研究成果報告書

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2 ( 1) 100% (, Feringa, Nature, 1999) 1 (, Nature Commun. 2010) 2 (, Nature, 2007) 3 (, Nature, 2003) 4 ( 2) 3 1 C2- (9,9ʼ- ) ( 3)2 ( 4)3 (N-) () ( 5) 3. * ne-handed helix * ptically Active group Positional Switching * * Random helix Rational Design to Control Helical Polymers 4. (i)(ii)

3 C2-symmetric Cs-symmetric Coil-shaped Screw-shaped (1) C 2-9,9-2 / [Chem. Commun. 2015] (2) C 2-9,9 - [ACS Macro Lett. 2015] α CD [2] [3] α CD CD α CD [2][3] [3] CD head-to-head [Chem. Lett. 2012]

4 rg. Lett Rotaxane-from method ACS macro Lett Rotaxane-from method [2] rg. Lett rg. Lett (BEK) (rg. Lett. 2013, Polym. J. 2014) ACS macro Lett. 2013

5 Polym. J poly-(r)-1a NMe Through Space Chirality Transfer ne-handed Folded Helix poly-(r)-1a poly-(r)-1b TFA DBU ptically Active wheel (Far) (Close) NMe H Random Coil poly-(r)-1b poly-(r)-1a CF 3C poly-(r)-1b Angew. Chem., Int. Ed., 2015 Chem.Lett. 2015; ACS macro Lett C. Wang, Y. Koyama, S. Uchida, T. Takata, Synthesis of Highly Reactive Polymer Nitrile N-xides for Effective Solvent-free Grafting, ACSMacro Lett. 2014, 3, , DI: / mz500069f K. Iijima, Y. Koyama, S. Uchida, T. Takata, Stimuli-Degradable Cross-Linked Polymers Synthesized by Radical Polymerization Using a Size-Complementary [3]Rotaxane Cross-Linker, Polym. J. 2014, 46, 67-72, DI: / pj S. Suzuki, K. Matsuura, K. Nakazono, T. Takata, Effect of a Side Chain Rotaxane Structureon the Helix-Folding of Poly(m-phenylene diethynylene), Polym. J. 2014, 46, , DI: / pj D. Aoki, S. Uchida, T. Takata, Mechanically linked Block/Graft Copolymers: Effective Synthesis via Functional Macromolecular[2]Rotaxanes, ACSMacro Lett. 2014, 3, , DI: / mz D. Aoki, S. Uchida, T. Takata, Synthesis and Characterization of a Mechanically Linked Transformable Polymer, Polym. J. 2014, 46, , DI: / pj Y. Abe, H. kamura, S.Uchida, T. Takata, Synthesis of main chain-type liquid crystalline polyrotaxanes: influoence of the wheel components and their mobility on liquid crystalline properties, Polym. J. 2014, 46, , DI: / pj K. Nakazono, T.Ishino, T.Takashima, D. Saeki, D. Natsui, N. Kihara, T. Takata, Directed ne-pot synthesis of Crown Ether Wheel-Containing Main Chain-type Polyrotaxanes with Controlled Rotaxanation ratio, Chem. Commun. 2014, 50, , DI: /C4CC06943A Y. Koyama, T. Yoshii, Y. Kohsaka, T. Takata, Photo-Degradable Cross-Linked Polymer Derived from a Vinylic Rotaxane Cross-Linker Possessing Aromatic Disulfide Axle, Pure & Appl. Chem. 2013, 85, , DI: /PAC-CN T. Arai, K. Jang, Y. Koyama, S. Asai, T. Takata, Versatile Supramolecular Cross-Linker: Rotaxane Cross-Linker that Directly Endows Vinyl Polymers with Movable Cross-Links, Chem. Eur. J. 2013, 19, , DI: /chem R. Seto, Y. Koyama, K. Xu, S. Kawauchi, T. Takata, Exact Helical Polymer Synthesis by Directionally Fixed Connection of C 2 -Chiral 9,9 -Spirobifluorene Unit with C 2 - or C s -Symmetric Unit, Chem. Commun. 2013, 49, , DI: /C3CC41685B, D. Aoki, K. Nakazono, Y. Koyama, S.Uchida, T. Takata, Synthesis and Characterization of Macromolecular [2]Rotaxane Having Polymer Chain, ACSMacro Lett. 2013, 2, , DI: /mz400197d H. Iguchi, S. Uchida, Y. Koyama, T. Takata, Polyester-containing α-cyclodextrin-based Polyrotaxane: Synthesis by Living Ring-opening Polymerization, Polypseudorotaxanation, and End-capping Using Nitrile N-xide, ACSMacro Lett. 2013, 2, , DI: / mz H. kuda, Y. Koyama, T. Takata, 9,9-Diaryl-4,5-diazafluorene-based Cardo Polymer; Synthesis and Characteristic Properties, J. Polym. Sci. Polym. Chem. 2013, 51, , DI: /pola.26870S. Cheawchan, Y. Koyama, S. Uchida, T. Takata, Polymer, 2013, 54, , DI: /j.polymer T. Yuki, Y. Koyama, T. Matsumura, T. Takata, Click Annulation of Pseudo[2]rotaxane to [2]Catenane Exploiting Homoditopic Nitrile N-xide, rg. Lett. 2013, 15, , DI: /ol u C. Wang, Y. Koyama, M. Yonekawa, S.

6 Uchida, T. Takata, Polymer Nitrile N-xide Directed toward Catalyst-and Solvent-Free Click Grafting, Chem. Commun. 2013, 49, , DI:10,1039/c3cc42992j Y. Koyama, T. Matsumura,. Ishitani, T. Takata, Fluorescence Control of Boron Enaminoketonate Using a Rotaxane Shuttle, rg. Lett. 2013, 15, , DI: / ol j Y. Akae, T. Arai, Y, Koyama, H, kamura, K. Johmoto, H. Uekusa, S. Kuwata, T. Takata, ne-pot Synthesis of Permethylated α CD-based Rotaxanes Having Alkylene Chain Axles and Their Structural Caracteristics, Chem. Lett. 2012, 41, DI: /cl Y. Abe, H. kamura, K. Nakazono, Y. Koyama, S. Uchida, T. Takata, Thermoresponsive Shuttling of Rotaxane Containing Trichloroacetate Ion, rg. Lett. 2012, 14, DI: /ol301771w M. Yonekawa, Y. Koyama, S. Kuwata, T. Takata, rg. Lett. 2012, 14, DI: /ol300125s 29 T. Takata, D. Aoki, S. Uchida, Transformable Polymer Architectures Functioned by Movable Linkages-Role of Rotaxane Linkage for Polymer Topology Change, High Tech Polymer Materials (HTPM)2014, Chinese Academy of Science (China) H. Sogawa, H. kuda, T. Takata, Structural Switch and Application of Exact Helical Foldamer Containing C 2 -chiral Spirobifluorene in the Main Chain, Chirality-2014, PragueCzech T. Takata, Y. Koyama, Macrocycle Catalyst for Highly Efficient Hydroaminatino via Cavity-Threading of Substrate as the Key Process, CRC International Symposium on Synthesis and Application of Functional Molecules and Materials Utilizing Biomolecules as a Motif, , Hokkaido University (Sapporo) T. Takata, Chiral Rptaxane Catalysts for Asymmetric Reactions, MC Asia 2014, , Beijing (China) T. Takata, T. Arai, K. Jang, Y. Koyama, Thermo-responsive Hydro Gels Networked by Rotaxane Cross-links, Polymer Network and Gel 2014 (PN&G2014), University of Tokyo (Tokyo) Toshikazu Takata, Intelligent Polymer Materials Characterized by Rotaxane Linkages, Yamagata University International Commemorative Symposium of GMAP Center, , Yamagata University (Yamagata) T. Takata, Synthetic Protocol of Cyclic Polymer from Linear Polymer and Reversible Linear-Cyclic Polymer Topology Conversion, 245 th ACS Annual Meeting, , New rleans (USA) T. Tkaata, Topological Chirality: Powerful Dynamic Chirality, 25 th International conference on Molecular chirality, , Shanghai (China) T. Takata, Transformable Polymer Architectures Functioned by Movable Linkages, The 13th Pacific Polymer Conference 2013, , Kaohsiung (Taiwan)

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