トポロジー変換可能な新規超分子ポリマーの合成と組織化・機能制御

• Project Area: Dynamical ordering of biomolecular systems for creation of integrated functions
• Project/Area Number: 26102512
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 高田 十志和 東京工業大学, 理工学研究科, 教授 (40179445)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2015: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: トポロジー変換 / ロタキサン / スターポリマー / 環状ポリマー / ミクロ相分離 / 高分子ロタキサン / 超分子化学 / 高分子化学

Outline of Annual Research Achievements

高分子では高分子鎖全体の形状（トポロジー）の違いによって物性が変化することが知られているが、同一の分子でこれらの構造を相互変換するものは知られていない。本研究では、ロタキサン構造を複数の高分子鎖の連結点に組み込み、その可動な連結点の特徴を活かして高分子のトポロジーが自在に変換できるユニークなシステムの創製を目指した。その結果、(1)腕鎖本数変換式スターポリマーの合成とそのトポロジー変換、(2)動的な結合点による線状-環状トポロジー変換を達成した。
(1)腕鎖本数変換式スターポリマーの合成
空間結合を連結点に有するスターポリマーを合成し、グラフト鎖が連結している輪成分の位置をコア周辺から軸末端へと移動させることで6本の腕鎖から3本の腕鎖へと腕鎖の本数と長さを変換・制御した。
(2)動的な結合点による線状-環状トポロジー変換
[1]ロタキサン構造を高分子の末端に導入した高分子[1]ロタキサンを合成した。さらに輪成分の位置を反対の末端へと制御することで線状-環状トポロジー変換を達成した。
本研究では、微少なロタキサン部位のスイッチがミクロ相分離構造やミセル形成などの集合体形成を変換・制御できる動的秩序形成システムを構築することに成功した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Synthesis of Macromolecular [2]Rotaxanes and their Component Mobility-Dependent Properties (2016)
  • Author(s): Z. Chen, D. Aoki, S. Uchida, H, Marubayashi, S, Nojima, T. Takata
  • Journal Title: Angew. Chem., Int. Ed. Volume: 55 Issue: 8 Pages: 2778-2781
  • DOI: 10.1002/anie.201510953
  • Peer Reviewed
• [Journal Article] Structural Analysis and Inclusion Mechanism of Native and Permethylated α-Cyclodextrin-Based Rotaxanes Containing Alkylene Axles (2016)
  • Author(s): Y. Akae, Y. Koyama, H. Sogawa, Y. Hayashi, S. Kawauchi, S. Kuwata, T. Takata
  • Journal Title: Chemistry A Eurpean Journal Volume: 22 Issue: 15 Pages: 5335-5341
  • DOI: 10.1002/chem.201504882
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Thermotriggered Catalyst-Free Modification of a Glass Surface with an Orthogonal Agent Possessing Nitrile N-Oxide and Masked Ketene Functions (2016)
  • Author(s): S. Cheawchan, S. Uchida, H. Sogawa, Y. Koyama, and T. Takata
  • Journal Title: Langmuir Volume: 32 Issue: 1 Pages: 309-315
  • DOI: 10.1021/acs.langmuir.5b03881
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Vinylic Macromolecular Rotaxane Cross-Linkers Endowing Network Polymers with Toughness (2015)
  • Author(s): Jun Sawada,Daisuke Aoki, Satoshi Uchida, Hideyuki Otsuka, and Toshikazu Takata
  • Journal Title: ACS Macro Letters Volume: 4 Issue: 5 Pages: 598-601
  • DOI: 10.1021/acsmacrolett.5b00242
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Effective Aproach to Cyclic Polymer from Linear Polymer: Synthesis and Transformation of Macromolecular [1]Rotaxane (2015)
  • Author(s): Takahiro Ogawa, Kazuko Nakazono, Daisuke Aoki, Satoshi Uchida, Toshikazu Takata
  • Journal Title: ACS Macro Lett. Volume: 4 Issue: 4 Pages: 343-347
  • DOI: 10.1021/acsmacrolett.5b00067
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Star/Linear Polymer Topology Transformation Facilitated by Mechanical Linking of Polymer chains (2015)
  • Author(s): Daisuke Aoki, Satoshi Uchida and Toshikazu Takata
  • Journal Title: Angew. Chem., Int. Ed. Volume: in press Issue: 23 Pages: 6770-6774
  • DOI: 10.1002/anie.201500578
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Novel Topological Cross-Linkers Synthesized for Vinyl Polymer Systems (2015)
  • Author(s): 打田 聖、澤田 隼、飯島 圭祐、青木 大輔、中薗 和子、高田 十志和
  • Journal Title: KOBUNSHI RONBUNSHU Volume: 72 Issue: 3 Pages: 93-103
  • DOI: 10.1295/koron.2014-0075
  • NAID: 130005129600
  • ISSN: 0386-2186, 1881-5685
  • Peer Reviewed
• [Journal Article] Linear-cyclic polymer structural transformation and its reversible control using a rational rotaxane strategy (2015)
  • Author(s): Takahiro Ogawa, Naoya Usuki, Kazuko Nakazono, Yasuhito Koyama, Toshikazu Takata
  • Journal Title: Chem. Commun. Volume: 51 Issue: 26 Pages: 5606-5609
  • DOI: 10.1039/c4cc08982k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of main chain-type liquid crystalline polyrotaxanes: Influence of the wheel components and their mobility on liquid crystalline properties (2014)
  • Author(s): Yoko Abe, Hisashi Okamura, Satoshi Uchida, Toshikazu Takata
  • Journal Title: Polym. J Volume: 46 Issue: 9 Pages: 553-558
  • DOI: 10.1038/pj.2014.23
  • NAID: 40020178485
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Characterization of A Mechanically Linked Transformable Polymer, (2014)
  • Author(s): Daisuke Aoki, Satoshi Uchida, Toshikazu Takata
  • Journal Title: Polym. J. Volume: 46 Issue: 9 Pages: 546-552
  • DOI: 10.1038/pj.2014.22
  • NAID: 40020178464
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Effect of a Side Chain Rotaxane Structure on the Helix-Folding of Poly(m-phenylene diethynylene) (2014)
  • Author(s): Sakiko Suzuki, Kazuki Matsuura, Kazuko Nakazono, Toshikazu Takata
  • Journal Title: Polym. J. Volume: 46 Issue: 6 Pages: 355-365
  • DOI: 10.1038/pj.2014.4
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Mechanically linked Block/Graft Copolymers: Effective Synthesis via Functional Macromolecular [2]Rotaxanes (2014)
  • Author(s): Daisuke Aoki, Satoshi Uchida, Toshikazu Takata
  • Journal Title: ACS Macro Lett Volume: 3 Issue: 4 Pages: 324-328
  • DOI: 10.1021/mz5001306
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] ロタキサン連結型腕鎖をもつスターポリマーの合成と腕鎖本数変換 (2016)
  • Author(s): 廣瀬拓真, 青木大輔, 高田十志和
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-24
• [Presentation] Synthesis and Topology Transformation of Mechanically Linked ABC Terpolymer (2016)
  • Author(s): 佐藤弘樹, 青木大輔, 高田十志和
  • Organizer: 日本化学会第96春季大会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-24
• [Presentation] International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules (2016)
  • Author(s): Toshikazu Takata
  • Organizer: 金沢大学ミニ国際シンポジウム
  • Place of Presentation: 金沢
  • Year and Date: 2016-03-10
  • Int'l Joint Research / Invited
• [Presentation] Reversible Topology Transformation of Linear －Cyclic Polymer Using Rotaxane Protocol－ (2015)
  • Author(s): Toshikazu Takata
  • Organizer: Pachifichem2015
  • Place of Presentation: Honolulu
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Dynamic Polymer Networks Engineered by Rotaxane Cross-Linkers (2015)
  • Author(s): Toshikazu Takata, Kazuko Nakazono, Daisuke Aoki, and Hiromitsu Sogawa
  • Organizer: 11th International Conference on Advanced Polymers via Macromolecular Engineering Registration (APME2015)
  • Place of Presentation: 横浜
  • Year and Date: 2015-10-18
  • Int'l Joint Research / Invited
• [Presentation] 熱応答性ロタキサン分子スイッチを用いた高分子の可逆的高次構造変換 (2015)
  • Author(s): 高田十志和, 朱 南, 中薗和子
  • Organizer: 第26回基礎有機化学討論会
  • Place of Presentation: 松山
  • Year and Date: 2015-09-24
• [Presentation] 可変な連結様式をもつブロックコポリマーの合成と構造・物性制御 (2015)
  • Author(s): 高田十志和
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 仙台
  • Year and Date: 2015-09-15
  • Invited
• [Presentation] ロタキサン連結スターポリマーの合成とそのトポロジー変換 (2015)
  • Author(s): 廣瀬拓真, 青木大輔, 高田十志和
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 仙台
  • Year and Date: 2015-09-15
• [Presentation] Role of Mechanical Linkage in Polymer Systems: Tough Polymer and Topology-Transformable Polymer (2015)
  • Author(s): Toshikazu Takata
  • Organizer: Japan-Taiwan Bilateral Symposium on Functional Polymer 2015 JTBS2015
  • Place of Presentation: 札幌
  • Year and Date: 2015-09-02
  • Int'l Joint Research / Invited
• [Presentation] ロタキサン型非共有結合連結がもたらす機能と物性 (2015)
  • Author(s): 高田十志和
  • Organizer: 名古屋大学応用化学系講演会
  • Place of Presentation: 名古屋
  • Year and Date: 2015-07-24
  • Invited
• [Presentation] 超分子ポリマーの組織化とトポロジー変換 (2015)
  • Author(s): 高田十志和
  • Organizer: 第95日本化学会春季年会
  • Place of Presentation: 千葉県船橋市
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 形を変えるブロックコポリマー：可変な連結様式の構築と特性制御 (2015)
  • Author(s): 高田十志和
  • Organizer: 東北ポリマー懇話会
  • Place of Presentation: 盛岡市上田
  • Year and Date: 2015-03-16 – 2015-03-17
  • Invited
• [Presentation] Intelligent Polymer Materials Characterized by Rotaxane Linkages (2015)
  • Author(s): Toshikazu Takata
  • Organizer: Yamagata University International Commemorative Symposium of GMAP Center
  • Place of Presentation: Yonezawa
  • Year and Date: 2015-01-23 – 2015-01-24
  • Invited
• [Presentation] 超分子連結の新手法と動的性質の活用による新材料創製 (2014)
  • Author(s): 高田十志和
  • Organizer: 特別講義
  • Place of Presentation: 千葉県習志野市
  • Year and Date: 2014-12-19
  • Invited
• [Presentation] 超分子ポリマーの組織化とトポロジー変換 (2014)
  • Author(s): 高田十志和
  • Organizer: 国際高等研究所講演会「分子基盤に基づく生体機能への揺らぎとダイナミックネットワークの解明」2014年度第1回研究会
  • Place of Presentation: 京都府木津川市
  • Year and Date: 2014-12-14 – 2014-12-15
  • Invited
• [Presentation] ロタキサン構造を架橋点とする新しい架橋高分子の構築法 (2014)
  • Author(s): 高田十志和
  • Organizer: エラストマー討論会
  • Place of Presentation: 豊田市
  • Year and Date: 2014-12-04 – 2014-12-05
• [Presentation] 高機能化を目指す高分子の合成と修飾 (2014)
  • Author(s): 高田十志和
  • Organizer: 大阪工研協会ニューフロンティア材料部会第94回例会
  • Place of Presentation: 大阪市
  • Year and Date: 2014-11-13
  • Invited
• [Presentation] Thermo-responsive Hydro Gels Networked by Rotaxane Cross-links (2014)
  • Author(s): Toshikazu Takata, Takayuki Arai, Keumhee Jang, and Yasuhito Koyama
  • Organizer: Polymer Network and Gel 2014 (PN&G2014)
  • Place of Presentation: Tokyo
  • Year and Date: 2014-11-10 – 2014-11-14
  • Invited
• [Presentation] Chiral Rotaxane Catalysts for Asymmetric Reactions (2014)
  • Author(s): Toshikazu Takata
  • Organizer: MC Asia 2014
  • Place of Presentation: Beijing
  • Year and Date: 2014-10-29 – 2014-10-31
  • Invited
• [Presentation] Macrocycle Catalyst for Highly Efficient Hydroamination via Cavity-Threading of Substrate as The Key Process (2014)
  • Author(s): Toshikazu Takata
  • Organizer: CRC International Symposium on Synthesis and Applications of Functional Molecules and Materials Utilizing Biomolecules as a Motif
  • Place of Presentation: Sapporo
  • Year and Date: 2014-09-03 – 2014-10-01
• [Presentation] Transformable Polymer Architectures Functioned by Movable Linkages- Role of Rotaxane Linkage for Polymer Topology Change - (2014)
  • Author(s): Toshikazu Takata, Daisuke Aoki, and Satoshi Uchida
  • Organizer: High Tech Polymer Materials (HTPM) 2014
  • Place of Presentation: Beijing
  • Year and Date: 2014-07-01 – 2014-07-04
• [Presentation] 高分子鎖の空間連結による動的超分子の創製とその特性 (2014)
  • Author(s): 高田十志和
  • Organizer: 早稲田大学軽井沢セミナー
  • Place of Presentation: 軽井沢
  • Year and Date: 2014-06-17 – 2014-06-18
  • Invited
• [Presentation] 高分子の高次構造精密解析を支える分光分析技術 - らせんポリマーの合成と構造 - (2014)
  • Author(s): 高田十志和
  • Organizer: 高分子学会関東支部第80回武蔵野地区高分子懇話会
  • Place of Presentation: 八王子
  • Year and Date: 2014-06-13
  • Invited
• [Presentation] ロタキサン化学 - 空間連結と動的特性が醸す特異機能の創出 - (2014)
  • Author(s): 高田十志和
  • Organizer: 東北大学理学部・理学研究科一般雑誌会講演会
  • Place of Presentation: 仙台
  • Year and Date: 2014-06-05
  • Invited
• [Presentation] ロタキサン触媒の特異機能 - 協同効果と０次反応 - (2014)
  • Author(s): 高田十志和
  • Organizer: 大阪大学基礎工学研究科講演会
  • Place of Presentation: 大阪
  • Year and Date: 2014-05-02
  • Invited
• [Book] 高分子テクノロジーハンドブック (2014)
  • Author(s): 西敏夫編 (高田十志和 ; インターロック高分子)
  • Publisher: エヌ・ティー・エス