Preparation of Polyrotaxane Fibers. Part II: Tensile Properties of Polyrotaxane Fibers Treated with Two Cross-linking Reagents

Polyrotaxane fibers prepared with wet spinning of polyrotaxane consisting of poly(ethylene glycol) and cyclodextrins were cross-linked with two different cross-linking reagents, i.e., divinyl sulfone (DVS) and ethylene glycol diglycidyl ether (EGDE), to improve the tensile properties of the fibers. By cross-linking with DVS, the values for the tenacity at break and the initial modulus were increased with cross-linking time, while the elongation at break was improved only moderately. On the other hand, drastic improvements in elongation at break were observed after EGDE cross-linking, up to 645% of its original length, although the tenacity at break and the initial modulus showed only slight improvements. After cross-linking, only minor changes in the degree of crystallinity of the fibers were observed by wide-angle X-ray scattering measurements.ArticleTEXTILE RESEARCH JOURNAL. 80(12):1131-1137 (2010)journal articl

Bioinspired oxidation-resistant catechol-like sliding ring polyrotaxane hydrogels

Adaptable hydrogels have been used in the biomedical field to address several pathologies, especially those regarding tissue defects. Here, we describe unprecedented catechol-like functionalized polyrotaxane (PR) polymers able to form hydrogels. PR were functionalized with the incorporation of hydroxypyridinone (HOPO) moieties into the polymer backbone, with a degree of substitution from 4 to 22%, depending on the PR type. The hydrogels form through the functionalized supramolecular systems when in contact with a Fe(III) solution. Despite the hydrogel formation being at physiological pH (7.4), the HOPO derivatives are extremely resistant to oxidation, unlike common catechols; consequently, they prevent the formation of quinones, which can lead to irreversible bounds within the matrix. The resulting hydrogels demonstrated properties lead to unique hydrogels with improved mechanical behavior obtained by metallic coordination crosslinking, due to the synergies of the sliding-ring PR and the non-covalent (reversible) catechol analogues. Following this strategy, we successfully developed innovative, cytocompatible, oxidative-resistant, and reversible crosslinked hydrogels, with the potential of being used as structural self-materials for a variety of applications, including in the biomedical field.publishe

Highly toughened polylactide with novel sliding graft copolymer by in situ reactive compatibilization, crosslinking and chain extension

YesThe “sliding graft copolymer” (SGC), in which many linear poly-ε-caprolactone (PCL) side chains are bound to cyclodextrin rings of a polyrotaxane (PR), was prepared and employed to toughen brittle polylactide (PLA) with methylene diphenyl diisocyanate (MDI) by reactive blending. The SGC was in situ crosslinked and therefore transformed from a crystallized plastic into a totally amorphous elastomer during reactive blending. Meanwhile, PLA-co-SGC copolymer was formed at interface to greatly improve the compatibility between PLA and SGC, and the chain extension of PLA also occurred, were confirmed by FTIR, GPC, SEM, and TEM. The resulting PLA/SGC/MDI blends displayed super impact toughness, elongation at break and nice biocompatibility. It was inferred from these results the crosslinked SGC (c-SGC) elastomeric particles with sliding crosslinking points performed as stress concentrators and absorbed considerable energy under impact and tension process.This work was supported by the National Natural Science Foundation of China (50933001, 51221002 and 51320105012)

Preparation and characterization of self-assembled conducting polymer nanofibers(Poster session 2, New Frontiers in Colloidal Physics : A Bridge between Micro- and Macroscopic Concepts in Soft Matter)

この論文は国立情報学研究所の電子図書館事業により電子化されました。アニソールを溶媒としたウィスカー法を使用して、ポリ(3-アルキルチオフェン)のナノファイバーを作製した。原子間力顕微鏡の観察からこのナノファイバーは高さが5nmと細く、アスペクト比が10^3にも達する非常によい1次元性を有することを確認した。紫外可視吸収スペクトルの変化がナノファイバーの形成過程とよい相関を示し、X線回折測定により結晶性ナノファイバーであることが明らかになったので、溶液中での高分子の結晶化がナノファイバーの形成の駆動力であると結論付けた。We prepared one-dimensional nanofibrillar structure of poly(3-alkylthiophenes) (P3ATs) via whisker precipitation in anisole. P3ATs self-assembled into nanofibers whose height and aspect ratio was 5nm and on the order of 10^3, respectively. UV-Vis absorption spectra showed the relationship between the change of absorption spectra and nanofiber formation in P3ATs solutions. X-ray diffraction measurements showed P3AT nanofibers involve microcrystalline structures. The results indicate that crystallization of P3ATs in a solution, which was driven by strong π-π interaction between polymer backbones, plays a crucial role in nanofiber formation

Multi-Stimuli-Responsive Mesoporous Membranes and Effect of Molecular Architecture on Thermo- and pH-Responsive Behavior of the grafted Block Copolymer brushes

In this study, we prepared ultrafiltration membranes with a decoupled responses of filtration property to temperature and pH. The membrane preparation method was developed based on our previous work. We utilized methanol-supercritical carbon dioxide (methanol-scCO2) selective swelling method to introduce nanopores to block copolymers containing poly(diethylene glycol) methyl ether methacrylate (PMEO2MA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and polystyrene (PS) blocks. Formation of the mesoporous barrier layer with PS being the mechanically stable part of the matrix was driven by selective swelling of the PMEO2MA-b-PDMAEMA domains. Due to the selective swelling of PMEO2MA or PDMAEMA domains to introduce pores, the interior of the pores are covered with PMEO2MA or PDMAEMA blocks after pore formation. The PMEO2MA-b-PDMAEMA polymer brushes are naturally attached on the pore walls and worked as functional gates. PMEO2MA is a non-toxic, neutral thermo-responsive polymer with LCST at 26 ᴼC. PDMAEMA is a typical weak polyelectrolyte with pKa value at 7.0-7.5 and also a thermo-responsive polymer revealed a LCST of 20-80 °C in aqueous solution. Therefore, these membranes were expected to have multi dimensions as function of the combination of temperature and pH. Moreover, to understand the detail of the temperature and pH depended conformation transitions of PMEO2MA-b-PDMAEMA brushes, those diblock copolymers were end-tethered on flat substrates and analyzed via neutron reflectivity (NR)

Synthesis of graft polyrotaxane by simultaneous capping of backbone and grafting from rings of pseudo-polyrotaxane

Graft polyrotaxanes, with poly(ε-caprolactone) (PCL) graft chains on the ring components were synthesized by the simultaneous ring-opening polymerization of ε-caprolactone from both ends of the backbone polymer, an end-functionalized polyethylene glycol (PEG) and the formation of inclusion complexes with α-cyclodextrin (α-CD). PEG with multiple functional groups at each end was prepared by the condensation of PEG-amine and D-gluconic acid; the PEG derivative formed an inclusion complex with α-CD. The polymerization of multiple hydroxy groups at the backbone ends resulted in a star-shaped end group, which served as a bulky capping group to prevent dethreading. In contrast, PEG with only one hydroxy group at each end did not produce polyrotaxanes, indicating that single PCL chains were too thin to confine α-CDs to the complex. In addition, the grafting polymerization proceeded properly only when robust hydrogen bonds formed between α-CDs were dissociated using a basic catalyst. Since the dissociation also induced dethreading, kinetic control of the polymerization and dissociation were crucial for producing graft polyrotaxanes. Consequently, this three-step reaction yielded graft polyrotaxanes in a good yield, demonstrating a significant simplification of the synthesis of graft polyrotaxanes

59. Theory and experiments on elasticity of topological gels(poster presentation,Soft Matter as Structured Materials)

この論文は国立情報学研究所の電子図書館事業により電子化されました。最近、物理ゲルでも化学ゲルでもない新しい種類のゲル「トポロジカルゲル」が注目を集めている。トポロジカルゲルは伸長時に極めて柔らかい初期弾性を示すことが見出されている。我々はトポロジカルゲルの特徴である「線状高分子が架橋点を自由に通り抜ける」効果(滑車効果)に着目し、化学ゲルの3chainモデルに基づく弾性理論を拡張して、トポロジカルゲルの伸張弾性理論を得た。トポロジカルゲル特有の極端に柔らかい非線形弾性を理論的に再現することに成功した。また貧溶媒中での硬い弾性は滑車効果の消失に起因することを見出した

Synthesis, structure, and mechanical properties of silica nanocomposite polyrotaxane gels

A significantly soft and tough nanocomposite gel was realized by a novel network formed using cyclodextrin-based polyrotaxanes. Covalent bond formation between the cyclic components of polyrotaxanes and the surface of silica nanoparticles (15 nm diameter) resulted in an infinite network structure without direct bonds between the main chain polymer and the silica. Small-angle X-ray scattering revealed that the homogeneous distribution of silica nanoparticles in solution was maintained in the gel state. Such homogeneous nanocomposite gels were obtained with at least 30 wt % silica content, and the Young’s modulus increased with silica content. Gelation did not occur without silica. This suggests that the silica nanoparticles behave as cross-linkers. Viscoelastic measurements of the nanocomposite gels showed no stress relaxation regardless of the silica content for <20% compression strain, indicating an infinite stable network without physical cross-links that have finite lifetime. On the other hand, the infinite network exhibited an abnormally low Young’s modulus, ~1 kPa, which is not explainable by traditional rubber theory. In addition, the composite gels were tough enough to completely maintain the network structure under 80% compression strain. These toughness and softness properties are attributable to both the characteristic sliding of polymer chains through the immobilized cyclodextrins on the silica nanoparticle and the entropic contribution of the cyclic components to the elasticity of the gels