Creation of Mechanochromic Elastomers Exploiting Unique Properties of Interlock Bonds

• Project/Area Number: 24685023
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Functional materials chemistry
• Research Institution: Toyama Prefectural University (2015-2016); Hokkaido University (2012-2014)
• Principal Investigator: Koyama Yasuhito 富山県立大学, 工学部, 准教授 (10456262)
• Co-Investigator(Renkei-kenkyūsha): TAKATA Toshikazu 東京工業大学, 物質理工学院, 教授 (40179445)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥25,480,000 (Direct Cost: ¥19,600,000、Indirect Cost: ¥5,880,000); Fiscal Year 2015: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2014: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2013: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2012: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
• Keywords: 超分子化学 / 高分子合成 / 有機化学 / らせん高分子 / 空間集積 / メカノクロミズム / ラセン高分子 / 空間結合 / エラストマー

Outline of Final Research Achievements

In this work, we investigated the development of mechano-chromic elastomers containing non-covalent, but chemically stable interlocked bonds at the cross-linking points. Building upon the use of stress-responsive properties (sliding elasticity) of polyrotaxane network, we planned the creation of new soft materials bearing both rotaxane-cross-linking points and functional units. As a result, we developed new polymeric materials with unique stress-responsivity. We also achieved the development of various stimuli-responsive rotaxane-based components and their related materials.

Research Products

• [Journal Article] One-pot synthesis of alternating peptides exploiting a new polymerization technique based on Ugi's 4CC reaction (2017)
  • Author(s): Y. Koyama, P. G. Gudeangadi
  • Journal Title: Chemical Communications Volume: 53 Issue: 27 Pages: 3846-3849
  • DOI: 10.1039/c6cc09379e
  • Peer Reviewed / Acknowledgement Compliant
• [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] Ionic Polymerization of a Sugar-based Cyclic Sulfite: Synthesis of (1→2)-D-Glucopyranan via Cationic Polymerization (2016)
  • Author(s): S. S. Shetty, Y. Koyama, T. Nakano
  • Journal Title: Chemistry Letters Volume: 45 Issue: 8 Pages: 1021-1023
  • DOI: 10.1246/cl.160416
  • NAID: 130005254539
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Properties of Modified Amylose Containing an Aryl Spacer at a Regular Interval in Its Main Chain (2016)
  • Author(s): Y. Koyama, T. Nakano
  • Journal Title: Chemistry Letters Volume: 45 Issue: 8 Pages: 1018-1020
  • DOI: 10.1246/cl.160383
  • NAID: 130005254531
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] One-Pot Synthesis of Glycyrrhetic Acid Polyglycosides based on Grafting-From Method Using Cyclic Sulfite (2016)
  • Author(s): S. S. Sangeetha, Y. Koyama
  • Journal Title: Tetrahedron Letters Volume: 57 Issue: 32 Pages: 3657-3661
  • DOI: 10.1016/j.tetlet.2016.07.001
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nitrile <i>N</i>-Oxide Agents for Click Reaction: Catalyst-Free Cycloaddition Reaction Involving C-C Bond Formation (2016)
  • Author(s): 小山靖人, 高田十志和
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 74 Issue: 9 Pages: 866-876
  • DOI: 10.5059/yukigoseikyokaishi.74.866
  • NAID: 130005421116
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed / Acknowledgement Compliant
• [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 rotaxane cross-linked polymers derived from vinyl monomers using a metal-containing supramolecular cross-linker (2015)
  • Author(s): Masahiro Ogawa, Hiromitsu Sogawa, Yasuhito Koyama, Toshikazu Takata
  • Journal Title: Polymer Journal Volume: 47 Issue: 8 Pages: 580-584
  • DOI: 10.1038/pj.2015.34
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Cyclodextrin-Based Size-Complementary [3]Rotaxanes: Selective Synthesis and Specific Dissociation (2014)
  • Author(s): Yosuke Akae, Yasuhito Koyama, Shigeki Kuwata, Toshikazu Takata
  • Journal Title: Chemistry A European Journal Volume: 20 Issue: 51 Pages: 17132-17136
  • DOI: 10.1002/chem.201405005
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of topologically crosslinked polymers with rotaxane-crosslinking points (2014)
  • Author(s): Y. Koyama
  • Journal Title: Polymer Journal Volume: 46 Issue: 6 Pages: 315-322
  • DOI: 10.1038/pj.2014.9
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Gigantic chiroptical enhancements in polyfluorene copolymers bearing bulky neomenthyl groups : importance of alternating sequences of chiral and achiral fluorene units (2014)
  • Author(s): Kento Watanabe, Yasuhito Koyama, Nozomu Suzuki, Michiya Fujiki and Tamaki Nakano
  • Journal Title: Polymer Chemistry Volume: 5 Issue: 3 Pages: 712-717
  • DOI: 10.1039/c3py01442h
  • Peer Reviewed
• [Journal Article] Photo-induced helix-helix transition of a polystyrene derivative (2014)
  • Author(s): Y. Wang, T. Sakamoto, Y. Koyama, Y. Takanashi, J. Kumaki, J. Cui, X. Wan, T. Nakano
  • Journal Title: Polymer Chemistry Volume: 5 Issue: 3 Pages: 718-721
  • DOI: 10.1039/c3py01492d
  • NAID: 120005540279
  • Peer Reviewed
• [Journal Article] Stimuli-Degradable Cross-Linked Polymers Synthesized by Radical Polymerization Using A Size-Complementary [3]Rotaxane Cross-Linker (2014)
  • Author(s): Keisuke Iijima, Yasuhito Koyama, Satoshi Uchida, Toshikazu Takata
  • Journal Title: Polym. J. Volume: 46 Issue: 1 Pages: 67-72
  • DOI: 10.1038/pj.2013.63
  • NAID: 40019921465
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Macromolecular [2]Rotaxane Having Polymer Chain (2013)
  • Author(s): Daisuke Aoki, Kazuko Nakazono, Yasuhito Koyama, Satoshi Uchida, Toshikazu Takata,
  • Journal Title: ACS MacroLett. Volume: 2 Issue: 6 Pages: 461-465
  • DOI: 10.1021/mz400197d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Exact Helical Polymer Synthesis by Directionally Fixed Connection of C2-Chiral 9,9’-Spirobifluorene Unit with C2- or Cs-Symmetric Unit (2013)
  • Author(s): Ryota Seto, Yasuhito Koyama, Kun Xu, Susumu Kawauchi, Toshikazu Takata
  • Journal Title: Chem. Commun Volume: 49 Issue: 48 Pages: 5486-5488
  • DOI: 10.1039/c3cc41685b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 41)Polyester-containing α-Cyclodextrin-based Polyrotaxane: Synthesis by Living Ring-opening Polymerization, Polypseudorotaxanation, and End-capping Using Nitrile N-Oxide (2013)
  • Author(s): Hiroyuki Iguchi, Satoshi Uchida, Yasuhito Koyama, Toshikazu Takata,
  • Journal Title: ACS MacroLett. Volume: 2 Issue: 6 Pages: 527-530
  • DOI: 10.1021/mz4002518
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 9,9-Diaryl-4,5-diazafluorene-Based Cardo Polymer ; Synthesis and Characteristic Properties (2013)
  • Author(s): Hitoshi Okuda, Yasuhito Koyama, Takahiro Kojima, Toshikazu Takata
  • Journal Title: Journal of Polymer Science, Part A ; Polymer Chemistry Volume: 51(21) Issue: 21 Pages: 4541-4549
  • DOI: 10.1002/pola.26870
  • Peer Reviewed
• [Journal Article] Click Annulation of Pseudo[2]rotaxane to [2]Catenane Exploiting Homoditopic Nitrile N-Oxide (2013)
  • Author(s): Tatsuya Yuki, Yasuhito Koyama, Tohru, Matsumura, Toshikazu Takata
  • Journal Title: Org. Lett. Volume: 15 Issue: 17 Pages: 4438-4441
  • DOI: 10.1021/ol401986u
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cascade fuctionalization of unsaturated bond-containing polymers using ambidentagents possessing both nitrile N-oxide and electrophilic functions (2012)
  • Author(s): Yasuhito Koyama, Kaori Miura, Sumitra Cheawchan, Akishige Seo, and Toshikazu
  • Journal Title: Chemical Communications Volume: 48 Issue: 83 Pages: 10304-10306
  • DOI: 10.1039/c2cc35158g
  • Peer Reviewed
• [Journal Article] Selective Synthesis of a [3]Rotaxane Consisting of Size-Complementary Components and Its Stepwise Deslippage (2012)
  • Author(s): Yosuke Akae, Hisashi Okamura, Yasuhito Koyama, Takayuki Arai, and Toshikazu
  • Journal Title: Organic Letters Volume: 14 Issue: 9 Pages: 2226-2229
  • DOI: 10.1021/ol300578q
  • Peer Reviewed
• [Journal Article] One-pot Synthesis of Permethylated &alpha;-CD-based Rotaxanes Having Alkylene Chain Axles and Their Structural Characteristics (2012)
  • Author(s): (Yosuke Akae), Takayuki Arai, Yasuhito Koyama, Hisashi Okamura, Kohei Johmoto, Hidehiro Uekusa, Shigeki Kuwata, and Toshikazu Takata
  • Journal Title: Chemistry Letters Volume: 41 Issue: 8 Pages: 806-808
  • DOI: 10.1246/cl.2012.806
  • NAID: 130004426645
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Thermoresponsive Shuttling of Rotaxane Containing Trichloroacetate Ion (2012)
  • Author(s): (Yoko Abe), Hisashi Okamura, Kazuko Nakazono, Yasuhito Koyama, Satoshi Uchida, and Toshikazu Takata
  • Journal Title: Organic Letters Volume: 14 Issue: 16 Pages: 4122-4125
  • DOI: 10.1021/ol301771w
  • Peer Reviewed
• [Journal Article] Catalyst- and Solvent-Free Click Synthesis of Cyclodextrin-Based Polyrotaxanes Exploiting a Nitrile N-Oxide (2012)
  • Author(s): Keumhee Jang, Kaori Miura, Yasuhito Koyama, and Toshikazu Takata
  • Journal Title: Organic Letters Volume: 14 Pages: 3088-3091
  • Peer Reviewed
• [Presentation] 主鎖にスペーサー構造を有する構造改変アミロースの合成と特異なゲスト包接挙動 (2016)
  • Author(s): 小山靖人
  • Organizer: 文部科学省 科学研究費 新学術領域研究「元素ブロック高分子材料の創出」第7回公開シンポジウム
  • Place of Presentation: 東京ビッグサイト
  • Year and Date: 2016-01-29
  • Invited
• [Presentation] 巨大分子間を無触媒で連結するニトリルオキシド反応剤の開発と応用 (2016)
  • Author(s): 小山靖人
  • Organizer: 平成28年度トメックス第15回研究会
  • Place of Presentation: 富山県民会館
  • Invited
• [Presentation] オリゴ糖の２次構造を利用した機能性材料の創製 (2016)
  • Author(s): 小山靖人
  • Organizer: バイオテクノロジー講演会
  • Place of Presentation: 富山県民会館
  • Invited
• [Presentation] Synthesis and Complexation Behavior of Modified Amylose Containing Alkyl Spacer at a Regular Interval in the Main Chain (2015)
  • Author(s): Y. Koyama, T. Nakano
  • Organizer: 15th International Conference on Chiroptical Spectroscopy
  • Place of Presentation: 北海道大学、札幌
  • Year and Date: 2015-08-31
  • Int'l Joint Research
• [Presentation] Synthesis and Properties of Modified Amylose Containing Alkyl Spacer at a Regular Interval in the Main Chain (2015)
  • Author(s): Y. Koyama, T. Nakano
  • Organizer: Spring Meeting of the Polymer Society of Korea
  • Place of Presentation: Daejoen, Korea
  • Year and Date: 2015-04-08
  • Int'l Joint Research / Invited
• [Presentation] 5.Syntheses and Applications of Supramolecular Polymers Exploiting Saccharide Skeletons (2015)
  • Author(s): Y. Koyama
  • Organizer: Special Lecture at Chulalongkorn University
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2015-01-27
  • Invited
• [Presentation] Polymer Nitrile N-Oxide Directed toward Catalyst- and Solvent-Free Click Grafting (2013)
  • Author(s): Yasuhito Koyama, Cheng-Gang Wang, Morio Yonekawa, and Toshikazu Takata
  • Organizer: International Symposium of Catalysis Research Center
  • Place of Presentation: 札幌、北海道大学
  • Year and Date: 2013-02-05
• [Presentation] Efficient Polymer Reaction Using Macrocycle Catalyst as a Result of Wheel Translation along the Polymer Axle (2013)
  • Author(s): Yasuhito Koyama, Ayumi Kawasaki, Norihito Miyagawa, Masaki Nagashima, Toshikazu Takata
  • Organizer: Joint Symposium of PCOSS, Xiamen Univ. and CRC, Hokkaido Univ
  • Place of Presentation: 北海道大学（札幌市）
  • Invited
• [Presentation] マクロサイクル触媒システム：軸成分の移動に伴う高分子軸上での効率的な触媒反応 (2013)
  • Author(s): 小山靖人，長嶋将毅, 川崎あゆみ，宮川賀人，高田十志和
  • Organizer: 第4回統合物質シンポジウム
  • Place of Presentation: 北海道大学（札幌市）
  • Invited
• [Presentation] ロタキサン連結点を持つ超分子ポリマーの創成と応用 (2013)
  • Author(s): 小山靖人
  • Organizer: 若手研究者のための有機化学札幌セミナー
  • Place of Presentation: 北海道大学（札幌市）
  • Invited
• [Presentation] 安定ニトリルオキシド反応剤を用いるゴムの無触媒架橋・グラフト法の開発 (2012)
  • Author(s): 小山靖人
  • Organizer: 第187回ゴム技術シンポジウム
  • Place of Presentation: 東京、東京電業会館(招待講演)
  • Year and Date: 2012-12-05
• [Presentation] Direct Grafting Method of Common Polymers Exploiting Nitrile N-Oxide-Terminated Vinyl Polymer (2012)
  • Author(s): Yasuhito Koyama, Cheng-Gang Wang, Morio Yonekawa, and Toshikazu Takata
  • Organizer: IKCOC-12
  • Place of Presentation: 京都、京都国際会議場
  • Year and Date: 2012-11-15
• [Presentation] 安定ニトリルオキシド反応剤を用いる汎用高分子の無触媒架橋・グラフト法の開発 (2012)
  • Author(s): 小山靖人・王晨綱・米川盛生・高田十志和
  • Organizer: 第102回有機合成シンポジウム
  • Place of Presentation: 東京、早稲田大学
  • Year and Date: 2012-11-08
• [Presentation] ニトジルオキシドで末端停止したビニルポリマーを用いる汎用ポリマーの直截的グラフト法 (2012)
  • Author(s): 小山靖人・王晨綱・米川盛生・高田十志和
  • Organizer: 第61回高分子討論会
  • Place of Presentation: 名古屋、名古屋工業大学(招待講演)
  • Year and Date: 2012-09-21
• [Presentation] マクロサイクル触媒:輪成分の移動に伴う高分子軸上での連続的触媒反応 (2012)
  • Author(s): 小山靖人・川崎あゆみ・宮川賀仁・高田十志和
  • Organizer: 第9回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 札幌、北海道大学
  • Year and Date: 2012-05-27
• [Book] 元素ブロック高分子材料 (2015)
  • Author(s): 小山靖人、中野環
  • Total Pages: 275
  • Publisher: 株式会社シーエムシー出版
• [Remarks] 研究室のweb cite
  • URL: http://www.pu-toyama.ac.jp/PH/koyama/
• [Remarks] http://researchmap.jp/read0103366/
• [Remarks]
  • URL: http://polymer.cat.hokudai.ac.jp/index.html
• [Patent(Industrial Property Rights)] フッ素ニトリルオキシド化合物 (2013)
  • Inventor(s): 神原將、野口剛、毛利晴彦、高田十志和、小山靖人、打田聖、王晨綱
  • Industrial Property Rights Holder: ダイキン工業株式会社十国立大学法人東京工業大学
  • Industrial Property Number: 2013-045759
  • Filing Date: 2013-03-07