Synthesis of Polymer Membranes Having Optically Active Nanopores Arrayed in Helical Manner for Membrane Separation

• Project/Area Number: 25390002
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Nanostructural chemistry
• Research Institution: Niigata University
• Principal Investigator: TERAGUCHI MASAHIRO 新潟大学, 自然科学系, 助教 (30334650)
• Co-Investigator(Renkei-kenkyūsha): AOKI TOSHIKI 新潟大学, 自然科学系, 教授 (80212372) ; KANEKO TAKASHI 新潟大学, 自然科学系, 教授 (90272856)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2014: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2013: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: らせんポリマー / 光学活性ポリマー / らせん選択重合 / 脱置換基反応 / 分離膜 / 光学分割膜 / ナノ空孔 / 誘起片巻きらせん構造 / 光学分割 / 光学活性イオン液体 / 溶媒効果

Outline of Final Research Achievements

Synthesis of stereoregular one-handed helical polymers by polymerization of chiral monomers using a chiral catalyst and achiral monomers using a chiral catalyst in helix-sense-selective manner, or a chiral-helix induction to achiral polymers in chiral solvents was investigated, and their free-standing membranes were fabricated by solvent casting method. By removal of the chiral substituents in the polymer in membrane reaction, synthesis of polymer membranes having chiral nanopores arranged in helical manner was achieved. These membranes showed an enantioselective permeability.

Research Products

• [Journal Article] Novel Isolated, L-Amino Acid-Ligated Rhodium Catalysts that Induce Highly Helix-Sense-Selective Polymerization of an Achiral 3,4,5-Trisubstituted Phenylacetylene (2016)
  • Author(s): Hongge Jia*, Yongqiang Shi, Liqun Ma, Xuan Gao, Yazhen Wang, Yu Zang, Jijun Peng, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Toshio Masuda
  • Journal Title: J. Polym. Sci., Part A: Polym. Chem. Volume: 54 Issue: 15 Pages: 2346-2351
  • DOI: 10.1002/pola.28106
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Influence of Hydrodynamic Environment on Chain Rigidity, Liquid Crystallinity, Absorptivity, and Photoluminescence of Hydrogen-Bonding-Assisted Helical Poly(phenylacetylene) (2016)
  • Author(s): Young-Jae Jin, Hyojin Kim, Mari Miyata, Guanwu Yin, Takashi Kaneko, Masahiro Teraguchi, Toshiki Aoki, Giseop Kwak*
  • Journal Title: RSC Advances Volume: 6 Issue: 43 Pages: 36661-36666
  • DOI: 10.1039/c6ra01940d
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Highly Selective Photocyclic Aromatization (SCAT) - GPC Method for Quantitative Determination of Microstructures of Copoly(Substituted Acetylenes) Backbone (2016)
  • Author(s): Guanwu Yin, Lijia Liu, Toshiki Aoki, Takeshi Namikoshi, Masahiro Teraguchi, Takashi Kaneko
  • Journal Title: Chem. Lett. Volume: 45
  • NAID: 130005253016
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Helical Conformation Stability of Poly[3,5-bis(hydroxymethyl)phenylacetylene]s Depending on the Length of Their Rigid and Linear π-Conjugated Side Groups (2015)
  • Author(s): Zhichun Shi, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko
  • Journal Title: Chemistry Letters Volume: 44 Issue: 10 Pages: 1413-1415
  • DOI: 10.1246/cl.150616
  • NAID: 130005101477
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Quantitative introduction of perfluoroalkyl groups to poly(diphenylacetylenes) membranes via three-step membrane reaction including click reaction and their gas permeability (2015)
  • Author(s): Masahiro Teraguchi, Takashi Sato, Motohiro Kiuchi, Takashi Kaneko, Toshiki Aoki
  • Journal Title: Chem. Lett. Volume: 44 Issue: 12 Pages: 1679-1681
  • DOI: 10.1246/cl.150841
  • NAID: 130005112514
  • Peer Reviewed
• [Journal Article] Highly efficient helix-sense-selective polymerization of an achiral phenylacetylene having a bulky group (2015)
  • Author(s): Yanqing Qu, Yu Zang, Mingyu Zhang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko, Liqun Ma, Hongge Jia
  • Journal Title: Chem. Lett. Volume: 44 Issue: 12 Pages: 1777-1779
  • DOI: 10.1246/cl.150863
  • NAID: 130005112520
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Catalytic Helix-Sense-Selective Polymerisation of Achiral Substituted Acetylenes Containing Bulky π-Conjugated Planar Substituents Yielding Soluble and Statically Stable One-Handed Helical Polymers (2015)
  • Author(s): Y. Zang,X. Wang,W. Zhang,T. Aoki,M. Teraguchi,T. Kaneko L. Maa and H. Jiaa
  • Journal Title: RSC Advances Volume: 5 Issue: 129 Pages: 106819-106823
  • DOI: 10.1039/c5ra20211f
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and Enantioselective Permeability of One-handed Helical Multihydroxy Poly(phenylacetylene) Membrane by In Situ Removal of the Original Chiral Substituents (2014)
  • Author(s): Lijia Liu, Kazuomi Mottate, Toshiki Aoki,* Takashi Kaneko,2 and Masahiro Teraguchi
  • Journal Title: Chemistry Letters Volume: 43 Issue: 2 Pages: 237-239
  • DOI: 10.1246/cl.130896
  • NAID: 130004867973
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Chiral Amplification during Asymmetric-Induced Copolymerization of Phenylacetylenes with Tight Cis-Cisoidal Main Chains (2013)
  • Author(s): Lijia Liu,* Kazuomi Mottate, Geng Zhang, Toshiki Aoki,* Masahiro Teraguchi, Takashi Kaneko
  • Journal Title: Macromol. Rapid Commun. Volume: 34 Issue: 14 Pages: 1140-1144
  • DOI: 10.1002/marc.201300318
  • Peer Reviewed
• [Presentation] Synthesis of self-standing 2D polymer membranes (7): By ADMET 2D polymerization of supramolecular polymers of cyclic trimers of phenylacetylenes prepared by highly selective photocyclic aromatization (2015)
  • Author(s): Shiori Sato, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societes (PACIFICHEM 2015)
  • Place of Presentation: Hawaii, USA,
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Helix-sense-selective photodegradation of racemic helical poly(substituted phenylacetylene)s by highly selective photocyclic aromatization (SCAT) using circularly polarized light (CPL) (2015)
  • Author(s): Mari Miyata, Masahiro Teraguchi, Takashi Kaneko, Toshiki Aoki
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societes (PACIFICHEM 2015)
  • Place of Presentation: Hawaii, USA,
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Synthesis of novel multistaranded copolymers by postpolymerization of template poly(substituted phenylacetylenes) (2015)
  • Author(s): Kaori Sono, Kana Matsui, Yu Zang, Toshiki Aoki, Masahiro Teraguchi, Takashi Kaneko
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societes (PACIFICHEM 2015)
  • Place of Presentation: Hawaii, USA,
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Helix-sense-selective polymerization of 3,5-bis(hydroxymethyl)phenylacetylene bearing rigid and branched aryl groups and their chiroptical properties (2015)
  • Author(s): Zhichun Shi, Masahiro Teraguchi, Toshiki Aoki, Takashi Kaneko
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societes (PACIFICHEM 2015)
  • Place of Presentation: Hawaii, USA,
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] ヒドロキシメチル基を有するポリ(1,3-フェニレンエチニレン)のらせん形成能と分子内架橋により固定化されたらせん構造の構築 (2015)
  • Author(s): 吉澤一平、寺口昌宏、青木俊樹、金子隆司
  • Organizer: 第64回高分子学会北陸支部研究発表会
  • Place of Presentation: 石川ハイテクセンター（石川県能美市）
  • Year and Date: 2015-11-15
• [Presentation] ホルミル基を有するポリ(1,3-フェニレンエチニレン)の合成と動的共有結合性分子内架橋によるらせん構造の固定化 (2015)
  • Author(s): 若田部悟史、寺口昌宏、青木俊樹、金子隆司
  • Organizer: 第64回高分子学会北陸支部研究発表会
  • Place of Presentation: 石川ハイテクセンター（石川県能美市）
  • Year and Date: 2015-11-15
• [Presentation] ラセミらせんポリ置換フェニルアセチレンの円偏光を用いる高選択光環化芳香族化分解(SCAT)によるキラルポリマー膜の合成 (2015)
  • Author(s): 宮田真理、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 東北大学川内キャンパス(宮城県仙台市)
  • Year and Date: 2015-09-17
• [Presentation] シスシソイダルらせんポリ置換アセチレンの高選択光環化芳香族化分解による超分子ポリマー膜の合成と選択透過性 (2015)
  • Author(s): 王建軍、大高絵里、宮田真理、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 東北大学川内キャンパス(宮城県仙台市)
  • Year and Date: 2015-09-17
• [Presentation] 自立型2Dポリマー(2DP)膜の合成(7)～シス-シソイダルポリフェニルアセチレンのペンダント末端官能基の高分子間重縮合体膜の合成と高選択光環化芳香族化分解(SCAT)およびグラフト化による可溶化～ (2015)
  • Author(s): 山下恭平、森谷まどか、勝然勇也、宮田真理、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 東北大学川内キャンパス(宮城県仙台市)
  • Year and Date: 2015-09-15
• [Presentation] 円偏光を用いた高選択光環化芳香族化分解(SCAT)によるラセミらせんポリ置換フェニルアセチレンの速度論的光学分割 (2015)
  • Author(s): 宮田真理、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第64回高分子学会年次大会
  • Place of Presentation: 札幌コンベンションセンター(北海道札幌市）
  • Year and Date: 2015-05-28
• [Presentation] 側鎖にフェニルニトロニルニトロキシド残基とニトロニルニトロキシド残基を有するポリ(1,3-フェニレンエチニレン)型キラルポリラジカルの合成とらせん折り畳み形成 (2015)
  • Author(s): 老田一生、寺口昌宏、青木俊樹、金子隆司
  • Organizer: 第64回高分子学会年次大会
  • Place of Presentation: 札幌コンベンションセンター(北海道札幌市）
  • Year and Date: 2015-05-28
• [Presentation] シス-トランソイダル型ポリフェニルアセチレン誘導体膜の脱水素環化反応によるグラフェンナノリボンの合成 (2015)
  • Author(s): 深井拓也、齋藤龍輔、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第64回高分子学会年次大会
  • Place of Presentation: 札幌コンベンションセンター(北海道札幌市）
  • Year and Date: 2015-05-27
• [Presentation] 主鎖のみに不斉を有する置換ポリジフェニルアセチレンおよびイオン液体含有アセチレンポリマーの合成と光学異性体選択透過性 (2015)
  • Author(s): 伊藤達也、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 日本膜学会第３７年会
  • Place of Presentation: 早稲田大学
  • Year and Date: 2015-05-14 – 2015-05-15
• [Presentation] らせん選択重合(HSSP)で得られた堅い平面板状イミノ置換基を有する片巻きらせんポリフェニルアセチレンの定量的高分子膜反応(RIM) (2014)
  • Author(s): 宮田真理、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎（長崎大学 文教キャンパス）
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] 低分子量体を用いた超高分子量シス-シソイダルポリフェニルアセチレン片巻きらせん選択重合体の分子構造の解明 (2013)
  • Author(s): 筒場豊和、寺口昌宏、金子隆司、青木俊樹
  • Organizer: 第62回高分子討論会
  • Place of Presentation: 金沢大学 角間キャンパス