| 高分子 Vol.71 No.4 |
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特集 進撃の環状 “巨” 分子
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| 展望 COVER STORY: Highlight Reviews |
| π共役系巨大マクロサイクル π-Conjugated Giant Macrocycles |
西長 亨・伊與田 正彦 Tohru NISHINAGA, Masahiko IYODA |
| ＜要旨＞ 芳香環が直接繰り返して、あるいはアセチレンやエチレンでπ拡張してつながった構造をもつπ共役系に対し、さらにその両端もつなげて環状にした巨大分子は、直鎖状のπ共役高分子にはない物性や機能を発現し、近年注目を集めている。本稿では、そのようなπ共役系巨大マクロサイクルについて、その合成および特異な物性や機能について紹介する。 Keywords: π-Conjugation / Macrocycles / C60 Complex / Two-Phton Absorption / Aromaticity / Ring Current |
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| ポリマーからポリカテナンを創る Creating Polycatenanes from Polymers |
磯辺 篤・矢貝 史樹 Atsushi ISOBE, Shiki YAGAI |
| ＜要旨＞ 環状分子のみからなるポリカテナンは、特異な機械的特性などが期待できることから、多くの研究者がその効率合成に取り組んでいる次世代ポリマーである。太く大きな高分子から環構造を合成することで、プローブ顕微鏡などを用いてその構造の可視化が可能になる。本項では、環状高分子からなるポリカテナンをいくつか取り上げ、その作製法や特徴を紹介する。 Keywords: Supramolecular Polymer / Self-Assembly / Toroid / Ring / Topology / Catenane |
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| トピックス COVER STORY: Topics and Products |
| ピラー［5］アレーン一次元チューブの創出 Creation of One-Dimensional Tubular Structures Based on Pillar[5]arenes |
大谷 俊介・生越 友樹 Shunsuke OHTANI, Tomoki OGOSHI |
| ＜要旨＞ Pillar[n]arenes, which were first reported by our group in 2008, are new macrocyclic compounds in supramolecular chemistry. Based on the highly symmetrical structures, one-dimensional (1D) tubular structures can be formed by connecting pillar[n]arenes via non-covalent interactions between the functional groups at the both rims. This article describes the formation and length control of self-assembled 1D tubular structures of pillar[5]arenes. Keywords: Macrocyclic Compound / Host-Guest Chemistry / Supramolecular Chemistry / One-Dimensional Tubular Structure |
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| 柔軟なトリペプチドからの巨大環状錯体形成 Formation of Giant Cyclic Complexes Using a Flexible Tripeptide |
三宅亮介 Ryosuke MIYAKE |
| ＜要旨＞ Herein, we describe the formation of giant cyclic complexes from a small, flexible tripeptide possessing three kinds of metal coordinating sites. Giant cavities (diameter: ca. 2 nm) was formed by connecting 14 artificial tripeptides and 14 Ni(Ⅱ) ions. A mesh-like structure should be important feature for the formation of the giant structures from the flexible tripeptide: three tripeptides connected to a octahedral Ni(Ⅱ) center by tridentate, bidentate, and monodentate binding sites to form the mesh-like structure. The structural and theoretical studies suggested that the metal coordination bonds at the tridentate binding site, which includes the O atoms of the amide groups in the peptide backbone, control the conformation of flexible tripeptides, supported by intramolecular hydrogen bonds. The design principle and possibility of metal complexes of short peptides to form giant structures is also discussed in this topic article. Keywords: Peptides / Formation of Giant Structures / Cyclic Metal Complexes / Flexible Tripeptide / Self-Assembly |
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| キラル環状π共役分子を芳香環構築で作る Creating Chiral Cyclic π-Conjugated Molecules by Aromatic Ring Construction |
野上 純太郎・田中 健 Juntaro NOGAMI, Ken TANAKA |
| ＜要旨＞ Cyclic π-conjugated molecules have an interesting π-conjugated structure with no ends and are expected to be applied as light-emitting materials and semiconductor materials. However, their syntheses require overcoming the large distortion of the molecule, which has been a challenging target in synthetic organic chemistry. Following the synthesis of carbon nanorings and carbon nanobelts, Isobe succeeded in synthesizing a chiral cyclic π-conjugated molecule and exhibited its extraordinary circularly polarized luminescence property. However, this molecule was obtained as a mixture of diastereomers and enantiomers using multiple coupling reactions. Our research group discovered in 2003 that a cationic rhodium(Ⅰ)/biaryl bisphosphine complex exhibits extremely high activity and selectivity for the [2+2+2] cycloaddition reaction of alkynes. Then, we applied this reaction to the intramolecular [2+2+2] cycloaddition reactions of cyclic polyynes and achieved the asymmetric synthesis of various chiral cyclic π-conjugated molecules. Keywords: Alkynes / Aromatic Ring Construction / Asymmetric Catalysis / Chiral Cyclic π-Conjugated Molecules / Cycloparaphenylenes / Polyynes / Rhodium / [2+2+2] Cycloaddition |
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| 環状分子とキラリティ Chiral Macrocycles Based on the Assembly of Phenylacetylenes as a Building Block |
上遠野 亮 Ryo KATOONO |
| ＜要旨＞ I describe herein chiral macrocycles in two parts, monocyclic and polycyclic. The first part shows chiral monomacrocycles based on a single ring that is helically folded in a molecule. Folding of a ring provides a diverse array of chiral fashions, while for linear molecules, folding is often associated with a helix as a representative. Through the cooperative transmission of external and internal chirality to a racemic pair of enantiomerically-folded macrocycles, a particular sense of (M)- or (P)-helicity can be preferred to show unique optical activities. In the second part, a variety of chiral polymacrocycles are demonstrated. There are several cases where a molecule possesses multiple rings or no rings, the stereochemistry is assured or not. Depending on the situations, several issues (new structure creation, unique helical-sense control with no use of stereogenic centers, and pluralistic transmission of chirality, etc.) are discussed. All macrocycles here are built up with phenylacetylene and terephthalamide units. Keywords: Terephthalamide / Macrocycle / Triple Bond (Phenylacetylene) / Chirality |
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| 二次核形成という素過程を利用した精密超分子重合 Precision Supramolecular Polymerization Using Secondary Nucleation |
佐々木 紀彦・杉安 和憲 Norihiko SASAKI, Kazunori SUGIYASU |
| ＜要旨＞ We have designed a porphyrin derivative that has fluorinated side chains. Interestingly, this molecule self-assembled into concentric toroids. AFM observation unveiled its growth mechanism in which secondary nucleation played an important role. Based on this understanding, we succeeded in controlling the size of the concentric toroid through seeded supramolecular polymerization. Keywords: Supramolecular Polymers / Living Supramolecular Polymerization / Secondary Nucleation / Porphyrins / Concentric Toroids |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| なにものにもこだわらない（または身軽さ） Aiming for Freedom to Everything (or Quick Working) |
稲葉 央 Hiroshi INABA |
| ＜要旨＞ My recent motto is “Aiming for freedom to everything”. Because of the previous experience, I became a cynical researcher who does not want to do trendy research. I want to enjoy research in a light-hearted way, without being particular about anything. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 細胞操作変数としての高分子基材の変形特性 Polymer Substrate Deformability as a Designing Parameter of Biomaterials for Cell Manipulation |
政池 彩雅・木戸秋 悟 Sayaka MASAIKE, Satoru KIDOAKI |
| ＜要旨＞ Recent developments in cell manipulation technology on the biomaterials through designing the mechanical properties of polymer materials are reviewed. We focus on the deformability of a polymer matrix or a substrate as an essential parameter for cell manipulation such as on cell adhesion, proliferation, motility, and differentiation. Various modes of cell manipulation by a elastic or viscoelastic polymer matrix are summarized. In particular, the effect of microscopic deformation of a solid polymer substrate surface on cell manipulation is discussed from the views of cell-traction-force-induced microscopic stain on the biomaterials surface. Relating to the mechanism on those cell manipulations, recent developments in molecular clutch theory are outlined, which explain the kinetic behaviors of growth and reduction of cell adhesion machinery depending on the condition of deformation velocity of the polymer matrix. The emerging research field that integrates cell biology and polymer materials engineering are reviewed in terms of mechanical design of cell manipulation materials. Keywords: Cell Manipulation / Deformability / Elasticity / Viscoelasticity / Cell Adhesion / Molecular Clutch |
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