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We study the segmental and monomer dynamics of polymer gels with controlled inhomogeneity under uniaxial deformation by means of quasi-elastic neutron scattering (QENS). In order to clarify the effect of the homogeneity of a network structure on the polymer dynamics in gels, we compare two types of polymer gels with controlled homogeneity: a homogeneous tetra-PEG gel (homo-gel) prepared from uniform tetra-arm pre-polymers and a heterogeneous tetra-PEG gel (hetero-gel) with a small amount of shorter tetra-PEG pre-polymer. The different inhomogeneity in the homo-gel and the hetero-gel has little effect on the average relaxation time of the chain dynamics in the undeformed state. The difference in the local dynamics in the gels is emphasized under uniaxial deformation: while the homo-gel shows a single relaxation mode, the hetero-gel exhibits a bimodal distribution of relaxation times with a slow dynamic mode ascribed to highly stretched short strands, which causes a more brittle macroscopic fracture compared with that in the case of the homo-gel.

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. Adding only 1 wt % of PR containing methacrylate functional groups (mPR) at the terminal of some of the polycaprolactone-grafted chains on CD promotes massive crazing, resulting in a significant improvement in fracture toughness while maintaining the modulus and transparency of the PMMA matrix. Dynamic mechanical analysis and atomic force microscopy studies reveal that mPR strongly interact with PMMA, leading to higher molecular mobility and enhanced molecular cooperativity during deformation. This molecular cooperativity may be responsible for the formation of massive crazing in a PMMA matrix, which leads to greatly improved fracture toughness.

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. The homogeneous dispersion of hpCDs results in a well-defined threading ratio of hpCDs on PEG, which is suggested by the fact that the dispersity of the molecular weight distribution of PR is almost the same as that of pure PEG. The well-defined hpCD threading ratio of the PRs can be controlled over a wide range by tuning the hpCD concentration in the pPR solutions.

Tougher when stressed Hydrogels are typically weak materials because they contain only a small fraction of polymeric material highly swollen with water. Strength can be increased by adding extra cross-linking or interpenetrating networks with some sacrificial bonds to enhance toughness; however, these properties deteriorate upon stretching and may be slow to recover after relaxation. Liu et al. developed polyethylene glycol hydrogels cross-linked with moderate fractions of polymers that form sliding rings. These allow the chain to orient in parallel when stretched, leading to rapid and reversible strain-induced crystallization and thus much tougher hydrogels. Science , aaz6694, this issue p. 1078

Polyrotaxane (PR) is a supramolecular assembly in which ring molecules are threaded onto an axial polymer chain. This paper reviews the molecular structure and dynamics of a PR composed of polyethylene glycol (PEG) and α-cyclodextrin (CD) based on data obtained from X-ray and neutron scattering experiments on PR solutions. The dynamics of CD and the PEG monomers in the PR were evaluated separately by quasielastic neutron scattering with deuterium labeling. Inclusion complex formation with CD increases the stiffness of the PEG backbone and restricts the diffusion of the PEG monomers that are covered by or in close proximity to the CD molecules. The sliding motion of the CD molecules along the PEG axis was explored using full atomistic molecular dynamics (MD) simulations, showing that the sliding dynamics were retarded by the interaction between the CD cavities and PEG. This paper reviews our X-ray and neutron scattering experiments on the molecular structure and dynamics of a supramolecular assembly, polyrotaxane (PR) composed of polyethylene glycol (PEG) and α-cyclodextrin (CD). Inclusion complex formation with CDs increases the stiffness of the PEG backbone and restricts the diffusion of the PEG monomers that are covered by or in close proximity to the CD molecules.

A novel kind of polyrotaxane–silica hybrid aerogel is successfully prepared via one-pot sol–gel synthesis in this work. The polyrotaxane can chemically interpenetrate with Si particles homogeneously in nanoscale, so as to shorten the gelation time and construct a flexible and mechanically strong skeleton. The supramolecular effect ascribable to the sliding motion of cyclic components in polyrotaxane is introduced into the hybrid aerogel for the first time. Compared with the brittle pure silica aerogel, the obtained polyrotaxane–silica hybrid aerogels show very low density, low thermal conductivity, and more than two orders magnitude improvement in the compression strength without compromising transparency.

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

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. The resultant SR/GO composite exhibited considerably high mechanical toughness and cyclic durability. These properties were approximately maintained after pulse laser irradiation to add electrical conductivity on the composite by photoreducing of the dispersed GO, and its electrical conductivity was higher than that of the SR/graphene, carbon nanotubes, or graphite composites. The potential of the SR/GO composite as a stretchable base substrate for wearable devices was demonstrated by producing a prototype humidity sensor, a human motion monitoring sensor, and an electrical heater based on the composite with conductive circuits drawn using pulse laser patterning.

A difluorenylsuccinonitrile-(DFSN)-based linker, whose central C-C bond is readily cleaved under mechanical stress to generate a relatively stable pink radical species, was introduced into polymer networks. DFSN-based cross-linked polymers exhibit improved mechanical properties as compared to those of the corresponding covalently cross-linked polymers owing to the energy dissipation induced by cleavage of the central DFSN bond. The toughening mechanism of DFSN-based elastomers is qualitatively visualized by the intensity of the pink color and can be quantitatively characterized by electron paramagnetic resonance. These results demonstrate that the extent of DFSN cleavage is the main factor improving the mechanical properties of the polymer networks.

The molecular dynamics of polyrotaxane (PR) dispersed homogeneously in a cross-linked epoxy resin were studied using dynamic mechanical analysis (DMA) and pulsed NMR spectroscopy. In PR, poly-e-caprolactone (PCL)-grafted α-cyclodextrins (CDs) are threaded on a polyethylene glycol (PEG) axis. At low temperatures, the PEG and PCL chains of the PR embedded in the epoxy network are in a glassy state. With increasing temperature, the PEG in the PR undergoes a glass-to-rubber transition and fluctuates in the glassy PCL-grafted CDs confined by the epoxy matrix, which causes viscoelastic relaxation. The glass transition temperature, Tg, of the PEG in the PR is much higher than that of pure PEG because of the strong confinement effect in the epoxy network. In addition, the Tg of the PEG drastically changes with coverage by the CDs on the PEG, suggesting that the topological constraint by the CDs also substantially influences the PEG dynamics. The viscoelastic relaxation ascribed to PEG enhances the deformability and toughness of the epoxy resin containing PR under uniaxial stretching. The molecular dynamics of PCL-grafted polyrotaxanes (PRs) homogeneously dispersed in a cross-linked epoxy network were investigated using viscoelastic mechanical measurements and relaxation time measurements with pulsed NMR spectroscopy. With increasing temperature, the PEG axial chains in the PRs exhibit a glass-rubber transition and start fluctuating in the CDs with glassy PCL graft chains, which causes viscoelastic mechanical relaxation.

Stiff yet recoverable water-containing materials can be found in many biological tissues including tendons, cartilages, and skins. However, it remains a challenge to develop hydrogels as load-beari...

We applied a slide-ring (SR) gel to a Mg2+ ion gel electrolyte and clarified the electrical and mechanical properties in order to achieve a Mg2+ ion gel electrolyte with both sufficient mechanical strength and high ionic conductivity. The SR gel is made from polyrotaxane, which has a structure that consists of cyclic molecules, α-cyclodextrins (CDs), threaded by an axial polymer chain, polyethylene glycol (PEG), and cross-linked by divinyl sulfone. Pure glymes and tetraethylene glycol dimethyl ether (tetraglyme: G4) dissolving Mg2+ ions had no ability to swell the SR gel, whereas diethylene glycol dimethyl ether (diglyme: G2) and triethylene glycol dimethyl ether (triglyme: G3) dissolving Mg2+ ions were able to swell the SR gel. The swelling behavior was strongly dependent on the interaction between Mg2+ ions complexed with glymes and ether oxygens of a PEG-based hydroxypropyl PR (HyPR) network. Upon tensile elongation, SR gel swollen with G3 solution dissolving Mg2+ ions could be extended by 300%, which indicated the unique property of high ductility. The ionic conductivity of SR gel swollen with G3 dissolving Mg2+ ions, which approximately satisfied a Vogel-Tamman-Fulcher (VTF) dependence, was 1.73 mS cm−1 at room temperature, and the molar conductivity was 67% of that for a pristine G3 solution dissolving Mg2+ ions.

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. The diffusion coefficient for the sliding motion is almost 6 times lower than that of the translational diffusion of CD in PR at room temperature. The retardation of the sliding motion is caused by the energy barrier on PEG produced by molecular interactions between CD and PEG. We propose a simple equation to describe the diffusion coefficient of the sliding dynamics in PR by combining the Einstein-Stokes diffusion model and a one-dimensional jump diffusion model. This work provides a general strategy for the molecular designs to control the sliding motion in PR.

Rotaxane is a topological supramolecule in which a ring molecule is threaded onto an axial chain. A unique feature of rotaxane is that the ring can slide along the chain. In this study, we investig...

Polyrotaxane (PR), consisting of many ring molecules and an axis polymer, is a typical supramolecular structure with unique topological characteristics. In this study, we demonstrated the drastic change of the macroscopic mechanical properties depending on the ring position of PR in bulk. Poly(ethylene oxide)

Unlike hard materials such as metals and ceramics, rubbery materials can endure large deformations due to the large conformational degree of freedom of the crosslinked three-dimensional polymer network. However, the effect of the branching factor of the network on the ultimate mechanical properties of rubbery materials has not yet been clarified. This study shows that tri-branching, which entails the lowest branching factor, results in a large elastic deformation near the theoretical upper bound. This ideal elastic limit is realized by reversible strain-induced crystallization, providing on-demand reinforcement. The findings indicate that the polymer chain is highly orientated along the stretching axis, whereat enhanced reversible strain-induced crystallization is observed in the tri-branched and not in the tetra-branched network. A mathematical theory of structural rigidity is used to explain the difference in the chain orientation. Although tetra-branched polymers have been preferred since the development of vulcanization, these findings highlighting the merits of tri-branching will prompt a paradigm shift in the development of rubbery materials., 20+3 pages, 4+5 figures; published version

Animal locomotion requires dynamic interactions between neural circuits, muscles, and surrounding environments. In contrast to intensive studies on neural circuits, the neuromechanical basis for animal behaviour remains unclear due to the lack of information on the physical properties of animals. Here, we proposed an integrated neuromechanical model based on physical measurements by taking Drosophila larvae as a model of soft- bodied animals. The biomechanical parameters of fly larvae were measured by the stress- relaxation test. By optimizing parameters in the neural circuit, our neuromechanical model succeeded in quantitatively reproducing the kinematics of larval locomotion that were obtained experimentally. This model could reproduce the observation of optogenetic studies reported previously. The model predicted that peristaltic locomotion could be exhibited in a low friction condition. Analysis of floating larvae provided results consistent with this prediction. Furthermore, the model predicted a significant contribution of intersegmental connections in the central nervous system, which contrasts with a previous study. This hypothesis allowed us to make a testable prediction for the variability in intersegmental connection in sister species of the genus Drosophila. Our model based on physical measurement provides a new foundation to study locomotion in soft-bodied animals and soft robot engineering.

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A mechanical tough polylactic acid (PLA) that substantially retains its stiffness and transparency was created through reaction with a polyrotaxane derivative. A graft polyrotaxane (GPR), composed of a linear Polyethylene glycol backbone threaded with cyclodextrins bearing grafted poly(e-caprolactone), was bonded to the hydroxyl end-groups of PLA with hexamethylene diisocyanate (HDI), which then solidified to form a PLA-bonded GPR that was distributed throughout the PLA matrix. The addition of 5 wt% GPR resulted in a seven-fold increase in Izod impact strength and a three-fold increase in fracture elongation, with only an 11% loss of stiffness; the transparency was comparable to neat PLA. Electron microscopy revealed that HDI facilitated the dispersal of GPR in the PLA matrix and avoided the sea-island phase-separated structure observed in the PLA/GPR blend devoid of HDI, and that the homogenized structure led to ductile deformation. A GPR content of only 5 wt% efficiently increased PLA-matrix-chain flexibility.

Gels with high mechanical performance have attracted great interest because of their potential biomedical applications. Tough gels reported thus far usually contain sacrificial species to dissipate energy, thus compromising the fatigue resistance. In this study, highly stretchable and recoverable gels can be achieved by cross-linking cyclodextrin (CD)-based polyrotaxane with a low host coverage, synthesized via a one-pot enzymatic end-capping reaction with 90% yield and ∼2% CD coverage (PR02). The low coverage allows the CD cross-links to freely slip on the axis over large distance (∼2/3 of the axis length) and thus allows the PR02 slide-ring network keep intact under large deformation via the pulley effect. The PR02-hydrogel can be stretched up to ∼1600% long, withstand ∼1 MPa stress, and fully recover instantly. PR02-DMSO gels exhibit a shape memory behavior that withstood large deformation. As the first research to control the final property of the network by precisely controlling the slide distance of...

The slide-ring (SR) effect in composite materials is demonstrated by comparing the mechanical properties of plasma-modified boron nitride (p-BN)/SR elastomers and p-BN/fixed crosslinked (FC) elastomer composite materials that include a large amount of plasma-surface-modified BN (∼56 vol%). The toughness of p-BN/SR was ∼7 times that of p-BN/FC. Such SR effect was not observed in the raw BN/SR composite material but only in the p-BN/SR composite material. Time-domain nuclear magnetic resonance measurements suggested that the plasma-surface modification of BN formed crosslinking points to the SR and suppressed the decrease in the molecular mobility of SR in the composite materials.

To develop flexible and tough composite materials with out-of-plane aligned thermally conductive pathways, a novel freeze-casting method was developed using dimethyl sulfoxide (DMSO), carbon nanofibers (CFs), slide-ring polymers (SRs), and cross-linkers. Porous composite materials composed of SR and plasma-surface-modified CFs were obtained. Using DMSO, which has a high melting point (19 °C) and high polymer solubility, the SR cross-linking reaction was performed during freeze-casting. The CFs were treated with plasma before composite preparation for better affinity and dispersibility to the composites. The obtained porous composites contained thermally conductive pathways in the out-of-plane direction and exhibited a low Young's modulus (0.14 MPa). The composite with a thermoplastic polyurethane (TPU) elastomer embedded into its pores exhibited a low Young's modulus (3.62 MPa), high toughness (10.0 MJ/m3), and high thermal conductivity in the out-of-plane direction (0.57 W/mK). The proposed freeze-casting method can be applied for the fabrication of various polymers and fillers and is promising for the development of flexible porous composite elastomers with out-of-plane aligned thermally conductive pathways.

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. The dynamic fracture behaviors of SR gels gives us the time scale of the sliding dynamics of the cross-links, which is at the micro-sec scale. The fast sliding motion of the cross-links leads to the elasticity of the SR gels. The SR concept can be applied to solvent-free elastomers and composite materials.

We studied the rheological and mechanical properties of a series of poly(vinyl alcohol) dual crosslink hydrogels, permanently crosslinked by glutaraldehyde and transiently crosslinked by borate ions, at various crosslinking densities. The contribution of the chemical and physical crosslinks to the dynamic moduli was first determined with linear oscillatory tests, and the additivity of the two contributions was validated. The single relaxation time of the system was interpreted as the physical bond breaking time which can be slowed down by reassociation of the open physical bonds before full relaxation. By comparing the Rouse relaxation time of the strand between two adjacent crosslinks with the healing time of the physical bonds, an increase in the relaxation time with decreasing density of physical crosslinks was explained. In all cases, the extensibility and stress at break of the gels were found to increase with the addition of physical crosslinks, but the extensibility increased the most for the small...

Supramolecular slide-ring (SR) elastomers without solvent were fabricated by cross-linking of polymer-grafted polyrotaxane in which α -cyclodextrins (CDs) with poly- e -caprolactone (PCL) side chains are threaded on a polyethylene glycol (PEG) axial linear chain. The cross-links in the SR elastomers are capable of sliding along the backbone in response to applied stress. Mechanical properties of the SR elastomers with different cross-linking densities were compared with those of fixed cross-link (FC) elastomers prepared from PCL-grafted hydroxypropyl cellulose (HPC) to understand the influence of the slidable cross-links. The SR elastomers are found to undergo less strain-hardening at large strains and demonstrate higher strains at break than the conventional FC elastomers with the same Young's moduli.

We propose using a slide-ring (SR) gel electrolyte to achieve a gel polymer electrolyte with both sufficient mechanical strength and high ionic conductivity. The SR gel is made from polyrotaxane, which has a structure that consists of cyclic molecules, α-cyclodextrins (CDs), threaded by an axial polymer chain, polyethylene glycol (PEG), and cross-linked by divinyl sulfone. The SR gel electrolyte was made from SR gels which were swollen by an electrolyte solution (ES) prepared with lithium salt and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI). The swelling behavior of SR gel in the ES by the formation of coordination bonds between lithium cations and oxygen atoms on CDs was investigated. The swelling behavior and ionic conductivity of the SR gel swollen with ES had a peak at 0.8 M lithium ion in the ES and the molar conductivity of the SR gel swollen with ES was 85% more than that of pristine ES. The puncture resistance of the SR gel electrolyte was also investigated; the puncture elongation was more than 1000% and the Young’s modulus increased with the lithium ion concentration due to an increase in the coordination bonds between lithium cations and the oxygen atoms on CDs.

We investigate the fracture toughness of slide-ring (SR) gels, in which polymer chains are cross-linked by ring molecules, at various strain rates to evaluate the sliding speed of the cross-linking points. SR gels show a drastic decrease of the fracture energy at crack velocities higher than a critical value, since the sliding motion of the rings cannot catch up with the high deformation rates. From the critical transition velocity, we estimated the characteristic time scale of the sliding dynamics to be micro-seconds under the single-layer fracture assumption.

We develop a three-dimensional continuum theory for a dual cross-link gel with permanent and transient bonds. This theory connects the breaking and re-forming kinetics of the transient bonds to the large deformation behavior of the gel. Although based on similar principles as our previous theory for the same gel, the new theory addresses a limitation of the previous theory and agrees equally well with experimental data. Specifically, in the new theory we assume that breaking and re-forming kinetics of transient bonds reaches a steady state. This assumption leads to fewer material parameters and enables the new theory to capture the healing process of the dual cross-link gel. In addition, the steady state assumption also allows the new theory to reduce to classical linear viscoelastic theory in the limit of infinitesimal strains, where the kinetics of bond breaking and re-formation can be linked directly to the relaxation function. We also extend the theory to account for strain stiffening under very large...