Construction and functional analysis of internal molecular asymmetric fields utilizing helical conjugated polymers

• Project/Area Number: 22350049
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Polymer chemistry
• Research Institution: Kansai University (2013); Kyoto University (2010-2012)
• Principal Investigator: SANDA Fumio 関西大学, 化学生命工学部, 教授 (70262318)
• Project Period (FY): 2010-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000); Fiscal Year 2013: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2012: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2011: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2010: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: 共役高分子 / 光学活性高分子 / 光電気機能 / ポリフェニレンエチニレン / 高分子合成 / らせん高分子 / 光学活性会合体 / ターフェニレン / 光応答性 / 高分子構造・物性 / ナノ材料 / 有機工業化学 / 合成化学 / らせん構造 / 光学活性聖 / 薗頭カップリグ重合 / フェニレン系ポリマー / ヒドロシリル化重合 / 酸化カップリング重合

Research Abstract

The author demonstrated the synthesis and chiroptical properties of various novel D-hydroxyphenylglycine-derived poly(phenyleneethynylene)s, as well as the photo-response and stabilization of the conformation by intramolecular crosslinking at the side chains. The key importance for helix formation for these polymers is amphiphilicity caused by the hydrophobic exterior and hydrophilic interior. p-Stacking between the phenylene moieties on the main chain and intramolecular hydrogen bonding between the amide/carbamate groups in the side chains also plays an important role in helix formation. Poly(phenyleneethynylene)s bearing azobenzene moieties in the main chains formed predominantly one-handed helically folded structures. The polymers underwent a reversible conformational change between folded and unfolded structures upon UV and visible irradiation.

Research Products

• [Journal Article] New Approach to the Polymerization of Disubstituted Acetylenes by Bulky Monophosphine-Ligated Palladium Catalysts (2014)
  • Author(s): Jesus Rodriguez Castanon, Natsuhiro Sano, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: ACS Macro Lett. Volume: 3 Pages: 51-54
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Conjugated Polymers Bearing m-Terphenylene Moieties by Acetylenic Coupling Polymerization : Chiral Aggregation and Optical Properties of the Product Polymers (2014)
  • Author(s): Yu Miyagi, Hiromitsu Sogawa, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 47 Pages: 1594-1603
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Conjugated Polymers Bearing m-Terphenylene Moieties by Acetylenic Coupling Polymerization: Chiral Aggregation and Optical Properties of the Product Polymers (2014)
  • Author(s): Yu Miyagi, Hiromitsu Sogawa, Masashi Shiotsuki, Fumio Sanda
  • Journal Title: Macromolecules Volume: 47 Issue: 5 Pages: 1594-1603
  • DOI: 10.1021/ma402123w
  • Peer Reviewed
• [Journal Article] Helix-sense-selective Polymerization of Achiral Acetylene Monomer Catalyzed by Rh Zwitterionic Complexes with Tethered Chiral Amino and Ether Groups (2013)
  • Author(s): Naoya Onishi, Toshiki Aoki, Takashi Kaneko, Masahiro Teraguchi, Natsuhiro Sano, Toshio Masuda, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Chem. Lett. Volume: 42 Pages: 278-280
  • NAID: 10031155779
  • Peer Reviewed
• [Journal Article] Polymerization of Phenylacetylenes Using Rhodium Catalysts Coordinated by Norbornadiene Linked to a Phosphino or Amino Group (2013)
  • Author(s): Naoya Onishi, Masashi Shiotsuki, Toshio Masuda, Natsuhiro Sano, and Fumio Sanda
  • Journal Title: Organometallics Volume: 32 Pages: 846-853
  • Peer Reviewed
• [Journal Article] Synthesis and Photoresponse of Helically Folded Poly(phenyleneethynylene)s Bearing Azobenzene Moieties in the Main Chains (2013)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 46 Pages: 4378-4387
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Poly(m-phenyleneethynylene-aryleneethynyle ne)s Bearing Hydroxy Groups and Examination of the Higher Order Structures (2013)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Takehiro Hirao, Takeharu Haino, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 46 Pages: 8161-8170
  • Peer Reviewed
• [Journal Article] Synthesis of Novel Optically Active Poly(phenyleneethynylene-aryleneethynylene)s Bearing Hydroxy Groups. Examination of the Chiroptical Properties and Conjugation Length (2013)
  • Author(s): Hiromitsu Sogawa, Yu Miyagi, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 46 Pages: 8896-8904
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Poly (m-phenyleneethynylene-aryleneethynylene) s Bearing Hydroxy Groups and Examination of the Higher Order Structures (2013)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Takehiro Hirao, Takeharu Haino, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 46 Issue: 20 Pages: 8161-8170
  • DOI: 10.1021/ma4017295
  • Peer Reviewed
• [Journal Article] 光学活性フェニレンエチニレン系共役高分子の合成と高次構造制御 (2013)
  • Author(s): 三田文雄
  • Journal Title: 関西大学理工学会誌 理工学と技術 Volume: 20 Pages: 35-37
  • NAID: 110009633781
• [Journal Article] Synthesis of End-Functionalized Polyacetylenes Bearing Polar Groups Employing Well-Defined Pd Catalysts (2012)
  • Author(s): Jesus Rodriguez Castanon, Keiko Kuwata, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Chem. Eur. J. Volume: 18 Pages: 14085-14093
  • Peer Reviewed
• [Journal Article] Stabilization of Higher-Order Structure of Poly(phenyleneethynylene)s by Metathesis Polymerization at the Side Chains (2012)
  • Author(s): Akinobu Hashimoto, Hiromitsu Sogawa, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Polymer Volume: 53 Pages: 2559-2566
  • Peer Reviewed
• [Journal Article] Characterization of the Polymerization Catalyst [(2,5-norbornadiene)Rh{C(Ph)=CPh_2 }(PPh_3)] and Identification of the End Structures of Poly(phenylacetylene)s Obtained by Polymerization Using This Catalyst (2012)
  • Author(s): Shohei Kumazawa, Jesus Rodriguez Castanon, Naoya Onishi, Keiko Kuwata, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Organometallics Volume: 31 Pages: 6834-6842
  • Peer Reviewed
• [Journal Article] Molecular Weight Dependence of Helical Conformation of Amino Acid-Based Polyphenylacetylenes (2011)
  • Author(s): Masashi Shiotsuki, Shohei Kumazawa, Naoya Onishi, and Fumio Sanda
  • Journal Title: J. Polym. Sci., Part A : Polym. Chem. Volume: 49 Pages: 4921-4925
  • Peer Reviewed
• [Journal Article] Synthesis of Polymers Bearing Proline Moieties in the Side Chains and Their Application as Catalysts for Asymmetric Induction (2011)
  • Author(s): Atsushi Ikeda, Kayo Terada, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: J. Polym. Sci., Part A : Polym. Chem. Volume: 49 Pages: 3783-3796
  • Peer Reviewed
• [Journal Article] Synthesis of Hydroxyphenylglycine-derived Novel Poly(silylenevinylene phenyleneethynylene)s (2011)
  • Author(s): Tokiko Ueda, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Polymer Volume: 52 Pages: 3570-3579
  • Peer Reviewed
• [Journal Article] Polymerization of Substituted Acetylenes and Features of the Formed Polymers (2011)
  • Author(s): Masashi Shiotsuki, Fumio Sanda, and Toshio Masuda
  • Journal Title: Polym. Chem. Volume: 2 Pages: 1044-1058
  • Peer Reviewed
• [Journal Article] Living Polymerization of Phenylacetylenes Catalyzed by Cationic Rhodium Complexes Bearing Tetrafluorobenzobarrelene (2011)
  • Author(s): Masashi Shiotsuki, Naoya Onishi, Fumio Sanda, and Toshio Masuda
  • Journal Title: Polym. J. Volume: 43 Pages: 51-57
  • NAID: 10027623795
  • Peer Reviewed
• [Journal Article] 後周期遷移金属触媒による置換アセチレンの精密重合 (2011)
  • Author(s): 塩月雅士, 尾西尚弥, Jesus Rodriguez Castanon, 増田俊夫, 三田文雄
  • Journal Title: 高分子論文集 Volume: 68 Pages: 210-222
  • NAID: 10029059772
  • Peer Reviewed
• [Journal Article] Synthesis, Chiroptical Properties, and Photoresponsiveness of Optically Active Poly(m-phenyleneethynylene)s Containing Azobenzene Moieties (2011)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Hideki Matsuoka, and Fumio Sanda
  • Journal Title: Macromolecules Volume: 44 Pages: 3338-3345
  • Peer Reviewed
• [Journal Article] Synthesis, Chiroptical Properties, and Photoresponsiveness of Optically Active Poly (m-phenyleneethynylene) s Containing Azobenzene Moieties (2011)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Hideki Matsuoka, Fumio Sanda
  • Journal Title: Macromolecules Volume: 44 Issue: 9 Pages: 3338-3345
  • DOI: 10.1021/ma200281e
  • Peer Reviewed
• [Journal Article] Synthesis of Hydroxyphenylglycine-derived Novel Poly(silylenevinylenephenyleneethynylene)s (2011)
  • Author(s): Tokiko Ueda, Masashi Shiotsuki, Fumio Sanda
  • Journal Title: Polymer Volume: 52 Issue: 16 Pages: 3570-3579
  • DOI: 10.1016/j.polymer.2011.06.010
  • Peer Reviewed
• [Journal Article] Synthesis of End-functionalized Poly(phenylacetylene)s with Well-characterized Palladium Catalysts (2010)
  • Author(s): Masashi Shiotsuki, Atsushi Nakagawa, Jesus Rodriguez Castanon, Naoya Onishi, Tatsurou Kobayashi, Fumio Sanda, and Toshio Masuda
  • Journal Title: J. Polym. Sci., Part A : Polym. Chem. Volume: 48 Pages: 5549-5556
  • Peer Reviewed
• [Journal Article] Amino Acid-Functionalized Ethyl Cellulose : Synthesis, Characterization, and Gas Permeation Properties (2010)
  • Author(s): Yoshitaka Ikeuchi, Fareha Zafar Khan, Naoya Onishi, Masashi Shiotsuki, Toshio Masuda, Yoshiyuki Nishio, and Fumio Sanda
  • Journal Title: J. Polym. Sci., Part A : Polym. Chem. Volume: 48 Pages: 3986-3993
  • Peer Reviewed
• [Journal Article] Recent Advances in Ring-Opening Metathesis Polymerization, and Application to Synthesis of Functional Materials (2010)
  • Author(s): Sutthira Sutthasupa, Masashi Shiotsuki, and Fumio Sanda
  • Journal Title: Polym. J. Volume: 42 Pages: 905-915
  • NAID: 10027447299
  • Peer Reviewed
• [Journal Article] Stabilization of Higher-order structure of Poly (phenyleneethynylene) s by Metathesis Polymerization at the Side Chains
  • Author(s): Akinobu Hashimoto, Hiromitsu Sogawa, Masashi Shiotsuki, Fumio Sanda
  • Journal Title: Polymer Volume: (掲載確定)
  • Peer Reviewed
• [Journal Article] Synthesis, Chiroptical Properties, and Photoresponsiveness of Optically Active Poly(m-phenyleneethynylene)s Containing Azobenzene Moieties
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Hideki Matsuoka, Fumio Sanda
  • Journal Title: Macromolecules Volume: (印刷中)
  • Peer Reviewed
• [Presentation] 主鎖に白金を含有する光学活性共役高分子の合成と特性 (2014)
  • Author(s): 宮城 雄, 曽川洋光, 三田文雄
  • Organizer: 第63回高分子学会年次大会
  • Place of Presentation: 名古屋国際会議場, 愛知
• [Presentation] 新規共役高分子の合成と特性 (2014)
  • Author(s): 三田文雄
  • Organizer: 関西大学先端科学技術シンポジウム
  • Place of Presentation: 関西大学（大阪）
• [Presentation] アミノ酸を不斉源とする水酸基含有ポリ(メタフェニレンエチニレンアリーレンエチニレン)の合成と二次構造 (2014)
  • Author(s): 曽川洋光, 三田文雄, 高田十志和
  • Organizer: 日本化学会第94回春季年会
  • Place of Presentation: 名古屋大学（愛知）
• [Presentation] Polymerization of Phenylacetylenes Using Well-defined Rhodium Catalysts (2013)
  • Author(s): Fumio Sanda, Shohei Kumazawa, Jesus Rodriguez Castanon, Naoya Onishi, Masashi Shiotsuki
  • Organizer: IUPAC International Symposium on Ionic Polymerization 2013
  • Place of Presentation: 淡路夢舞台国際会議場（兵庫）
  • Invited
• [Presentation] Synthesis and Stimuli-Response of Helically Folded Poly(phenyleneethynylene)s (2013)
  • Author(s): Fumio Sanda
  • Organizer: International Symposium on Stimuli-Responsive Materials
  • Place of Presentation: Santa Rosa, USA
  • Invited
• [Presentation] Synthesis and Photoresponse of Helically Folded Poly(phenyleneethynylene)s Bearing Azobenzene Moieties (2013)
  • Author(s): Fumio Sanda, Hiromitsu Sogawa, Masashi Shiotsuki
  • Organizer: The 13th Pacific Polymer Conference
  • Place of Presentation: Kaohsiung, Taiwan
  • Invited
• [Presentation] Development of Bulky Monophosphine-Ligated Palladium Catalysts for the Polymerization of Disubstituted Acetylenes (2013)
  • Author(s): Jesus Rodriguez Castanon, Masashi Shiotsuki, Fumio Sanda
  • Organizer: 第62回高分子学会年次大会
  • Place of Presentation: 国立京都国際会館（京都）
• [Presentation] 含金属光学活性共役ポリマーの合成と特性 (2013)
  • Author(s): 宮城 雄, 曽川洋光, 三田文雄
  • Organizer: 第62回高分子学会年次大会
  • Place of Presentation: 国立京都国際会館（京都）
• [Presentation] Application of Bulky Phosphine-Ligated Palladium Catalysts to the Polymerization of 1-Chloro-2-Arylacetylenes (2013)
  • Author(s): Jesus Rodriguez Castanon, Masashi Shiotsuki, Natsuhiro Sano, Fumio Sanda
  • Organizer: 第62回高分子討論会
  • Place of Presentation: 金沢大学（石川）
• [Presentation] 金属を含有する光学活性共役高分子の合成と特性 (2013)
  • Author(s): 宮城 雄, 曽川洋光, 三田文雄
  • Organizer: 第62回高分子討論会
  • Place of Presentation: 金沢大学（石川）
• [Presentation] Synthesis of Optically Active Poly(m-phenyleneethynylene-aryleneethynylene)s Bearing Hydroxy Groups and Examination of the Higher Order Structures (2012)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Fumio Sanda
  • Organizer: World Polymer Congress MACRO 2012, 44th International symposium on Macromolecules
  • Place of Presentation: Virginia Tech, Blacksburg, VA, USA
• [Presentation] Synthesis and Properties of Optically Active Poly(m-phenyleneethynylene-aryleneethynylene)s Bearing Hydroxy Groups with Various Conjugation Lengths (2012)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Fumio Sanda
  • Organizer: The Seventh International Forum on Chemistry of Functional Organic Chemicals (IFOC07) 2012

  • Place of Presentation: The University of Tokyo, Tokyo, Japan
• [Presentation] Synthesis and Chiroptical Properties of Hydroxyphenylglycine-Based Helical Poly (Phenyleneethynylene) s (2011)
  • Author(s): Fumio Sanda, Akinobu Hashimoto, Hiromitsu Sogawa, Ruiyuan Liu, Masashi Shiotsuki, Toshio Masuda
  • Organizer: IUPAC 7th International Conference on Novel Materials and Synthesis (NMS-VII) & 21st International Symposium on Fine Chemistry and Functional Polymers (FCFP-XXI)
  • Place of Presentation: Fudan大学(上海,中国)(招待講演)
  • Year and Date: 2011-10-18
• [Presentation] らせん共役高分子側鎖上でのメタセシス重合による高次構造の安定化 (2011)
  • Author(s): 橋本明徳, 曽川洋光, 塩月雅士, 三田文雄
  • Organizer: 第60回高分子討論会
  • Place of Presentation: 岡山大学(岡山県)
  • Year and Date: 2011-09-28
• [Presentation] アミノ酸由来のジインモノマーの酸化カップリング重合による新規共役ポリマーの合成 (2011)
  • Author(s): 上田季子, 塩月雅士, 三田文雄
  • Organizer: 第60回高分子学会年次大会
  • Place of Presentation: 大阪国際会議場(大阪府)
  • Year and Date: 2011-05-26
• [Presentation] らせん共役高分子側鎖上での開環メタセシス重合による高次構造の安定化 (2011)
  • Author(s): 橋本明徳, 曽川洋光, 塩月雅士, 三田文雄
  • Organizer: 第60回高分子学会年次大会
  • Place of Presentation: 大阪国際会議場(大阪府)
  • Year and Date: 2011-05-25
• [Presentation] Synthesis and properties of amino acid based optically active photo-responsive poly(phenyleneethynylene)s (2010)
  • Author(s): Hiromitsu Sogawa, Masashi Shiotsuki, Fumio Sanda
  • Organizer: The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu Convention Center, Hawaii, USA
  • Year and Date: 2010-12-18
• [Presentation] アゾベンゼン含有光学活性ポリ(メタフェニレンエチニレン)の合成と特性 (2010)
  • Author(s): 曽川洋光, 塩月雅士, 三田文雄
  • Organizer: 第59回高分子討論会
  • Place of Presentation: 北海道大学
  • Year and Date: 2010-09-15
• [Presentation] アミノ酸を不斉源とする光学活性ケイ素含有共役ポリマーの合成 (2010)
  • Author(s): 上田季子, 塩月雅士, 三田文雄
  • Organizer: 第56回高分子研究発表会(神戸)
  • Place of Presentation: 兵庫県民会館
  • Year and Date: 2010-07-16
• [Presentation] アゾベンゼン含有新規光学活性ポリフェニレンエチニレンの合成と特性 (2010)
  • Author(s): 飛塚祐哉, 曽川洋光, 塩月雅士, 三田文雄
  • Organizer: 第56回高分子研究発表会(神戸)
  • Place of Presentation: 兵庫県民会館
  • Year and Date: 2010-07-16
• [Presentation] アミノ酸を不斉源とする新規光学活性ポリ(フェニレンエチニレン)の合成と特性 (2010)
  • Author(s): 曽川洋光, 塩月雅士, 三田文雄
  • Organizer: 第59回高分子学会年次大会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2010-05-27
• [Presentation] フェニレンエチニレン系光学活性共役高分子の合成と高次構造制御
  • Author(s): 三田文雄
  • Organizer: 長州ポリマー研究会第3回講演会
  • Place of Presentation: 山口大学
  • Invited
• [Presentation] 共役高分子の精密合成と高次構造制御
  • Author(s): 三田文雄
  • Organizer: 高分子合成シンポジウム京都2014
  • Place of Presentation: メルパルク京都（京都）
  • Invited
• [Presentation] 光学活性ポリフェニレンエチニレンの合成とモノマー単位の共役長が高次構造に及ぼす影響の検討
  • Author(s): 曽川 洋光・塩月 雅士・三田 文雄
  • Organizer: 第61回高分子学会年次大会
  • Place of Presentation: パシフィコ横浜
• [Presentation] m-ターフェニレン構造を有する光学活性共役ポリマーの合成と特性
  • Author(s): 宮城 雄・曽川 洋光・塩月 雅士・三田 文雄
  • Organizer: 第61回高分子学会年次大会
  • Place of Presentation: パシフィコ横浜
• [Presentation] 光学活性ポリフェニレンエチニレンの合成と側鎖間相互作用
  • Author(s): 橋本明徳・曽川洋光・三田文雄
  • Organizer: 第58回高分子研究発表会（神戸）
  • Place of Presentation: 兵庫県民会館
• [Presentation] 光学活性ポリフェニレンエチニレンの合成とモノマー単位の共役長が高次構造に及ぼす影響の検討
  • Author(s): 曽川 洋光, 塩月 雅士, 三田 文雄
  • Organizer: 第61回高分子討論会
  • Place of Presentation: 名古屋工業大学
• [Presentation] 種々の光学活性ポリ(メタフェニレンエチニレンアリーレンエチニレン)の合成と共役長が高次構造に及ぼす影響の検討
  • Author(s): 曽川 洋光, 塩月 雅士, 三田 文雄
  • Organizer: 第61回高分子討論会
  • Place of Presentation: 名古屋工業大学
• [Presentation] m-ターフェニレン構造を有する光学活性共役ポリマーの合成と特性
  • Author(s): 宮城 雄, 曽川 洋光, 塩月 雅士, 三田 文雄
  • Organizer: 第61回高分子討論会
  • Place of Presentation: 名古屋工業大学
• [Presentation] アミノ酸を不斉源に活用する光学活性共役高分子の合成と側鎖でのネットワーク形成による高次構造の安定化
  • Author(s): 三田文雄・橋本明徳・曽川洋光・塩月雅士
  • Organizer: 第62回ネットワークポリマー講演討論会
  • Place of Presentation: 三重大学
• [Book] Substituted Polyacetylenes,Toshio Masuda in Conjugated Polymers: A Practical Guide to Synthesis (2013)
  • Author(s): Fumio Sanda, Masashi Shiotsuki, Klaus Müllen, John R. Reynolds, Toshio Masuda Eds
• [Book] Conjugated Polymers: A Practical Guide to Synthesis (2013)
  • Author(s): Fumio Sanda, Masashi Shiotsuki, Toshio Masuda
  • Total Pages: 24
  • Publisher: Royal Society of Chemistry
• [Book] Encyclopedia of Polymeric Nanomaterials (2013)
  • Author(s): Fumio Sanda
  • Total Pages: 2
  • Publisher: Springer-Verlag
• [Remarks]
  • URL: http://www2.itc.kansai-u.ac.jp/~sanda/index.html
• [Remarks]
  • URL: http://adv.polym.kyoto-u.ac.jp/
• [Remarks]
  • URL: http://adv.polym.kyoto-u.ac.jp/