| 高分子 Vol.63 No.4 |
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特集 制限空間と高分子
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| 展望 COVER STORY: Highlight Reviews |
| ナノ空間を利用した結晶化を必要としない結晶構造解析 Crystallization-Free Crystallography Utilizing Nano-Space of Porous Complexes |
猪熊 泰英・藤田 誠 Yasuhide INOKUMA, Makoto FUJITA |
| ＜要旨＞ 有機配位子と金属イオンを組み合わせることでさまざまなナノ空間を設計できる細孔性錯体を使った新しい結晶構造解析の手法が開発された。結晶化の困難な液体化合物や微量天然物まで解析可能なこの手法が生み出されるまでの研究背景と最新の解析例、そして今後の展開について概説する。 Keywords: X-Ray Crystallography / Porous Coordination Networks |
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| 金属錯体ナノ空間内での高分子化学 Polymer Chemistry in Coordination Nanospaces |
植村 卓史 Takashi UEMURA |
| ＜要旨＞ 金属イオンと有機配位子との自己集合によって構築される多孔性金属錯体のナノ空間を重合反応場として利用することで、得られる高分子の一次および高次構造の制御を可能にした。また、ナノ空間に拘束された高分子が通常のバルク状態とは大きく異なる物性を示すことを発見し、新しいナノ材料開発につながる重要な知見を得た。 Keywords: Metal-Organic Framework / Nanochannel / Controlled Polymerization / Nanoconfinement / Nanocomposite |
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| トピックス COVER STORY: Topics and Products |
| Porous Organic Cages - Soluble Molecular Pores | Andrew I. Cooper and Tom Hasell |
| ＜要旨＞ Most synthetic materials that give rise to molecular scale porosity are extended frameworks or networks. There are relatively few examples of discrete porous molecules. In the last few years, our group has reported a range of such porous “cage” molecules, and a number of these will be highlighted here, within the context of related research. The solubility of the cages allows them to be solution processed in ways that would not be possible for a macromolecular network. They can be blended with other soluble materials, deposited inside porous supports, and cast as films or coatings. The solubility also allows the cages to be directed into different crystal polymorphs, using appropriate directing solvents, or combined as co-crystals in a modular ‘mix-and-match’ strategy. Keywords: Intrinsic Microporosity / Gas Sorption / Gas Separation / Porous Organic Cages / Polymers / Crystal Engineering / Adsorption |
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| MOFを用いた新しい結晶重合 Novel Crystalline-State Polymerization of Metal Organic Frameworks (MOF) |
佐田 和己・小門 憲太 Kazuki SADA, Kenta KOKADO |
| ＜要旨＞ Polymerization in confined space has been attracting considerable interest. In this short review, we propose a new kind of crystalline-state polymerization by using metal organic framework (MOF) crystals. MOF is nano-porous crystalline materials constructed by metal ions and rigid organic linkers equipped with two or more ligation sites to form robust 3D host framework with nano-pores. The void space between them is wide and stable, which prompted us to investigate cross-linking of the organic linkers by two chemical reactions; (1) azide-tagged MOF (AzM) cross-linked by multi-alkyne cross-linkers via click reaction and (2) cyclodextrin MOF (CD-MOF) cross-linked by glycidyl ethers. They represent new crystalline-state polymerization techniques, because the cross-linking takes place between the host components fixed at the wall of the host framework and the guest monomers included in the host framework. Moreover, they provide polyhedral gels with well-defined edges and faces. The shape and size of the starting MOF crystals are retained after cross-linking and decomposition of coordination bonds. Keywords: Metal Organic Framework (MOF) / Crystalline-State Polymerization / Inclusion Polymerization / Confined Space / Click Reaction / Cyclodextrins |
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| 孤立化されたπ共役系高分子の物性と機能 Functions and Properties of Isolated π-Conjugated Polymers |
杉安 和憲 Kazunori SUGIYASU |
| ＜要旨＞ We have synthesized π-conjugated polymers, in which the conjugated backbones are sheathed within its own cyclic side chains. The structure is reminiscent of electric power cords; as such, π-π stacking between the polymer backbones is prevented, and thus, the materials reflect the electronic properties of the single polymer structure. Herein, we describe our recent studies on such ‘isolated’ conjugated polymers with focusing on their electronic and photophysical functions. Keywords: Conjugated Polymers / Molecular Wires / Conducting Mechanism / Fluorescent Materials |
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| アントラセン環の殻をもつ“芳香環ミセル” Aromatic Micelles with Anthracene Shells |
近藤 圭・吉沢 道人 Kei KONDO, Michito YOSHIZAWA |
| ＜要旨＞ Micelles are spherical assemblies of amphiphilic molecules with hydrophilic heads and hydrophobic tails. Inspired by the micelle structures, we designed new amphiphiles providing two or three anthracene panels connected through meta-phenylene spacers functionalized with hydrophilic groups. A new class of micelle-like molecular capsules was formed by the assembly of the bent amphiphilic molecules in water by π-stacking and hydrophobic interactions. The micellar capsules could accommodate various organic molecules (e.g., fluorescent dyes), and the resultant nano-composites exhibited unique emission properties through efficient host-guest interactions. Keywords: Anthracene / Assembly / Capsule / Fluorescence / Micelle |
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| アミノ酸／ペプチド超分子で操る金属集積 Metal Array Fabrication Based on the Self-Assembly of Metalated Amino Acids and -Peptides |
高谷 光・中村 正治・磯崎 勝弘 Hikaru TAKAYA, Masaharu NAKAMURA, Kastuhiro ISOZAKI |
| ＜要旨＞ Various types of metalated amino acids and peptides, in which a variety of functional transition-metal complexes covalently tethered to their α-side chain, were sucssessfully synthesized and their self-assembly properties for the fabrication of well-ordered metal arrays were investigated. Intermolecular hydrogen bonds induced self-assembly of these amino acids and peputide to afford β-sheet type supraolecular aggregation with well aligned metal complexes, resulting in perfect controll of 1D- and 2D-metal sequences as demostrated by using cryo-TEM-based electron diffraction and synchrotron WAX and SAXS analyses. Enhanced Enhanced catalysis were observed catalysis were observed in the Pd- and Pt-binding amino acids/peptide supramolecular aggregates. Keywords: Amino Acid / Peptide / Metal Array / Supramolecuar Gel |
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| 自己集合性ポルフィリンナノ空間を利用したフラーレン類の配列制御 Controlled Arrangements of Fullerenes within Nano Space of Self-Assembling Porphyrins |
谷 文都 Fumito TANI |
| ＜要旨＞ In order to construct controlled arrangements of fullerenes, we have prepared cyclic porphyrin dimers (M2-CPD, M=Ni, H2), which include fullerenes with high affinities (Kassoc ≈ 105 M-1). These dimers have two self-assembling 4-pyridyl groups at the opposite meso positions. In crystals, inclusion complexes of C60 and PCBM within the nickel dimer (C60⊂Ni2-CPD and PCBM⊂Ni2-CPD) result in a linear array of the fullerene molecules in the self-assembled porphyrin nanotube, which is formed by the stacking of the cyclic dimer through the non-classical hydrogen-bonding interactions between pyridyl nitrogens and pyrrole β C-H groups. In contrast, the inclusion complexes of C60 and C70 within the free-base dimer (C60⊂H4-CPD and C70⊂H4-CPD) afford zigzag arrays of the fullerene molecules without the formation of nanotube structure. Owing to the well-controlled arrangement of C60 above mentioned, C60⊂Ni2-CPD and C60⊂H4-CPD exhibit high electron mobility (Σμ > 0.1 cm2V-1s-1) along the array. Moreover, C60⊂H4-CPD undergoes photoinduced electron transfer from the porphyrin to C60 to produce a charge-separated state. Keywords: Fullerene / Porphyrin / Self-assembly / Nanotube / Supramolecule / Host-Guest Chemistry / Photoinduced Electron Transfer / Charge Mobility |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| おもろい OMOROI (means “Fascinating”) |
伊田 翔平 Shohei IDA |
| ＜要旨＞ In my high school days, the teacher guided me to the world of chemistry. Here, I look back on my career started following the teacher's direction. He might have expect that I make an academic career in polymer science. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 超分子性相互作用を取り入れた高分子複合体の自己組織化 Self-Assembly of Complex Polymer Systems with Supramolecular Interactions |
松下 裕秀 Yushu MATSUSHITA |
＜要旨＞ Recent progress in complex structure formation via self-assembly of block copolymers coupled with supramolecular interaction is reported. The content comprises of three parts, (I) Morphology control of complex systems having hydrogen bonding interaction, (II) Formation of periodic structures from block coplymer/metal compounds, or block copolymer/metal nanoparticle hybrids with supramolecular interactions, and (III) Creation of nonoporous materials by way of hybrids based on self-assmbly of block copolymers. Furthermore, category (I) includes three sub-themes that all deal with hydrogen bonding interactions, i.e., 1) block copolymer/homopolymer or low molecular weight organic compound blends, 2) block copolymer/block copolymer blends, and 3) block copolymer type supramacromolecules, while category (II) is composed of 1) block copolymer/metal salt hybrids, and 2) block copolymer/matal nanoparticles or semiconductor nanoparticle hybrids. |
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