Development of Materials with Novel Properties and Functions Based on Controlled Double-Stranded Helical Structure

基于可控双链螺旋结构的新型性能和功能材料的开发

• 批准号: 20225006
• 负责人: YASHIMA Eiji
• 金额: $ 58.32万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (S)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008-06-04 至 2013-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20225006/
• 关键词: 機能性高分子; 超分子; キラリティー; 不斉触媒; キラル識別; ラセン構造; 二重ラセン; 光学活性; 高分子; ヘリケート; 転写; らせん; 生体関連高分子

In this project, we have developed a conceptually new and versatile method for constructing a variety of artificial double-stranded helical polymers and oligomers with specific functions involving chiral recognition, asymmetric catalysis, and self-replication. We have successfully synthesized a series of complementary double-stranded helical polymers and oligomers with a controlled helicity that showed unique DNA-like perfect sequence and molecular length recognition and replication via amplification of the helical chirality. The determination of the helical structures is also achieved by direct microscopic observations of the polymers. We also discovered an intriguing double helical molecule that exhibited a reversible spring-like extension-contraction motion triggered by external stimuli. We developed practically useful chiral materials for separating enantiomers and producing single enantiomers as asymmetric catalysts.

在这个项目中，我们开发了一种概念上新的和通用的方法，用于构建各种人工双链螺旋聚合物和寡聚物，具有特定的功能，包括手性识别，不对称催化和自我复制。我们已经成功地合成了一系列互补的双链螺旋聚合物和低聚物，具有可控的螺旋度，显示出独特的DNA样的完美序列和分子长度的识别和复制通过扩增的螺旋手性。螺旋结构的测定也通过聚合物的直接显微观察来实现。我们还发现了一种有趣的双螺旋分子，它表现出由外部刺激触发的可逆的弹簧样伸展-收缩运动。我们开发了具有实用价值的手性材料作为不对称催化剂，用于分离对映体和制备单一对映体。

项目成果

Effect of Polyelectrolyte Function on Helical Structures of Optically Active Poly(phenylacetylene) Derivatives Bearing Basic or Acidic Functional Pendant Groups

• DOI: 10.1021/ma201913g
• 发表时间: 2011-09
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Katsuhiro Maeda;Mitsuo Muto;Takahiro Sato;E. Yashima

Template Effects on the Formation of a Complementary Double Helix.

模板对互补双螺旋形成的影响。

• 发表时间: 2010
• 作者: H.Yamada;R.Ito;Y.Furusho;E.Yashima
• 通讯作者: E.Yashima

Design and Synthesis of [2]Catenanes Utilizing Amidinium-Carboxylate Salt Bridge Formation and Acid/Base Control of Their Catenane Structure.

利用脒-羧酸盐桥的形成和酸/碱控制其索烷结构的[2]索烷的设计和合成。

• 发表时间: 2010
• 作者: Y.Furusho;Y.Nakatani;E.Yashima
• 通讯作者: E.Yashima

Control of Extension/Contraction Motion of Boron Helicates Consisting of Oligophenol Strands.

由低聚酚链组成的硼螺旋物的伸展/收缩运动的控制。

• 发表时间: 2010
• 作者: K.Miwa;Y.Furusho;E.Yashima
• 通讯作者: E.Yashima

Two-Dimensional Bilayer Smectic Ordering of Rigid Rod−Rod Helical Diblock Polyisocyanides

• DOI: 10.1021/ma1009116
• 发表时间: 2010-07
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Motonori Banno;Zongquan Wu;Kanji Nagai;Shin-ichiro Sakurai;K. Okoshi;E. Yashima