Supermolecular Ladder Chiral Double Helical Polymer by Helix-sense-selective Polymerization Controlled by Achiral Values

非手性值控制的螺旋有义选择性聚合制备超分子梯手性双螺旋聚合物

• 批准号: 16350061
• 负责人: AOKI Toshiki
• 金额: $ 9.09万
• 依托单位: Niigata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16350061/
• 关键词: Helix-sense-selective Polymerization; Supermolecule; Ladder Polymer; Chiral polymer; Double Helical Polymer; Control of Polymerization; Asymmetric Recognition

The investigators of this research project found an induced chirality in the main chain when a phenylacetylene having a bulky chiral substituent was polymerized. We thought this chiral structure did not contain asymmetric centers and was caused only by one-handed helical conformation. However, this chiral polymer contained two kinds of chiral structures and therefore the recognition ability and the precise structure of the chiral main chain itself could not be confirmed.To clarify it we realized synthesis of a chiral helical polyphenylacetylene which does not have any other chiral moieties by helix-sense-selective polymerization of an achiral monomer with a chiral catalytic system. In addition, we found the helix sense can be controlled by changing not only chiral amounts but also achiral amounts. And the chiral main-chain of the resulting polymer was found to be maintained by intramolecular hydrogen bonds, i.e., this polymer has a supermolecular ladder chiral double helical polymer structure. Therefore this main chain chirality disappeared when a polar solvent was added.In this study, we studied further the following points on the new synthetic method and the new polymer obtained by the method.(1) Generalization of the helix-sense-selective polymerization(2) Discussion of the mechanism of the helix-sense-selective polymerization(3) Development of new functions of the supermolecular ladder chiral double helical polymer(4) Discussion of the molecular structure of the supermolecular ladder chiral double helical polymer

这项研究项目的研究人员发现，当具有大量手性取代基的苯乙炔聚合时，主链上有诱导手性。我们认为这种手性结构不包含不对称中心，只是由单手螺旋构象引起的。然而，这种手性聚合物含有两种手性结构，因此手性主链本身的识别能力和精确结构无法确定。为了阐明这一点，我们通过手性催化体系中的非手性单体螺旋选择性聚合，合成了不含任何其他手性基团的手性螺旋聚苯乙炔。此外，我们还发现，不仅可以通过改变手性量，还可以通过改变非手性量来控制螺旋的感觉。所得聚合物的手性主链由分子内氢键维持，即该聚合物具有超分子梯形手性双螺旋聚合物结构。在本研究中，我们进一步研究了以下几点：(1)螺旋选择性聚合的概化；(2)螺旋选择性聚合机理的探讨；(3)超分子梯形手性双螺旋聚合物新功能的开发；(4)超分子梯形手性双螺旋聚合物分子结构的讨论

项目成果

Helix-sense-selective polymerization of a phenylacetylene bearing an achiral and bulky galvinoxyl moiety

• DOI: 10.1246/cl.2005.854
• 发表时间: 2005-06-05
• 期刊: CHEMISTRY LETTERS
• 影响因子: 1.6
• 作者: Umeda, Y;Kaneko, T;Aoki, T
• 通讯作者: Aoki, T

Synthesis of Chiral Helical Poly(hydroxyl-containing phenylacetylene) Membranes by in-Situ Depinanylsilylation and Their Enantioselective Permeabilities

• DOI: 10.1021/ma050089z
• 发表时间: 2005-06
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: M. Teraguchi;Kazuomi Mottate;Sunyoung Kim;T. Aoki;T. Kaneko;Shingo Hadano;T. Masuda

Synthesis of chiral helical poly[p‐(oligopinanylsiloxanyl)phenylacetylene]s and enantioselective permeability of their membranes

• DOI: 10.1002/pola.20356
• 发表时间: 2004-09
• 期刊: Journal of Polymer Science Part A
• 作者: T. Aoki;Tomoyuki Fukuda;K. Shinohara;T. Kaneko;M. Teraguchi;M. Yagi

Enantioselective permeability through membranes from a poly(substituted phenylacetylene) having a chiral helical backbone and achiral bidentate ligands as pendant groups

• DOI: 10.1246/cl.2007.220
• 发表时间: 2007-02-05
• 期刊: CHEMISTRY LETTERS
• 影响因子: 1.6
• 作者: Hadano, Shingo;Teraguchi, Masahiro;Aoki, Toshiki
• 通讯作者: Aoki, Toshiki

主鎖のらせんのみに起因する不斉を持つポリフェニルアセチレンの合成-アキラルフェニルアセチレンのらせん選択重合とキラル置換ポリフェニルアセチレンの脱置換基-

仅因主链螺旋而具有手性的聚苯乙炔的合成 - 非手性苯乙炔的螺旋选择性聚合和手性取代聚苯乙炔的去取代 -

• 发表时间: 2005
• 期刊: 高分子加工 54(12)
• 作者: 寺尾 潤;神戸宣明;青木俊樹
• 通讯作者: 青木俊樹