| 高分子 Vol.69 No.8 |
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特集 空間を操る
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| 展望 COVER STORY: Highlight Reviews |
| 分子を認識・配列・活性化する超空間の創出 Creation of Superspace that Recognizes, Arranges, and Activates Molecules |
塩谷 光彦 Mitsuhiko SHIONOYA |
| ＜要旨＞ 近年、天然酵素を範として、分子を認識・配列・活性化する超空間を構築するためのさまざまな挑戦が行われてきた。本稿では、分子を細孔内に捕捉する多孔性結晶の例、および筆者らが開発した、複数の異なる分子認識部位が配置された新タイプの多孔性結晶Metal-Macrocycle Frameworkを紹介し、今後の展望を述べる。 Keywords: Superspace / Porous Crystal / Molecular Recognision / Molecular Arrangement / Molecular Activation |
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| メソポーラス有機シリカの応用 Applications of Periodic Mesoporous Organosilicas |
稲垣 伸二 Shinji INAGAKI |
| ＜要旨＞ メソポーラス有機シリカは、さまざまな機能をもつ有機基を骨格に導入可能であることと、界面活性剤ミセルを鋳型にして形成される比較的大きな細孔径を有するという二つの特長を併せもつ。これらの特長を活かした応用例として、光捕集アンテナ、錯体触媒の固定化担体、質量分析用脱離／イオン化基板、ドラッグデリバリーシステムについて紹介する。 Keywords: Mesoporous Organosilica / Light Harvesting / Metal Complex / Solid Support / Laser Desorption / Ionization / Mass Spectrometry / Drug Delivery System |
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| トピックス COVER STORY: Topics and Products |
| 液晶の中にナノ空間を創る Nanospace in Liquid Crystals |
河野 慎一郎・田中 健太郎 Shin-ichiro KAWANO, Kentaro TANAKA |
| ＜要旨＞ Shape-persistent macrocyclic mesogens in thermotropic liquid crystals have potential uses in highly customizable nanochannels through stacking, which could lead to novel porous soft materials for use as molecular recognition sites, organizers of entrapped molecules, and nanoreactors in flowable media. We have synthesized thermotropic liquid-crystalline (LC) macrocycles composed of carbazole and salphen with 1.4 nm sized inner cavity which can accommodate guest molecules. The LC behavior is also drastically affected by the metal coordination in the salphen ligand. Furthermore, we have an extended discrete inner cavity of a columnar LC macrocycle with a larger pi-conjugated building block. The inner cavity was as large as 2.5 nm in diagonal. The giant macrocycle with branched alkyl chains showed the thermotropic LC properties below 213℃. To best of our knowledge, the giant macrocycle contained the largest discrete inner space among the thermotropic columnar liquid crystals composed of the macrocyclic mesogens. Keywords: Nanospace / Liquid Crystals / Macrocycles / Supramolecular Chemistry / Host-Guest Complex |
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| 中空錯体の組織化で創る多孔性ソフトマテリアル Porous Soft Materials Comprised of Self-Organized Metal-Organic Cages |
細野 暢彦 Nobuhiko HOSONO |
| ＜要旨＞ There is a common perception that porous materials are solid and crystalline. Is this really true? Recently, porous soft materials that possess both permanent porosity and fluidity have emerged as a new class of porous materials. We have developed porous soft materials using metal-organic cages (MOCs) as a “modular pore” to be organzed into porous soft materials. To give fluidity and malleability to the MOCs, polymers are attached directly on the MOCs, which results in polymer-grafted MOCs. The polymer-grafted MOCs allow formation of viscous fluids that have a nanoporous cavity in their molecular structure. Furthermore, the MOCs form into a lyotropic liquid crystalline phase that has regular ordering in the cavity structure. This bottom-up synthetic approach for the porous soft materials using MOC enables us to synthesize new porous soft materials that satisfy both processability and ordered pore structures, which have been considered difficult properties to be achieved simultaneously in the conventional porous solids. Keywords: Porous Material / Metal-Organic Cage / Polymer Hybrid / Graft Polymerization / Liquid Crystal / Self-Organization |
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| 金属担持多孔性共役系高分子の電極触媒材料への展開 Development of Metal-Doped Conjugated Microporous Polymers for Electrocatalytic Applications |
神谷 和秀 Kazuhide KAMIYA |
| ＜要旨＞ Conjugated microporous polymers (CMPs) have attracted increasing attention as novel polymeric materials due to their unique physicochemical properties, such as their nano-porous structure, mechanical robustness and high design flexibility. Recently, we have demonstrated that triazine-linked CMPs can support a wide variety of metals in their pores via coordination bonds. Interestingly, the metal-doped CMPs (M-CMPs) exhibited unique electrocatalytic functions depending on the metal species: for example, single Pt-doped CMP and Ni-doped CMP could serve as an electrocatalyst for oxygen-tolerant hydrogen oxidation and carbon dioxide reduction, respectively. Considering the abundance in choice of monomers, M-CMPs are becoming the promising platform of heterogeneous electron-transfer catalysts. Keywords: Conjugated Microporous Polymer / Covalent Organic Frameworks / Electrocatalysts / Hydrogen Oxidation Reactions / CO2 Electrolysis |
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| 水素結合で組み立てる多孔質分子結晶 Porous Molecular Crystals Constructed Through Well-Organized Hydrogen Bonding |
久木 一朗 Ichiro HISAKI |
| <Abstract> Porous molecular crystals constructed through hydrogen bonding, which are often called hydrogen-bonded organic frameworks (HOFs), have recently attracted much attention. HOFs with permanent porosity were thought for long time to be difficult to construct due to the weakness of reversible hydrogen bonds. However, well-designed hydrogen bonds, combined with the use of rigid, shape-persistent π-conjugated moieties, enables us to construct exotic HOFs with permanent porosity. This article describe the author’s approach to construct such HOFs based on C3-symmetric π-conjugated molecules possessing o-bis(4-carboxyphenyl)aryl moieties in their periphery. Structures and properties of HOFs with a 2D hexagonal network, interpenetrated 3D pcu-network, and more complicated networks are presented. Keywords: Porous Framework / Permanent Porosity / Hydrogen Bond / Topology / Molecular Crystal / Gas Sorption / Acid Responsiveness |
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| 芳香環ナノ空間：生体分子の識別能 Biomolecular Recognition by Aromatic Nanospaces |
角田 瑠輝・吉沢 道人 Ryuki SUMIDA, Michito YOSHIZAWA |
| ＜要旨＞ Here we report the resent progress in the research of our molecular capsules with well-defined, aromatic nanospaces. The capsules are quantitatively formed by the self-assembly of two metal ions and four bent bispyridine ligands with two polyaromatic panels. In water, the aromatic nanospace displays unusual high affinity toward androgens (i.e., male hormones). For example, androgenic testosterone is quantitatively and exclusively encapsulated by the capsule even from a complex mixture with progesterone and β-estradiol, known as representative female hormones. In addition, long, linear, and flexible fatty acids with oligo- and polyunsaturated carbon-carbon double bonds (e.g., α-linolenic acid and EPA) are selectively bound by the capsule cavity in water, through effective hydrophobic effects and CH-π/π-π interactions. Notably, otherwise labile polyunsaturated fatty acids (e.g., DHA) are significantly stabilized against light, heat, and oxygen upon encapsulation by the capsule. Keywords: Capsule / Nanospace / Polyaromatic / Recognization / Biomolecule / Water |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 研究の原動力 Driving Force for Research Work |
林原 瞳 Hitomi HAYASHIBARA |
| ＜要旨＞ This column is about my research experience and where my motivation comes from. While doing Ph.D., rarely appearing and unexpected phenomena were very interesting to me so that I decided to continue my study till successfully obtaining my Ph.D. After entering a company, I have the dream that one day the product I develop will be manifactured and goes on sale. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 高分子ブラシによる表面の機能化と課題 Functional Surface Acheicved by Polymer Brushes |
小林 元康 Motoyasu KOBAYASHI |
| ＜要旨＞ Two decades have already passed since the well-defined polymer brushes had been prepared by surface-initiated controlled polymerization. Surface-tethered polymers with high graft density called as polymer brushes have been attracted much attention due to its specific chain structures in a good solvent and wide application of surface modification with various functionality, such as wettability control, antifouling, adhesion, lubrication, and biomaterial. This article reviews recent development of the science and applications of polymer brushes, and also current issues and future challenges. Keywords: Polymer Brushes / Surface Modification / Antifouling / Polyelectrolyte Brushes / Hydrophilic Surface / Nanoparticles |
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