| 高分子 Vol.63 No.12 |
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特集 「あつまり」と「ふるまい」から問う：高分子らしさとは？
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| 展望 COVER STORY: Highlight Reviews |
| 単一高分子の自己秩序形成 Self-Organization in a Single Molecular Chain |
吉川 研一 Kenichi YOSHIKAWA |
| ＜要旨＞ 生体のゲノム分子は、全長がmm-cmときわめて長い。このような長いDNAは、従来の分子生物学の研究対象のキロ塩基対程度のDNAとは異なり、顕著な“高分子特性”を示す。「単一のDNAの折り畳み構造」、「1分子鎖相分離」、「細胞サイズの混雑効果」などの話題を紹介。合成高分子系でも同様な特性は実現可能と予想される。 Keywords: Genomic DNA / Single Macromolecules / Self-Organization / Nano-Ordered Structure / Folding Transition / Micro-Confinement |
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| 液晶高分子の協同的なふるまい－光応答の視点から Cooperative Effects in Photoresponsive Liquid Crystalline Polymers |
関 隆広 Takahiro SEKI |
| ＜要旨＞ 側鎖型の液晶高分子材料では、強い分子配向の協同性をともなって、側鎖の分子レベルの動きがメゾスコピック、あるいは巨視的な動きへと変換される。アゾベンゼンの光異性化応答をトリガーとした液晶高分子の動的機能に関して、分子配向作用、物質移動作用、運動作用に焦点をあてて、最近のトピックスを中心に多様な展開を概観する。 Keywords: Liquid Crystalline Polymers / Photoresponsive Films / Azobenzene / Linearly Polarized Light / Photoalignment / Photo-Driven Migrations / Photomechanical Effects |
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| 超分子相互作用を駆使した新しい温度応答性高分子の開発 Novel Molecular Design for Thermo-Sensitive Polymers on the Basis of Supramolecular Interaction |
佐田 和己・小門 憲太 Kazuki SADA, Kenta KOKADO |
| ＜要旨＞ 超分子化学的にデザインした自己会合性の高いホモポリマーを利用し、媒質と高分子の両者と親和性の高い第三成分（エフェクター）を添加することで、容易に高分子の温度応答性が制御できることを示し、温度応答性高分子の新しい分子設計を提案する。 Keywords: Thermo-Sensitive Polymer / Supramolecular Interaction / LCST(Lower Critical Solution Temperature) / UCST(Upper Critical Solution Temperature) / Solubility / Hydrogen Bond / Charge Transfer Interaction |
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| 会合性高分子にみる高分子らしさ Polymer Characteristics Observed in Associating Polymers |
古賀 毅 Tsuyoshi KOGA |
| ＜要旨＞ 高分子鎖に沿って多くの会合基を有する会合性高分子では、「高分子らしさ」が分子内会合という「あつまり」によって消失するが、それが外部からの刺激によって解放されるとき、劇的な物性変化という特異な「ふるまい」を見せる。そのような会合性高分子に関する研究例を紹介し、「高分子らしさ」について考察する。 Keywords: Associating Polymer / Intramolecular Micelle / Force-Elongation Relation / Rheology / Shear Thickening / Shear-Induced Gelation / Shake Gel / Molecular Simulation |
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| リビング超分子重合の実現 Living Supramolecular Polymerization |
杉安 和憲・大城 宗一郎・竹内 正之 Kazunori SUGIYASU, Soichiro OGI, Masayuki TAKEUCHI |
| ＜要旨＞ ポリマーの精密合成を可能にするリビング重合の学術的・産業的なインパクトは、すでに歴史によって証明されている。超分子ポリマーに対しても「リビング超分子重合」が実現すれば、超分子ポリマーの発展に大きなブレークスルーをもたらすと期待される。リビング超分子重合について現状と可能性を踏まえた上で、筆者らの研究例を紹介する。 Keywords: Supramolecular Polymerization / Living Polymerization / Far-from-Equilibrium Thermodynamic Systems |
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| トピックス COVER STORY: Topics and Products |
| らせん高分子の動的特性を活用したキラル識別材料 Chiral Discrimination Materials Based on Dynamic Nature of Helical Polymers |
前田 勝浩 Katsuhiro MAEDA |
| ＜要旨＞ Here we describe a unique polyacetylene-based chiral stationary phase (CSP) whose elution order can be reversibly switched. The macromolecular helicity was induced in a polyacetylene bearing 2,2’-biphenol-derived pendants in the solid state as well as in solution by noncovalent interactions with a nonracemic alcohol through significant amplification of the chirality, which could be retained even after complete removal of the alcohol. The helical handedness of the polymer could be further reversibly switched in the solid state upon interaction with the opposite enantiomeric alcohol and its subsequent removal, which enabled this polymer to be the first switchable CSP for HPLC. Keywords: Helical Polymer / Memory / Chiral Stationary Phase / Enantioseparation / Chiral Discrimnation |
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| 電荷を有するπ電子系の規則配列による次元制御型集合体の創製 Dimension-Controlled Assemblies of Orderly Arranged Charged π-Electronic Systems |
前田 大光 Hiromitsu MAEDA |
| ＜要旨＞ Arrangement of well-designed charged π-electronic systems in ordered structures is highly important for the introduction of multiple π-systems in supramolecular assemblies. Ion binding enables the fabrication of charged π-systems by complexation of electronically neutral π-systems with (inorganic) ions. In fact, anion complexes of anion-responsive π-systems have been found to provide various ion-based assembled structures as supramolecular gels and thermotropic liquid crystals by combination with appropriate cationic species. Derived from favorable overlap of charged π-planes, ion-based materials with the contributions of charge-by-charge and charge-segregated arrangements provided effective charge carrier mobilities, showing semi-conductive properties. Highly ordered arrangement of charged π-electronic systems has been found to be a key factor to exhibit the enhanced performance as fascinating electronic materials. Keywords: π-Electronic Systems / Ion Binding / Soft Materials / Supramolecular Assemblies |
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| Tetra-PEGゲルに見るゲルと一本鎖の関係 Relationship Between Physical Properties of Tetra-PEG Gels and Polymer Chains |
酒井 崇匡・片島 拓弥 Takamasa SAKAI, Takuya KATASHIMA |
| ＜要旨＞Polymer gels are swollen 3D polymer networks. Because a polymer network consists of polymer chains connected by crosslinks, the physico-chemical properties of polymer gels are inherently related to those of a polymer chain. However, the full understanding of these relationships have been inhibited by the inherent heterogeneity of polymer networks. In this paper, in order to discuss the relationship between the mechanical properties of polymer gels and the single polymer chain, we utilize Tetra-PEG gels, which are polymer gels with well-controlled network structures. The ultimate elongation ratio of the Tetra-PEG gels increased with increases in polymer volume fraction and degree of polymerization of network strands, and was independent of the connectivity. These results do not obey the Kuhn model, in which the principal concept is based on a single polymer chain. We propose a new semi-empirical model, where the initial length of a network strand is not defined only by the degree of polymerization of a network strand, but influenced by the polymer volume fraction. Keywords: Tetra-PEG Gel / Polymer Gels / Ideal Network / Ultimate Elongation Ratio |
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| 光で分子集合を操る Controlling a Molecular Assembly by Light |
矢貝 史樹 Shiki YAGAI |
| ＜要旨＞ Diarylethenes have rarely been used in the design of photoresponsive molecular assemblies featuring a well-defined morphology transition because of rather small structural changes upon photoisomerization. We demonstrate that a supramolecular design based on the parallel conformation of diarylethenes enables the construction of photoresponsive dye assemblies that undergo a remarkable nanomorphology change. The parallel conformer of diarylethene was stabilized by cooperative stacking of perylene bisimide dyes through complementary hydrogen bonds. UV/Vis spectroscopy, atomic force microscopy, and molecular modeling showed that our diarylethene and perylene building blocks coassembled in nonpolar solvent, affording well-defined helical nanofibers comprising dimeric J-aggregates of perylene dyes. Upon irradiating the coassembly solution with UV and visible light in turn, a reversible morphology transition between nanofibers and nanoparticles took place. Furthemore, our system involves the generation of a new self-assembly pathway by means of photocontrol. Keywords: Supramoleuclar Polymer / Functional Dye / Photochromism / Self-Assembly / Hydrogen Bond / Nanostructures / Supramolecular Chemistry |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 直感に任せて Leave My Life to Intuitions |
平井 悠司 Yuji HIRAI |
| ＜要旨＞ Now I’m satisfied with my research situation, which is the results of leaving my life to intuitions. My research will be moving ahead at an accelerated pace by the beautiful nature of Hokkaido and my students. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| π共役系分子を用いる有機電界効果トランジスタの最前線 Recent Progresses in Organic Field Effect Transistors Based on π-Conjugated Organic Molecules |
森 裕樹・西原 康師 Hiroki MORI, Yasushi NISHIHARA |
| ＜要旨＞ Organic field-effect transistors (OFETs) have gained considerable interest as the key elements for realizing future ubiquitous electronics because they have a large number of advantages such as the flexibility, light-weight, and ease of design. In this article, recent material developments in this field, including phenacene-type molecules, thienoacene derivatives, and a series of donor-acceptor (D-A)-type polymers, are summarized. Phenacene-type molecules possess a low HOMO level and a wide band gap. Recently, among phenacene-type molecules, picene, [6]phenacene, and [7]phenacene have been recognized as unique molecules because using them high field-effect mobility in the transistors can be realized. In addition, in some cases the FET properties were found to be highly improved by an incorporation of alkyl chains to the parent motif and one can expect to apply these molecules to a solution-process owing to a high solubility in common organic solvents. Furthermore, recent progress of diketopyrrolopyrrole (DPP) and isoindigo (IID)-based D-A polymers showing high mobility are introduced. Keywords: Phenacene / Organic Field-Effect Transistors / High Mobility / p-Channel Characterictics / Picene / Cross-Coupling / Polymers |
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