| 高分子 Vol.64 No.11 |
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特集 ひねりの効いた分子機能
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| 展望 COVER STORY: Highlight Reviews |
| 超階層構造制御されたらせん共役ポリマー Helical Conjugated Polymers with Super-Hierarchically Controlled Structures |
赤木 和夫 Kazuo AKAGI |
| ＜要旨＞ π電子が主鎖上に非局在する共役ポリマーは、今日、電子・光機能材料として基礎および応用研究が広範囲に展開されている。同時に、次代の機能ポリマーとして、従来にない高分子構造の構築、新機能の発現、格段に優れた高機能化が強く望まれている。本稿では、超階層構造が制御されたらせん共役ポリマーを焦点に、次世代機能ポリマーを展望する。 Keywords: Conjugated Polymers / Helical Structures / Hierarchical Control / Circular Polarization / Dissymmetry Factor in Luminescence |
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| つる巻き重合による多糖超分子の合成とらせん機能の発現 Synthesis and Helical Function of Polysaccharide Supramolecules by Vine-Twining Polymerization |
門川 淳一 Jun-ichi KADOKAWA |
| ＜要旨＞ らせん状多糖のアミロースなどは種々の化合物と複合体（超分子）を形成することが知られている。近年、アミロースとゲスト高分子からの超分子（包接錯体）形成手法に関する研究が発展してきた。本報では、アミロース生成重合場での動的包接錯体形成手法およびその過程でのアミロースらせんによる機能発現を中心に解説する。 Keywords: Polysaccharide / Amylose / Enzymatic Polymerization / Inclusion Complex / Supramolecule |
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| 筒状炭素性分子（あるいはカーボンナノチューブ分子）の「ひねった」構造 Helicity in Tubular Carbonaceous Molecules (or Finite Carbon Nanotube Molecules) |
松野 太輔・磯部 寛之 Taisuke MATSUNO, Hiroyuki ISOBE |
| ＜要旨＞ sp2炭素のシートが筒状となった構造には、炭素ネットワークの連なり方に由来した特異なキラリティが生じる。本稿では、このキラリティの構造化学に焦点をあて、今後、生まれ来るであろうあまたの機能性への土台を提供したい。このキラリティの端緒となるカーボンナノチューブ（CNT）の構造から、より精緻な構造化学を要す分子性物質「有限長CNT分子」上でのキラリティまでを解説する。 Keywords: Carbon Nanotube / Chirality / Helicity / Moleculr Entity / Finite Carbon Nanotube Molecules |
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| トピックス COVER STORY: Topics and Products |
| π共役平面をひねって一回転させる Twisting of π-Conjugated Plane to One Rotation |
廣戸 聡・忍久保 洋 Satoru HIROTO, Hiroshi SHINOKUBO |
| ＜要旨＞ We have established the facile and efficient protocol to synthesize distorted π-conjugated molecules. Oxidation of amino-substituted porphyrins proceeded with high regioselectivity to produce pyrazine fused dimers. X-ray diffraction analysis revealed its highly twisted structure. Electrochemical and optical measurements indicated the twisting mostly influences on HOMO. The sequential use of our protocol has achieved the synthesis of unidirectionally twisted porphyrin tetramers efficiently. NMR analysis suggested that the racemization barrier of twisting increases on oligomerization. To the best of our knowledge, this is the first observation of a similar phenomenon observed in polymer science for twisted π-conjugated molecules. The present findings represent an important advance towards the long-term goal of preparing π-conjugated molecular wires, whose properties can be fine-tuned through molecular twisting. Keywords: Distorion / π-Conjugated Molecule / Twist / Oxidation / Porphyrin / Anthracene / Oligomer |
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| 面性不斉分子が創る光学活性π電子系 Optically Active π-Electron Systems Based on Planar Chiral Compounds |
森崎 泰弘 Yasuhiro MORISAKI |
| ＜要旨＞ Planar chirality is one of the unique properties of [2.2]paracyclophane compounds derived from suppression of the rotation of stacked phenylenes. Recently, we have developed the optical resolutions of rac-disubstituted [2.2]paracyclophane and rac-tetrasubstituted [2.2]paracyclophane. In addition, we have synthesized various optically active conjugated polymers, oligomers, and cyclic compounds based on the planar chiral [2.2]paracyclophane skeleton. The obtained optically active compounds exhibited good optical profiles, with a large molar extinction coefficient and photoluminescence quantum efficiency. The optically active higher-ordered structure provided chiroptical properties of high performance, such as a large specific rotation and molar ellipticity in the ground state and intense circularly polarized luminescence (CPL) with large dissymmetry factors in the exited state. The results suggest that planar chiral [2.2]paracyclophane-based optically active higher-ordered structures, such as the one-handed helix and propeller-shaped cyclic structure, are promising scaffolds for obtaining CPL and that appropriate modifications can enhance the CPL characteristics. Keywords: Cyclophane / Circularly Polarilzed Luminescence / Conjugated Polymer / Higher Ordered Structure / Optical Resolution / Photoluminescence / Planar Chirality |
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| 柔軟な高分子主鎖の構造変化を活用した超分子アロステリックシグナル増幅センシング Supramolecular Allosteric Signal-amplification Sensing Based on the Structural Changes of Flexible Polymer Backbones |
福原 学 Gaku FUKUHARA |
| ＜要旨＞ Supramolecular sensing with polymers has attracted much attention not only in fundamental science but also in a number of practical applications, since polymers can amplify binding events to greatly enhance signal gains upon interactions with analytes. We have recently developed a novel polymer-based sensing strategy, “supramolecular allosteric signal-amplification sensing”. In this Topics, the novel sensing systems with recent our examples are highlighted. Keywords: Allosterism / Polythiophene / Curdlan / Chirality / Amino Acids / Peptides / Oligosaccharides |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 研究の境界領域 Interdisciplinary Research Fields |
春藤 淳臣 Atsuomi SHUNDO |
| ＜要旨＞ I have traveled around several research fields. New findings and insights may exist in between the interdisciplinary research fields. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 液晶のトポロジカル欠陥と高分子の相互作用 Interaction between Topological Defects of Liquid Crystals and Polymers |
菊池 裕嗣・樋口 博紀・奥村 泰志・東口 顕士 Hirotsugu KIKUCHI, Hiroki HIGUCHI, Yasushi OKUMURA, Kenji HIGASHIGUCHI |
| ＜要旨＞ Around the topological defects of a liquid crystal, there are gradients of the director distortions and the orientational order, where a long range elastic force field is created. When polymers are placed in the field, an attractive force along the gradient, toward the defect core, is imposed to the particles. By this long-range force, the particles are migrated and finally trapped by the defect. The polymer-stabilized liquid crystal blue phases, which show fast electro-optic effect, are stabilized by this kind of effect. Recent research progresses on the related phenomena are briefly reviewed in this paper. Keywords: Liquid Crystal / Topological Defect / Particles / Blue Phase |
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