthesized by Bartlett
Usually synthesized by DA reaction
P. D. Bartlett, et al., J. Am. Chem. Soc. 1942, 64, 2649.
G. Wittig, et al., Angew. Chem. 1956, 68, 40.

Origin of regioselectivity: negative hyperconjugation

ynolate-aryne triple cycloaddition reaction

Umezu, S.; Gomes, G. B.; Yoshinaga, T.; Sakae, M.; Matsumoto, K.; Iwata, T. Alabugin, I.; Shindo, M. Angew. Chem. Int. Ed., 2017, 56, 1298.

This work

ʀVariety of silyl-substituted triptycenes were synthesized
utilizing the ynolate-aryne triple cycloaddition reaction.
ʀTransformations of the triptycenes were investigated.

Results 1. Synthesis and transformations of silyl triptycenes

R
Et
i-Pr
n-Bu
t-Bu
hexyl
Me
Me
Me

SiR’3
SiMe3 (TMS)
SiMe3 (TMS)
SiMe3 (TMS)
SiMe3 (TMS)
SiMe3 (TMS)
SiEtMe2
SiEt3 (TES)
Sit-BuMe2 (TBS)a: not obtained, b: not determined

2. Generation of triptycyne (triptycene-aryne)Conclusion

ʀ Silyl-substituted triptycenes were successfully
synthesized utilizing the ynolate-aryne triple
cycloaddition reaction even when using stericsilyl group.
ʀ Triptycynes was also successfully generated
from two types of triptycenes.

130

Future planʀTriptycyne will be applied for the ynolate-aryne triple
cycloaddition reaction.

triptycene
12%
-a
15%
-a
11%
48%
52%
50%

anthrone
-b
10%
-b
13%
-b
-b
-b
-b

Switching Photomechanical Property by Structural Transformation
Kenta Goto and Fumito Tani
Institute for Materials Chemistry and Engineering (IMCE), Kyushu University
g2k@ms.ifoc.kyushu-u.ac.jp

Introduction

Objective

X-ray structure of 2

a)
N

O

O

N

N

O
O

1

N

N

O

We suggested that the photo-mechanical motion of 1 originatedfrom the electrostatic repulsion among 1-1·-, 1·--1·-, and 1-1·-.
When we spatially separate the donor group of NR2 from theacceptor imide moiety by long alkyl chain, van der Waals force
would be dominant or interplay with electrostatic interactions.
NDI having long alkylamino chain would give an answer as to thequestion "how long we can separate the donor group of NR2 fromcore moiety.” Solution for these problems have possibilities ofcontrolling photo-mechanical motion by chemical modification.

b)
hν

dark
air

O
O
N

1·−

N

c)
N

hν

dark

O

air

Fig.1 a) Chemical structure of 1 and 1·- b) Color changeof the crystal 1 upon photo-irradiation (l = 370 nm) c)
Photomechanical motion of the crystal 1.

2 C4[1] Nath, N. K.; Panda, M. K.; Sahoo, S. C.; Naumov, P.
CrystEngComm, 2014, 16, 1850-1858.
[2] Matsunaga, Y.; Goto, K.; Kubono, K.; Sako, K.; Shinmyozu, T.
Chemistry-A European Journal, 2014, 20, 7309-7316.

C5
C6
C7
••

Materials that are capable of change their shape and size, or of
actuation by physical stimuli are of particular importance as media
for conversion energy to mechanical work. Such mechanically
responsive or actuating materials are promising candidates as
dynamically active elements providing a wide range of applications
such as artificial muscles, actuators, and electromechanical devices. If
physical stimulus is photo-irradiation, mechanical response materials
are classified into three mechanisms. One is cis-trans isomerization,
the others are ring opening and closure reactions, and cycloaddition
reactions.1
We recently found the photochemical reaction of naphthalene
diimides (NDI) having alkylamino side chains in the solid states.2
Upon irradiation of light (l = 370 nm), the compound 1 showed color
change from to yellow to black (Fig. 1b). This came from theformation of radical anion of 1 as evidenced by UV-Vis-Nir
spectroscopy. Furthermore, the crystal 1 showed photo-mechanicalmotion (Fig. 1c).

C18

O
N
O
O
N
O
O
N
O
O
N
O

O
N
O
O
N
O
O
N
O
O
N
O

O
N
O

O
N
O

Driving force of photomechanical response

NMe2
NMe2
NMe2
NMe2

C2 : Electrostatic interactions
Cn : van der Waals force andelectrostatic interactions
NMe2

Thermal analysis and structural data
CP MAS 13C NMR 400 MHz, 15 kHz

DTA rate: 5 °C·min-1

Viewed along b axis22-H

(h k l) (2 0 -3)▽ 2q = 27.8° d = 3.21 ÅAr moiety locates in this plane.
Ar moiety in the next layer is orthogonally stacked.

VT-XRD 2q: 3-25°; rate: 5 °C·min-1

Viewed along a axis

1

X-ray crystal structure of 2
(h k l) (2 0 -1)

2: C26H32N4O4, Mr = 464.56, triclinic, P-1 (no. 2),
a = 8.1678(14), b = 8.6441(12), c = 17.157(3) Å,a = 79.786(8)° b = 85.420(9)°, g = 83.726(10)°, U= 1182.7(3) Å3, Z = 2, T = 123 K, Dc = 1.304 g cm-3,µ (Mo Ka) = 0.891 cm-1, GOF = 1.135, R1 =0.0622 (I > 2(s)I), wR2 = 0.1445 (all reflections).

Structural transformation

Kinetic analysis$%

Uv-Vis spectrum: thin layer 2 (○; prep. 2000 rpm, 30 sec) and heat treated 2-H (▲; 120 °C, 10 min)B + 𝑞𝑞 →C

B ∶ Radical anion dimer
C ∶ Mixed valence species
𝑞𝑞 ∶ quencher$(

C + 𝑞𝑞 → D
𝑘𝑘.
𝜅𝜅 =
𝑘𝑘/

Structuraltransformation

Mass valance> 105 °C
H-aggregate

J-aggregate

2

2-H

Photochemical reaction
2

Immediately

2

2-H

Calculated□ 2 MV▲ 2-H MV

Photo-mechanical response
2-Hhν

Decay after
irradn. for
30 minObserved○ 2 AD◆ 2-H AD𝑞𝑞 D − 𝑞𝑞 = C + 2[D]B D − B = C + [D]d[B]= −𝑘𝑘. [B][𝑞𝑞]d𝑡𝑡dC= 𝑘𝑘. B 𝑞𝑞 − 𝑘𝑘/ C 𝑞𝑞
d𝑡𝑡
KL.
B
1
C =
1−
[B]
BD
𝜅𝜅 − 1

Reaction description

Upon
irradiation
λ = 370 nm

Reference 1■ 2q = 22.8° d = 3.89 ÅThis plane contains Ar moiety and side-chains.
The side-chains have up- and downstairs
conformations from the Ar ring.

Conditions
Irradiation: λmax = 370 nm, 30 sec, in the air

2nd irradn.

7th irradn.

8th irradn.

3 min

15 min40 mindark, airAfter 1 min

2 min

hν

Summary
The crystals of 2 were found to have the thermal transition at 105.7 °C as observed by DTA. The crystals and thin layer of 2 were fully
converted to be 2-H by heat treatment at 120 °C for 10 min. Above the transition point, 2 was completely transformed by changing theirordered structure from H-aggregate to J-aggregate. The photochemical reaction of 2 and 2-H showed that the decay process was different
between each other. Assuming the presence of a quencher, the kinetic equation was resolved. The ratio of the reaction rate (k) of 2-H
was smaller than that of 2. The delay in the decay of 2-H may reflect in photo-mechanical response. While the crystals of 2 showed
immediately mechanical response, the crystals of 2-H slowly responded bending, and sometimes swing. Using thin layered 2 and 2-H
would reveal these photo-mechanical response more clearly.

Acknowledgements
Taisuke Matsumoto (XRD, IMCE); Keiko Ideta (CP MAS NMR,
IMCE); Dr. Shinji Kanegawa & Prof. Osamu Sato (IR, IMCE);
Prof. Yoshihito Shiota & Prof. Kazunari Yoshizawa (Theoretical
Calculation, IMCE)This work was supported by a Grant-in-Aid for Scientific
Research(C) (no. 16K05699) from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.

131

Molecularly Fingerprinted Oxide Nanowires
K. Nagashima1, Y. He1, A. Inoue1, H. Yoshida2,
G. Zhang1, T. Takahashi1, S. Takeda2 and T. Yanagida1
1IMCE, Kyushu Univ. 2ISIR, Osaka Univ.

Introduction

Functional group

Breath component

Aim of this study

Conventional Sensor

Breath Analysis by Molecule Recognition Electronics
molecule
recognition sensor

RecognitionHigh

Molecularyerimprinted polymer

Aim ofthis study

Breath analysis

Various similar molecules

Healthy

Problem

Robustness
Electrical detection by interaction with functional groupLow

Oxide semiconductor
gas sensor

Blood test
Patient

Our ApproachLowt3

Nanowire discriminator
assisted sensor system

Non-invasive, Real-time, Repeatable self-diagnosis
Biomarkers in Breatht2

t1

Synthesis of molecule discriminator using
Objective
moleculary fingerprinted oxide nanowires

t1

Moleculary Fingerprinted Oxide Nanowires

t2

Breath molecules vs. Health conditiont3

Sensing

Volatile Organic Compounds (VOCs)
Over

Nanowire discriminator

872 species

Ta

J. Breath Res.8 014001 (2014)

AldehydeὉKetone
closely related to serious disease

Tb

Innovative technology toward early discover ofserious diseases & self medication!!

(Lung cancer marker)

Molecule recognition + Thermal robustness‘Molecule Recognition’ & ‘Robustness’

Fabrication of moleculary fingerprinted oxide nanowires

2. Moleculary fingerprinted oxide sol-gel coating

ZnO nanowires

Precursor polymer: Ti(OBu)4 67μL

ZnO seed layer

Benzaldehyde

Molecule selection& condensation

Key point is

Various moleculeblend

1. Hydrothermal ZnO nanowire growthTarget molecule

Tc

Experimental
Si substrate

High

No
meaning

Inherent difficulty to electrically discriminate similar molecules

step 1

rget: Benzaldehyde
Benza
Target:10mg

step 3w/o TiO2 layer

ZnO-TiOx-sol-gel nanowires

ZnO-sol-gel nanowires

important step 2

ZnO nanowires

ZnO-TiOx nanowires

Cross-sectional view

Cross-sectional view

60ºC, 1hr
Hydrolysis agent: TiCl4 10μL
Water 100ml HMTA, C6H12N4 25mM
Zinc nitrate (Zn(NO3)2·6H2O) 25mM
Polyethyleneimine (PEI), (C2H5N)n 2.5mM 95ºC, 24hrs

ZnO nanowires
Spin coat: 4000rpm, 1min
Baking:130ºC 1h→400ºC, 1hr

Solvent: 2-propanol 970μL

Target removal
400ºC

Molecule Recognition

Characterization
Top viewὉFourier transform infrared spectroscopy (FTIR)

Evaluation of Benzaldehyde adsorption

010

10

C-O

amorphous

Ti-O-Ti

TiO 010100

O-Ti-O

amorphous

5nm

ZnO

Intensity (a.u.)

Zn+Ti

ᶣ
ᶣ

100nm

15

20

25

30

100
80

ZnO dissolve

60
40
20
0

35

106

>600cycles

105
104
103

102

Target: Benzaldehyde
Thermal stress: 400ºC 5min/cycle

101
100

Retention time (min)

Zn

107

Peak area

fingerprint NW
fingerprint TF
w/o fingerprint NW
w/o fingerprint TF
no sol-gel NW
no sol-gel TF

100nm

100nm

002

NW: Nanowire TF: Thin film

Intensity (a.u.)

ZnO
0.418nm

TiO

Zn KD

Ti KD

100nm

894 Ti-O-Zn

100nm

Normalized peak area

520ppb 30min
300K

FTIR spectrum

1μm

Cycle thermal stress measurement
100

120

6.0

m/z 106

1.4

GCMS spectra

100nm

500nm

1μm

Evaluation of ‘Molecule collection ability’ & ‘Robustness’

O KD

fingerprint NW
fingerprint TF
w/o fingerprint NW
w/o fingerprint TF
no sol-gel NW
no sol-gel TF

HAADF

TiO+amorphous
amorphous

ZnO
nanowire

1μm

1μm

TiCl4 + 2H2O→TiO2 + 4HCl

STEM image-EDS mapping

1μm

Top view

ZnO nanowires dissolve withoug TiO2 layer by byproductCharacterization of Molecular Fingerprinted Oxide Nanowires

FESEM image

1μm

1μm

Top view

ὉGas chromatograph mass spectroscopy (GCMS)

Results & Discussionᶣᶣ

Cross-sectional view

ὉTransmission electron microscopy (TEM)

heating

or

CH2
CH3

Top view

2.9

TiO2 based
scaffold

1μm

1μm

ὉField emission scanning electron microscopy(FESEM)
ὉEnergy dispersive x-ray spectroscopy (EDS)

De-alcohol

0.5As-grown

Dehydration& polymerization

Cross-sectional view

Pretreatment for moleculary fingerprinted oxide nanowires

Sol-gel mechanism: metal alkoxide reaction

0.6

RF sputter
50W 0.3Pa 3min

0

200

400

600

800

1000

Number of cycles

Ti

Efficient molecule collection
by moleculary fingerprinted nanowires

0 50 100 150 200 250
Distance (nm)Excellent thermal robustness ofmolecular fingerprint

200 times (vs. no sol-gel film)

Moleculary fingerprinted layer is amorphous (ZnxTiy)O

Moleculary fingerprinted oxide nanowires with ‘Efficient molecule collection ability’Ὁ‘High thermal robustness’
Molecule Recognition from Molecule Blend

Recognition Mechanism of Molecule Fingerprint

Mol 2

C=O

Aromatic C-H

894

Interaction at C=O & Aromatic C-H
2000

1500

1000

737
610

500

60
40
20
0

Adsorption

Only non-specific adsorption

Several adsorption states
How does it recognize?

Benzaldehyde

Step2
High T desorption

8
6
4
2
0

Wavenumber (cm-1)

Absolute & partial recognition

Step1
Low T desorption

10

0.5

T2 (=T1)
Mol 2

1106

80

Molecule recognition by desorption process

0.4

T1

100

0.5

T2 (>T1)

Mol 1

1293
1455
1426 1326
1686

Non-fingerprinted Nanowires
12

0.1

400

Propanal

1.3

300

T1
Nanowire

Nanowire

Mol 1

200

Temperature (ºC)

3-methyl-2-butenal

Normalized peak area

100

Hexanal

9.6

40

TolueneFingerprinted Nanowires
120

10.7

400

Benzaldehyde

8.8

300

Temperature (ºC)

Target

100

200

m/z
/ 106

Structurally & Chemicallysimilar molecules

Before adsorption

Normalized peak area

100

1698

After adsorption

Aromatic C-C
O-C-O

/ 106
m/z

Benzaldehyde liquid

Non-fingerprinted
nanowires

Intensity (a.u.)

Intensity (a.u.)

83.1ºC40

62.5ºC

Transmittance or Absorbance (-)

309.2ºC

Fingerprinted
nanowiresMolecule blend

FTIR spectra for molecule adsorbed nanowires

78.8

Target molecule-fingerprint interaction

Toluene desorption Target desorption

Desorption profile

2 step desorption process

C=O

Aromatic
C-H

Multi-point recognition mechanism

Excellent recognition by molecule fingerprint
Structural & Chemical recognition

Benzaldehyde

TolueneBenzaldehyde

TolueneIs it possible to discriminate from toluene?

Highly reliable molecule recognition ability of moleculary fingerprinted oxide nanowires

Summary

Isolation of target molecule by controlling
desorption temperature

We successfully synthesized ‘Highly discriminable’ & ‘Thermally robust’ moleculary fingerprinted oxide nanowires
Structural & Chemical molecule recognition / Thermal robustness 400ºC >600 cycles

132

133

134

IRCCS

統合物質創製化学研究推進機構

阿波賀邦夫

エネルギー・資源研究プラットホーム〒464-8602

名古屋市千種区不老町 名古屋大学大学院理学研究科
TEL 052-789-2291 FAX 052-789-5947

中野

新反応・新触媒研究プラットホーム

環〒001-0021

北海道札幌市北区北 21 条西 10 丁目 北海道大学触媒科学研究所
TEL 011-706-9155 FAX 011-706-9156

島川祐一

マテリアル研究プラットホーム〒611-0011

京都府宇治市五ヶ庄 京都大学化学研究所附属元素科学国際研究センター
TEL 0774-38-3110 FAX 0774-38-3118

吉澤一成

ケムバイオ研究プラットホーム〒819-0395

福岡市西区元岡 744 九州大学先導物質化学研究所
TEL 092-802-2529 FAX 092-802-2528

機構事務室〒464-8602

名古屋市千種区不老町 名古屋大学物質科学国際研究センター
TEL 052-789-5907 FAX 052-789-5900

IRCCS, Integrated Research Consortium on Chemical Sciences