| 高分子 Vol.66 No.12 |
| >> Japanese | >> English |
特集 進化する超分子ポリマー
|
| 展望 COVER STORY: Highlight Reviews |
| 精密超分子重合 Precise Supramolecular Polymerization |
宮島大吾・相田卓三 Daigo MIYAJIMA, Takuzo AIDA |
| ＜要旨＞ 1980年代に報告された超分子重合は逐次重合機構で進行するため、分子量の制御が不可能だと考えられていた。しかし最近分子量の精密制御ができる例がいくつか報告され、関連研究が第二の黎明期に入った。本稿では最新の研究を俯瞰し、今後研究がさらに発展していくために必要な技術・方向性についても言及する。 Keywords: Supramolecular Polymerization / Chain-growth Polymerization / Step-Growth Polymerization / Stereoselective Polymerization / Hydronge-Bond |
| ページトップへ▲ |
| ホスト－ゲスト相互作用により機能する高分子材料 Supramolecular Materials Functionalized by Host-Guest Interactions |
原田 明 Akira HARADA |
| ＜要旨＞ 近年、非共有結合を利用してさまざまな超分子ポリマーが構築されている。その中でホスト－ゲスト相互作用により構築された超分子ポリマーは、さらに超分子マテリアルの設計、合成に発展している。本稿では、これらの超分子材料の合成と機能について概説する。 Keywords: Supramolecular Materials / Host-Guest Intaeraction / Cyclodextrin / Self-Healing / Artificial Muscle |
| ページトップへ▲ |
| 多成分夾雑系に挑む超分子ヒドロゲル Supramolecular Hydrogels Toward Multi-Component Systems |
浜地 格・重光 孟 Itaru HAMACHI, Hajime SHIGEMITSU |
| ＜要旨＞ 超分子ポリマーから形成される超分子ヒドロゲル研究が、生細胞やそれに模倣した多成分夾雑系へと挑戦の幅を広げている。本稿では、『機能性分子・材料と超分子ヒドロゲルの多成分複合化による新規ソフトマテリアルの創出』や『細胞や生体内での超分子ファイバーの形成』など、近年の新潮流を概説する。 Keywords: Supramolecular Polymer / Hydrogel / Self-Assembly / Multi-Component / Biological Application |
| ページトップへ▲ |
| トピックス COVER STORY: Topics and Products |
| 一次元にも二次元にもリビング超分子重合 Living Supramolecular Polymerization in One and Two Dimensions |
杉安和憲 Kazunori SUGIYASU |
| ＜要旨＞ We have recently identified a very unique dynamic behavior of a metastable supramolecular assembly consisting of a porphyrin derivative. The metastable assembly, which was nanoparticles, could transform into either nanofiber or nanosheet in time, as if it had a capacity of “differentiation”. We uncovered the energy landscape for this dynamic behavior, based on which we could control which way the nanoparticle would differentiate. Furthermore, we succeeded in “living polymerization” of both 1D and 2D nanostructures through seeded-growth approach. Keywords: Supramolecular Polymers / Living Supramolecular Polymerization / Nucleation-Elongation / Porphyrins |
| ページトップへ▲ |
| ホスト－ゲスト相互作用を駆動力に形成する超分子ポリマー Supramolecular Polymers formed via Host-Guest Interaction |
灰野岳晴 Takeharu HAINO |
| ＜要旨＞A bisporphyrin molecular cleft captures an electron-deficient guest through a donor-acceptor interaction. A monomer, which possesses a bisporphyrin cleft and an electron-deficient guest, self-assembles to form supramolecular polymers that are cross-linked with coordination bonds. The resulting supramolecular polymers generate well-entangled solutions with associating and networking polymers. The free-standing films of the supramolecular polymer networks are fabricated with Young’s modulus of 1 GPa. A self-assembled coordination capsule exists as a racemic mixture of the (P)- and (M)-enantiomeric forms. When a chiral guest is captured within the capsule, the chiral interior recognizes the shape of the guest, which results in the diastereomeric complex with high diastereoselectivity. The multiple guests, introduced onto a polymer main chain, are encapsulated within the coordination capsules, resulting in supramolecular graft copolymers. The steric communication among the graft sites results in the helical organization of the supramolecular graft polymers, and gives rise to the unique chiral amplifications known as the majority-rules effect. Keywords: Supramolecular Polymer / Graft Polymer / Porphyrin / Self-Assembled Capsule / Chiral Recognition / Chiral Amplification |
| ページトップへ▲ |
| ヘムタンパク質超分子ポリマーの創製 Construction of a Hemoprotein Supramolecular Polymer |
林 高史 Takashi HAYASHI |
| ＜要旨＞ Hemoproteins such as myoglobin, hemoglobin, cytochrome P450 and horseradish peroxidase include protoheme (heme b) as a cofactor. This heme cofactor is removable from the proteins and the resulting apoproteins can be converted into reconstituted proteins upon addition of appropriate porphyrinoid cofactors. Our group has focused on the preparation of various supramolecular hemoprotein polymers using this process. For example, an external heme-linked apoprotein where the heme molecule is covalently bound to the protein surface is found to provide a linear hemoprotein polymer via the heme-heme pocket interaction. In addition, 2D and 3D hemoprotein assemblies, a branched polymer and cross-linked polymer, respectively, can also be generated using similar methodology. In other studies, our group has immobilized the hemoprotein polymer onto various surfaces such as gold and other metal-based particles and carbon materials to prepare functionalized electrodes. In the present article, supramolecular polymerization using a hemoprotein as a monomer will serve as a new strategy for generating functional materials and catalysts. Keywords: Supramolecular Polymer / Hemoprotein / Artificial Cofactor / Reconstituted Protein |
| ページトップへ▲ |
| グローイングポリマー Polymer Science and I: A Personal Account |
| “できること”から“やるべきこと”へ Shifting from “What I Can Do” to “What I Should Do” |
榊原圭太 Keita SAKAKIBARA |
| ＜要旨＞ This essay is the short story of my life as a researcher, including why I decided to go on to a doctoral course, what I felt during post-doctoral research, and how I changed mind about “what I should do”. |
| ページトップへ▲ |
| 高分子科学最近の進歩 Front-Line Polymer Science |
| 超分子形成メカニズムと外部刺激応答性 Cooperativity in Self-Assemblies and Dynamic Response to External Stimuli |
廣瀬崇至・松田建児 Takashi HIROSE, Kenji MATSUDA |
| ＜要旨＞ Cooperative self-assembly is a key concept to create supramolecular systems that are highly responsive to external stimuli. Supramolecular structural change in solution can be usually detected using spectroscopic measurement—such as UV-Vis absorption, circular dichroism (CD) and NMR spectra—depending on concentration or temperature. The process of self-assembly can be quantitatively analyzed by applying appropriate thermodynamic models considering multistage open association of equilibrium polymers. When the process of self-assembly is highly cooperative, elongation of a supramolecular polymer has clear thresholds for concentration and temperature. Recently, we have developed a thermodynamic model for two-dimentional (2-D) self-assemblies formed at the liquid/solid interface. Concentration dependence of surface coverage of adsorbates on graphite substrate can be determined using scanning tunneling microscopy (STM). We found that surface coverage depending on concentration becomes prominently sharp when the system of 2-D self-assembly is highly cooperative. On the basis of this concept, highly photoresponsive 2-D self-assembly was achieved by using 2-D molecular ordering composed of photochromic diarylethene derivatives. Keywords: Cooperative Self-Assembly / Nucleation–Elongation Model / Liquid–Solid Interface / External Stimuli |
| ページトップへ▲ |
| Copyright(C) 2017 The Society of Polymer Science, Japan All Rights Reserved. |