Strain-Induced Orientation of Host Rings that Determines the Sliding of Guest Polymers and Plasticity of Glassy Polyrotaxane.

The unique motility of mechanically interlocked polymers enables their mechanical properties to profoundly transform. This property has been exploited less in glassy materials than in rubbery materials. This study demonstrated that in the glassy state the rings must orient before sliding and clarified the requisite structural changes by the synchrotron microbeam X-ray diffraction mapping of a ductile cyclodextrin (CD)-based glassy polyrotaxane.

Strain-induced crystallization and phase separation used for fabricating a tough and stiff slide-ring solid polymer electrolyte.

The demand for mechanically robust polymer-based electrolytes is increasing for applications to wearable devices. Young's modulus and breaking energy are essential parameters for describing the mechanical reliability of electrolytes. The former plays a vital role in suppressing the short circuit during charge-discharge, while the latter indicates crack propagation resistance.

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.

Cross-Linking-Filler Composite Materials of Functionalized Hexagonal Boron Nitride and Polyrotaxane Elastomer.

This study demonstrates cross-linking-filler composites in which covalent bonds between the fillers and polymer chains act as the main cross-linking points for the development of flexible and thermally conductive materials. Cross-linking-filler composites are fabricated using functionalized hexagonal boron nitride (hBN) fillers and polyrotaxane, called slide-ring polymers. The hBN particles modified with a carbon layer were produced by plasma processing in hydroquinone aqueous solution and functionalized with isocyanate groups.

Stabilization and Movable Ligand-Modification by Folate-Appended Polyrotaxanes for Systemic Delivery of siRNA Polyplex.

To achieve a systemic targeted delivery of siRNA using polymeric carriers, there is a dilemma between ligand modification and stabilization of the polyplex. Namely, ligand modification often leads to destabilization of the polyplex in the blood circulation. In fact, we previously developed cyclodextrin (CD)/polyamidoamine dendrimer conjugates (CDE) as siRNA carriers, and the interaction of CDE/siRNA was decreased by the conjugation with folate-polyethylene glycol, leading to the destabilization.

A neuromechanical model for Drosophila larval crawling based on physical measurements.

Background: Animal locomotion requires dynamic interactions between neural circuits, the body (typically muscles), and surrounding environments. While the neural circuitry of movement has been intensively studied, how these outputs are integrated with body mechanics (neuromechanics) is less clear, in part due to the lack of understanding of the biomechanical properties of animal bodies. Here, we propose an integrated neuromechanical model of movement based on physical measurements by taking Drosophila larvae as a model of soft-bodied animals.

High-yield one-pot synthesis of polyrotaxanes with tunable well-defined threading ratios over a wide range.

In this work, we report a high-yield one-pot synthesis of polyrotaxane (PR), composed of (2-hydroxypropyl)-α-cyclodextrin (hpCD) and polyethylene glycol (PEG), with well-defined hpCD threading ratios controllable across a wide range from 0.64% to 10%. In hpCD/PEG aqueous solutions, hpCDs are well dispersed and threaded spontaneously into hpCDs to form a pseudo-PR (pPR) structure.

Fracture Behavior of Polyrotaxane-Toughened Poly(Methyl Methacrylate).

The fracture behavior of polyrotaxane (PR)-modified poly(methyl methacrylate) (PMMA) was investigated. PR is a supramolecule with rings threaded onto a linear backbone chain, which is capped by bulky end groups to prevent the rings from de-threading. The ring structure is α-cyclodextrin (CD), and it can be functionalized to enhance its affinity with the hosting polymer matrix.

Polymer Brush Formation Assisted by the Hierarchical Self-Assembly of Topological Supramolecules.

The development of methods for the polymer brush layer formation on material surfaces to improve the surface properties has been researched for decades. Here, we report a novel approach for the formation of a polymer brush layer on materials and the alteration of the surface properties using a pseudo-polyrotaxane nanosheet (PPRNS). In the PPRNS, β-cyclodextrin (CD) selectively covered the central poly(propylene oxide) segment of the carboxyl-terminated poly(ethylene oxide)--poly(propylene oxide)--poly(ethylene oxide) (COOH-EOPOEO) triblock copolymer to form columnar crystals.

Hydrogen-Bonded Structure of Water in the Loop of Anchored Polyrotaxane Chain Controlled by Anchoring Density.

Hydrogen-bonded network of water surrounding polymers is expected to be one of the most relevant factors affecting biocompatibility, while the specific hydrogen-bonded structure of water responsible for biocompatibility is still under debate. Here we study the hydrogen-bonded structure of water in a loop-shaped poly(ethylene glycol) chain in a polyrotaxane using synchrotron soft X-ray emission spectroscopy. By changing the density of anchoring molecules, hydrogen-bonded structure of water confined in the poly(ethylene glycol) loop was identified.

Direct enhancement of intercomponent interactions in polyrotaxane and its pronounced effects on glass state properties.

Strong interactions between the host cyclodextrin and the threading guest polymer were introduced by selective modifications to the polymer of a polybutadine-based polyrotaxane. The changes in the intercomponent interactions influenced the mobility of the threading polymer that was confined in the glassy host framework, resulting in different mechanical properties.

Softness, Elasticity, and Toughness of Polymer Networks with Slide-Ring Cross-Links.

Slide-ring (SR) gels cross-linked by ring molecules are characterized by softness (low Young's modulus), elasticity (low hysteresis loss), and toughness (large fracture energy). In this article, the mechanical and fracture properties of SR gels are reviewed to clarify the physical understanding of the relationship between the molecular-level sliding dynamics of the slide-ring cross-links and macroscopic properties of SR gels. The low Young's modulus and large fracture energy of SR gels are expressed by simple equations as a function of the degree of sliding movement.

Tough hydrogels with rapid self-reinforcement.

Most tough hydrogels are reinforced by introducing sacrificial structures that can dissipate input energy. However, because the sacrificial damage cannot rapidly recover, the toughness of these gels drops substantially during consecutive cyclic loadings. We propose a damageless reinforcement strategy for hydrogels using strain-induced crystallization.

Molecular Recognition of Fluorescent Probe Molecules with a Pseudopolyrotaxane Nanosheet.

Pseudopolyrotaxane nanosheets (PPRNS) are ultrathin two-dimensional (2D) materials fabricated via supramolecular self-assembly of β-cyclodextrin (β-CD) and poly(ethylene oxide)--poly(propylene oxide)--poly(ethylene oxide) triblock copolymers. In this study, the molecular loading of various fluorescent probe molecules onto PPRNS was systematically investigated. H NMR study for R6G absorption to PPRNS indicated that the small hydrophobic groups, such as the methyl group, of R6G were absorbed by PPRNS.

Synthesis of Poly(Methyl Methacrylate)-Based Polyrotaxane via Reversible Addition-Fragmentation Chain Transfer Polymerization.

A polyrotaxane (PR) with poly(methyl methacrylate) (PMMA) as the main chain polymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Because of the special mechanism of RAFT, the suprastructure of a PMMA-based PR is established by synthesizing inclusion complexes of methyl methacrylate and gamma-cyclodextrin (γCD) into the middle of the poly-N-(3-dimethylamino) propyl methacrylamide segments. The presence of threaded γCD was determined via diffusion ordered spectroscopy from the alignment of the mobility of γCD and the main chain polymer.

Slide-Ring Material/Highly Dispersed Graphene Oxide Composite with Mechanical Strength and Tunable Electrical Conduction as a Stretchable-Base Substrate.

The development of stretchable elastomer composites with considerable mechanical strength and electrical conductivity is desired for future applications in communication tools, healthcare, and robotics. Herein, we have developed a novel stretchable elastomer composite by employing a slide-ring (SR) material as a matrix for restoration and graphene oxide (GO) as a precursor for a conductive filler. Highly dispersed GO in an organic solvent, prepared via a new method developed by the authors, allowed the uniform dispersion of GO into the matrix by simply mixing the solvent and SR.

Molecular Dynamics Simulation and Theoretical Model of Elasticity in Slide-Ring Gels.

In this study, molecular dynamics (MD) simulations were carried out on the uniaxial deformation of slide-ring (SR) networks with slidable cross-links to understand the relationship between the sliding of the cross-linking points and the Young's moduli of SR gels, which are lower than those of covalently cross-linked gels with the same cross-linking densities. The slidability of the cross-links in SR gels was characterized by the rate of change of the segment number between the cross-links, , estimated by the MD simulation. We have successfully constructed a molecular model for the elasticity of SR gels and proposed a simple equation for the Young's moduli of SR gels as a function of .

Precise control of cyclodextrin-based pseudo-polyrotaxane lamellar structure axis polymer composition.

Self-assembly of cyclodextrin (CD) with guest polymers has attracted much attention owing to its biocompatibility and accessibility. In this study, we investigate the composition effect of poly(ethylene oxide)m-b-poly(propylene oxide)n-b-poly(ethylene oxide)m (EOmPOnEOm) triblock copolymers on lamellar or plate structures formed by complexation with β-CD. EO5PO29EO5, EO14PO29EO14, and EO75PO29EO75 show periodic lamellar morphology consisting of single-crystalline pseudo-polyrotaxane (PPR) nanosheets with a thickness equal to the central PO length.

Anisotropic Amorphous X-ray Diffraction Attributed to the Orientation of Cyclodextrin.

The beauty of cyclic molecules is reflected in their host-guest complexation reactions, as well as their unique X-ray diffraction patterns. Cyclodextrins, the longest known host molecules with rigid ring structures, show anisotropic X-ray diffraction characteristic of their single-molecule structure, rather than their intermolecular relationships. Amorphous derivatives of α-cyclodextrin exhibit broad and strong halo diffractions in the solid, melted, and dilute solution states.

Interfacial Energy Measurement on the Reconstructive Polymer Surface: Dynamic Polymer Brush by Segregation of Amphiphilic Block Copolymers.

Herein, the interfacial energy of a reconstructive polymer surface formed by segregation is analyzed by measuring the change in the size of elastomer thin films floating on water. When a system in which amphiphilic diblock copolymers are mixed with the hydrophobic elastomer is in contact with water, surface reconstruction is triggered by the segregation of copolymers with a gain in the hydration energy of the hydrophilic blocks. The hydrophilic brush layer spontaneously formed at the elastomer-water interface is named the dynamic polymer brush.

Adhesion Force Analysis of Dynamic Polymer Brushes.

Spontaneous surface segregation of amphiphilic diblock copolymers at the water interface from the elastomeric portion was utilized for the fabrication of hydrophilic brushes, named as "dynamic polymer brush". Observation of the dynamic polymer brushes appears only when immersed in water and demands advanced experimental techniques for embedded interfaces such as neutron reflectivity. Measurement of the hydrophobic interaction at the polymer/water interface is not only an alternative method to monitor the brush but also reveals its unique surface properties.

Prolonged Glass Transition due to Topological Constraints in Polyrotaxanes.

Topological constraints in polyrotaxanes significantly affected their glass transition dynamics. The effects of the constraints were systematically studied using a series of different coverage glass-forming polyrotaxanes consisting of a common polymer and threaded ring molecule of varying ratios. Although their ratios were similar and hence exhibited similar values by differential thermal analysis, mechanical relaxation was considerably prolonged with increasing coverage.

Direct Determination of Cross-Link Density and Its Correlation with the Elastic Modulus of a Gel with Slidable Cross-Links.

The universal relationship between the elastic modulus and the cross-link density of a conventional rubber/gel has been demonstrated experimentally to be inapplicable to gels with slidable cross-links. Herein, we describe the synthesis of slide-ring (SR) gel networks devoid of intramolecular cross-links by the cross-coupling of two differently functionalized polyrotaxanes. The cross-link density was determined from the characteristic UV absorption attributed to the asymmetric cross-linked moiety.

Molecular Dynamics of Polyrotaxane in Solution Investigated by Quasi-Elastic Neutron Scattering and Molecular Dynamics Simulation: Sliding Motion of Rings on Polymer.

In this study, we investigated the molecular dynamics of polyrotaxane (PR), composed of α-cyclodextrins (CDs) and a poly(ethylene glycol) (PEG) axial chain, in solution by means of quasi-elastic neutron scattering (QENS) measurements and full-atomistic molecular dynamics (MD) simulations. From QENS experiments, we estimated the diffusion coefficients of CD and PEG monomers in PR, which are in quantitative agreement with those obtained by MD simulations. By analyzing the simulation results, we succeeded, for the first time, in observing and quantifying the sliding motion of CD along a PEG chain.

Autonomously isolated pseudo-polyrotaxane nanosheets fabricated via hierarchically ordered supramolecular self-assembly.

We succeeded in obtaining autonomously isolated nanosheets consisting of pseudo-polyrotaxane (PPR) fabricated via hierarchically ordered supramolecular self-assembly of β-cyclodextrin and a poloxamer by introducing charged groups to the axis ends of the poloxamer. The isolated PPR nanosheets exhibited a tunable structural coloration and were aligned using a strong magnetic field.