高分子 Vol.63　No.4 April 2014

高分子　Vol.63　No.4

特集
受限空间与高分子

展望

利用纳米空间的不需要晶化的晶体结构分析

猪熊泰英,藤田诚

<Abstract> 我们开发了一种新型晶体结构的分析方法,它是利用有机配体与金属离子的组合的方法可以设计出多种多样纳米空间的细孔性错体,该分析方法是利用这些细孔性错体的.这种分析方法可以分析出晶化较困难的液体化合物及微量天然物质,本文概述了这种分析方法诞生的研究背景和最新的分析事例及今后的展望.
Keywords: X-Ray Crystallography / Porous Coordination Networks

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金属错体纳米空间内的高分子化学

植村桌史

<Abstract> 我们利用了金属离子与有机配位子的自我集合而形成的多孔性金属错体的纳米空间作为聚合反应场,控制了高分子聚合物的一元及多元结构. 而且我们发现了束缚在纳米空间的高分子聚合物显示与通常的主体高分子不同的特性,发现了新纳米材料开发的重要线索.
Keywords: Metal-Organic Framework / Nanochannel / Controlled Polymerization / Nanoconfinement / Nanocomposite

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话题

Porous Organic Cages - Soluble Molecular Pores

Andrew I. Cooper and Tom Hasell

<Abstract> 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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Novel Crystalline-State Polymerization of Metal Organic Frameworks (MOF)

Kazuki SADA, Kenta KOKADO

<Abstract> 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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Functions and Properties of Isolated π-Conjugated Polymers

Kazunori SUGIYASU

<Abstract> 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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Aromatic Micelles with Anthracene Shells

Kei KONDO, Michito YOSHIZAWA

<Abstract> 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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Metal Array Fabrication Based on the Self-Assembly of Metalated Amino Acids and -Peptides

Hikaru TAKAYA, Masaharu NAKAMURA, Kastuhiro ISOZAKI

<Abstract> 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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Controlled Arrangements of Fullerenes within Nano Space of Self-Assembling Porphyrins

Fumito TANI

<Abstract> 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 (K_assoc ≈ 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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高分子科学与我: 个人独白

OMOROI(日意为“陶醉”)

伊田翔平

<Abstract> 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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高分子科学最新进展

利用超分子性相互作用的高分子复合物的自组装

松下裕秀

<Abstract> 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.
Keywords: Self-Assembly / Block Copolymer / Microphase Separation / Supramolecular Interaction / Hydrogen Bonding / Hierarchical Structure / Hybrids / Metal Nanoparticles

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