Entropy-Driven Design of Highly Impact-Stiffening Supramolecular Polymer Networks with Salt-Bridge Hydrogen Bonds.

Impact-stiffening materials that undergo a strain rate-induced soft-to-rigid transition hold great promise as soft armors in the protection of the human body and equipment. However, current impact-stiffening materials, such as polyborosiloxanes and shear-thickening fluids, often exhibit a limited impact-stiffening response. Herein, we propose a design strategy for fabricating highly impact-stiffening supramolecular polymer networks by leveraging high-entropy-penalty physical interactions. We synthesized a fully biobased supramolecular polymer comprising poly(α-thioctic acid) and arginine clusters, whose chain dynamics are governed by highly specific guanidinium-carboxylate salt-bridge hydrogen bonds. The resulting material exhibits an exceptional impact-stiffening response of ∼2100 times, transitioning from a soft dissipating state (21 kPa, 0.1 Hz) to a highly stiffened glassy state (45.3 MPa, 100 Hz) with increasing strain rates. Moreover, the material's high energy-dissipating and hot-melting properties bring excellent damping performance and easy hybridization with other scaffolds. This entropy-driven approach paves the way for the development of next-generation soft, sustainable, and impact-resistant materials.

A systematic review and meta-analysis of clinical efficacy of early and late rehabilitation interventions for ischemic stroke.

INTRODUCTION: At present, stroke has become the first cause of death and disability among Chinese adults. With the coming of the aging population in China, the disease burden brought by stroke will be increasingly aggravated. And stroke is a leading cause of disability. There is a golden plastic period after stroke, during which timely and safe intervention and rehabilitation therapy can effectively improve the disability status. However, there is still controversy about the duration of interventional rehabilitation after stroke. This study conducted a meta-analysis on the influence of intervention in early and late ischemic stroke rehabilitation. METHOD: Chinese language databases such as CNKI, Wanfang, and VIP, and English language databases such as Embase, PubMed, Web of Science, and The Cochrane Library were searched, and RCT related to early and late rehabilitation of ischemic stroke from the establishment of the database to October 2023 was collected. Review Manager 5.4.1 was used for relevant analysis. The main outcomes were Barthel Index or Modified Barthel Index, Fugl-Meyer Assessment scale, NIHSS, China Stroke Scale. Standardized Mean Difference (SMD) was used as an effective indicator of continuity variables, and the estimated interval was expressed by 95% confidence interval (CI). RESULTS: A total of 1908 patients were included in 16 studies. The results showed that, compared with late rehabilitation, early rehabilitation improved clinical efficacy. Barthel Index or Modified Barthel Index score was [SMD = 1.40, 95%CI(1.16,1.63), p < 0.001]; the score of Fugl-Meyer Assessment Scale was [SMD = 1.18, 95%Cl (0.85, 1.52), P < 0.001]; the score of NIHSS was [SMD= -0.44, 95% CI(-0.65, -0.24), P < 0.001]; the result of China Stroke Scale score was [SMD= -0.37, 95%CI(-0.56, -0.18), P < 0.001]. CONCLUSION: In comparison with late rehabilitation, early rehabilitation can significantly improve self-care abilities, daily activities, and neurological functions of ischemic stroke patients. TRIAL REGISTRATION: This meta-analysis has been registered with Prospero, and the registration number is CRD42022309911. The registration period is March 22, 2022.

Entropy-Mediated Polymer-Cluster Interactions Enable Dramatic Thermal Stiffening Hydrogels for Mechanoadaptive Smart Fabrics.

Thermal stiffening materials that are naturally soft but adaptively self-strengthen upon heat are intriguing for load-bearing and self-protection applications at elevated temperatures. However, to simultaneously achieve high modulus change amplitude and high mechanical strength at the stiffened state remains challenging. Herein, entropy-mediated polymer-mineral cluster interactions are exploited to afford thermal stiffening hydrogels with a record-high storage modulus enhancement of 13 000 times covering a super wide regime from 1.3 kPa to 17 MPa. Such a dramatic thermal stiffening effect is ascribed to the transition from liquid-liquid to solid-liquid phase separations, and at the molecular level, driven by enhanced polymer-cluster interactions. The hydrogel is further processed into sheath-core fibers and smart fabrics, which demonstrate self-strengthening and self-powered sensing properties by co-weaving another liquid metal fiber as both the joule heater and triboelectric layer.

Tuning the properties of hydrogels made from poly(acrylic acid) and calcium salts.

Hydrogels consisting of poly(acrylic acid) (PAA) and calcium ions are a promising class of materials with shapeable, stretchable and self-healing behaviour originating from the reversible and dynamic nature of the electrostatic and hydrogen bonds in the structure. In the dry state, such materials - referred to as "mineral plastics"- can be transparent, hard and flame-resistant, while addition of water will result in rehydration and complete recoverage of the initial gel-like state. These desirable characteristics strongly depend on the molar mass of the used type of PAA and the experimental conditions at which the hydrogels are prepared. In this work, we show how the macroscopic properties of the materials can be adjusted by controlling the initial concentration of dissolved PAA and/or its molecular weight, and how rheological measurements can be used to monitor the resulting physical properties. Furthermore, we have employed isothermal titration calorimetry (ITC) to investigate thermodynamic aspects of the hydrogel formation to gain a better understanding of the underlying mechanism(s). Our results reveal that, and explain why, PAA molar masses between 50 and 100 kDa are particulary suitable for the formation of hydrogels with optimized properties, thus establishing a rational basis for targeted design of such materials with tailor-made characteristics.

Colloidally Stable Monolayer Nanosheets with Colorimetric Responses.

Despite the discovery of chromogenic-layered materials for decades of years, fabrication of colloidally stable monolayer organic 2D nanosheets in aqueous media with colorimetric responses is still challenging. Herein reported is the first solution synthesis of chromic monolayer nanosheets via the topochemical polymerization of self-assembled amphiphilic diacetylenes in aqueous media. The polydiacetylene (PDA) nanosheets are ≈3-4 nm thick in solution and only ≈1.9 nm thick in the dried state, while the lateral size can reach several micrometers. Moreover, the aqueous stability endows PDA nanosheets with excellent processability, which can further assemble into films via vacuum filtration or act as an ink for high-resolution inkjet printing. The filtrated films and printed patterns exhibit fully reversible blue-to-red thermochromism, and the film also displays an interesting reversible colorimetric transition in response to near-infrared light, which is not reported for other PDA-only systems. The present colloidal PDA nanosheets should represent a new kind of chromic organic 2D nanomaterials that may be applied as novel building blocks for developing intelligent hybrid materials and may also find diverse sensing, display and/or anticounterfeiting applications.

Microdynamic changes of moisture-induced crystallization of amorphous calcium carbonate revealed via in situ FTIR spectroscopy.

Amorphous calcium carbonate (ACC) is the most important intermediate phase in the nucleation/crystallization process of CaCO3, and thus the proper interpretation of how ACC transforms into final crystals at the molecular level is crucial to understand various biomineralization phenomena. Herein, we successfully monitored the moisture-induced crystallization process of ACC via in situ FTIR spectroscopy, which is very sensitive to the specific changes of the different vibrational modes of carbonates and water molecules. In combination with the tools of perturbation correlation moving window and two-dimensional correlation spectroscopy, it is found that the driving force of ACC crystallization is the fracture of hydrogen bonds formed by H2OCO32-. The bending vibrations of carbonate are more sensitive to moisture permeation than the stretching modes, and the whole crystallization process can be divided into three sequential stages, i.e., the hydrated ACC first loses its structural water and converts to the dehydrated ACC, which then gradually transforms into vaterite, followed by the final growth of vaterite crystals. Anhydrous ACC microdomains are found to be already existing in the as-prepared ACCs.

The influence of a thermoresponsive polymer on the microdynamic phase transition mechanisms of distinctly structured thermoresponsive ionic liquids.

The study of a ternary solution involving a thermoresponsive polymer, a thermoresponsive ionic liquid (IL), and a solvent will not only help with interpreting their distinct phase transition behavior, but also promote the development of novel thermoresponsive systems. In this paper, we investigate the influence of a conventional thermoresponsive polymer, poly(2-isopropyl-2-oxazoline) (PIPOZ), on the phase transition behavior of two thermoresponsive ILs ([P4,4,4,6][MC3S], [P4,4,4,4][SS]) with different structures. Although the addition of PIPOZ reduces the transition temperatures of both ILs, our analyses demonstrate that there exists a large difference in the microdynamic phase transition mechanisms between [P4,4,4,6][MC3S]/PIPOZ and [P4,4,4,4][SS]/PIPOZ aqueous solutions. Both PIPOZ and [P4,4,4,6][MC3S] experience unexpectedly an unusual over-hydration process before a two-step phase transition of the mixture solution, which can be explained by the presence of a new kind of intermolecular bridging hydrogen bond (IL-water-polymer), whereas only PIPOZ undergoes dehydration around the transition temperature of the [P4,4,4,4][SS]/PIPOZ aqueous solution. Further spectral analyses reveal that both [P4,4,4,6][MC3S] and PIPOZ engage in the phase separation of the ternary solution jointly, whereas PIPOZ takes part in the phase transition of [P4,4,4,4][SS]/PIPOZ solution more independently.

Alignment of Amorphous Iron Oxide Clusters: A Non-Classical Mechanism for Magnetite Formation.

Despite numerous studies on the nucleation and crystallization of iron (oxyhydr)oxides, the roles of species developing during the early stages, especially primary clusters and intermediate amorphous particles, are still poorly understood. Herein, both ligand-free and ligand-protected amorphous iron oxide (AIO) clusters (<2 nm) were synthesized as precursors for magnetite formation. Thermal annealing can crystallize the clusters into magnetite particles, and AIO bulk phases with domains of pre-aligned clusters are found to be direct precursors to crystals, suggesting a non-classical aggregation-based pathway that differs from the reported oriented attachment or particle accretion mechanisms.

Hydrogels from Amorphous Calcium Carbonate and Polyacrylic Acid: Bio-Inspired Materials for "Mineral Plastics".

Given increasing environmental issues due to the large usage of non-biodegradable plastics based on petroleum, new plastic materials, which are economic, environmentally friendly, and recyclable are in high demand. One feasible strategy is the bio-inspired synthesis of mineral-based hybrid materials. Herein we report a facile route for an amorphous CaCO3 (ACC)-based hydrogel consisting of very small ACC nanoparticles physically cross-linked by poly(acrylic acid). The hydrogel is shapeable, stretchable, and self-healable. Upon drying, the hydrogel forms free-standing, rigid, and transparent objects with remarkable mechanical performance. By swelling in water, the material can completely recover the initial hydrogel state. As a matrix, thermochromism can also be easily introduced. The present hybrid hydrogel may represent a new class of plastic materials, the "mineral plastics".

Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2†nm).

Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO3 core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.

From globules to crystals: a spectral study of poly(2-isopropyl-2-oxazoline) crystallization in hot water.

One easy strategy to comprehend the complex folding/crystallization behaviors of proteins is to study the self-assembly process of their synthetic polymeric analogues with similar properties owing to their simple structures and easy access to molecular design. Poly(2-isopropyl-2-oxazoline) (PIPOZ) is often regarded as an ideal pseudopeptide with similar two-step crystallization behavior to proteins, whose aqueous solution experiences successive lower critical solution temperature (LCST)-type liquid-liquid phase separation upon heating and irreversible crystallization when annealed above LCST for several hours. In this paper, by microscopic observations, IR and Raman spectroscopy in combination with 2D correlation analysis, we show that the second step of PIPOZ crystallization in hot water can be further divided into two apparent stages, i.e., nucleation and crystal growth, and perfect crystalline PIPOZ chains are found to only develop in the second stage. While all the groups exhibit changes in initial nucleation, only methylene groups on the backbone participate in the crystal growth stage. During nucleation, a group motion transfer is found from the side chain to the backbone, and nucleation is assumed to be mainly driven by the cleavage of bridging C=O···D-O-D···O=C hydrogen bonds followed by chain arrangement due to amide dipolar orientation. Nevertheless, during crystal growth, a further chain ordering process occurs resulting in the final formation of crystalline PIPOZ chains with partial trans conformation of backbones and alternative side chains on the two sides. The underlying crystallization mechanism of PIPOZ in hot water we present here may provide very useful information for understanding the crystallization of biomacromolecules in biological systems.

Conformational changes in the heat-induced crystallization of poly(2-isopropyl-2-oxazoline) in the solid state.

Poly(2-isopropyl-2-oxazoline) (PIPOZ) with an isomeric structure of poly(N-isopropylacrylamide) (PNIPAM) represents an important class of stimuli-responsive synthetic polymers. Unlike PNIPAM, PIPOZ exhibits an unusual heat-induced crystallization behaviour at around 120 °C in the solid state, whose dynamic mechanism involving all group motions and conformational changes is still poorly understood. In this paper, IR spectroscopy in combination with two-dimensional analysis methods - the perturbation correlation moving window (PCMW) and two-dimensional correlation spectroscopy (2DCOS) - was used to monitor and study the conformational changes in the crystallization of PIPOZ in the solid state. The incorporated water molecules are found to be not necessary to assist the solid-state crystallization of the PIPOZ film. PCMW and 2DCOS analyses reveal that following the breaking of minor CH3O[double bond, length as m-dash]C hydrogen bonds, all the group moieties exhibit highly synergetic motions during crystallization, and methylene groups on the backbone do not show significant changes throughout the crystallization process. Raman spectroscopic and molecular dynamics simulation results further support this conclusion. The chain alignment of PIPOZ chains is shown to be mainly achieved by the lateral distortion of coplanar side chains or the ordered chain arrangement of amide dipoles together with the torsion of the backbone through C-N linkages. Upon heating, gauche conformations of methylene groups on the backbone are always dominating, resulting in an ordered PIPOZ chain with alternate side chains and a slightly distorted backbone.

Peeling-Stiffening Self-Adhesive Ionogel with Superhigh Interfacial Toughness.

Self-adhesive materials that can directly adhere to diverse solid surfaces are indispensable in modern life and technologies. However, it remains a challenge to develop self-adhesive materials with strong adhesion while maintaining its intrinsic softness for efficient tackiness. Here, a peeling-stiffening self-adhesive ionogel that reconciles the seemingly contradictory properties of softness and strong adhesion is reported. The ionogel contains two ionophilic repeating units with distinct associating affinities, which allows to adaptively wet rough surface in the soft dissipating state for adhering, and to dramatically stiffen to the glassy state upon peeling. The corresponding modulus increases by 117 times driven by strain-rate-induced phase separation, which greatly suppresses crack propagation and results in a super high interfacial toughness of 8046 J m-2 . The self-adhesive ionogel is also transparent, self-healable, recyclable, and can be easily removed by simple moisture treatment. This strategy provides a new way to design high-performance self-adhesive materials for intelligent soft devices.

Self-compliant ionic skin by leveraging hierarchical hydrogen bond association.

Robust interfacial compliance is essential for long-term physiological monitoring via skin-mountable ionic materials. Unfortunately, existing epidermal ionic skins are not compliant and durable enough to accommodate the time-varying deformations of convoluted skin surface, due to an imbalance in viscosity and elasticity. Here we introduce a self-compliant ionic skin that consistently works at the critical gel point state with almost equal viscosity and elasticity over a super-wide frequency range. The material is designed by leveraging hierarchical hydrogen bond association, allowing for the continuous release of polymer strands to create topological entanglements as complementary crosslinks. By embodying properties of rapid stress relaxation, softness, ionic conductivity, self-healability, flaw-insensitivity, self-adhesion, and water-resistance, this ionic skin fosters excellent interfacial compliance with cyclically deforming substrates, and facilitates the acquisition of high-fidelity electrophysiological signals with alleviated motion artifacts. The presented strategy is generalizable and could expand the applicability of epidermal ionic skins to more complex service conditions.

Making Sticky-Slippery Switchable Fluorogels Through Self-Adaptive Bicontinuous Phase Separation.

Developing gel materials with tunable frictional properties is crucial for applications in soft robotics, anti-fouling, and joint protection. However, achieving reversible switching between extreme sticky and slippery states remains a formidable challenge due to the opposing requirements for energy dissipation on gel surfaces. Herein, a self-adaptive bicontinuous fluorogel is introduced that decouples lubrication and adhesion at varying temperatures. The phase-separated fluorogel comprises a soft fluorinated lubricating phase and a stiff yet thermal-responsive load-bearing phase. At ambient temperature, the fluorogel exhibits a highly slippery surface owing to a low-energy-dissipating lubricating layer, demonstrating an ultralow friction coefficient of 0.004. Upon heating, the fluorogel transitions into a highly dissipating state via hydrogen bond dissociation, concurrently releasing adhesive dangling chains to make the surface highly sticky with an adhesion strength of ≈362 kPa. This approach provides a promising foundation for creating advanced adaptive materials with on-demand self-adhesive and self-lubricating capabilities.

A Solid-Liquid Bicontinuous Fiber with Strain-Insensitive Ionic Conduction.

Stretchable ionic conductors are crucial for enabling advanced iontronic devices to operate under diverse deformation conditions. However, when employed as interconnects, existing ionic conductors struggle to maintain stable ionic conduction under strain, hindering high-fidelity signal transmission. Here, it is shown that strain-insensitive ionic conduction can be achieved by creating a solid-liquid bicontinuous microstructure. A bicontinuous fiber from polymerization-induced phase separation, which contains a solid elastomer phase interpenetrated by a liquid ion-conducting phase, is fabricated. The spontaneous partitioning of dissolved salts leads to the formation of a robust self-wrinkled interface, fostering the development of highly tortuous ionic channels. Upon stretch, these meandering ionic channels are straightened, effectively enhancing ionic conductivity to counteract the strain effect. Remarkably, the fiber retains highly stable ionic conduction till fracture, with only 7% resistance increase at 200% strain. This approach presents a promising avenue for designing durable ionic cables capable of signal transmission with minimal strain-induced distortion.

Low-Hysteresis and Tough Ionogels via Low-Energy-Dissipating Cross-Linking.

Low-hysteresis merits can help polymeric gel materials survive from consecutive loading cycles and promote life span in many burgeoning areas. However, it is a big challenge to design low-hysteresis and tough polymeric gel materials, especially for ionogels. This can be attributed to the fact that higher viscosities of ionic liquids (ILs) would increase chain friction of polymeric gels and eventually dissipate large amounts of energy under deformation. Herein, a chemical design of ionogels is proposed to achieve low-hysteresis characteristics in both mechanical and electric aspects via hierarchical aggregates formed by supramolecular self-assembly of quadruple H-bonds in a soft IL-rich polymeric matrix. These self-assembled nanoaggregates not only can greatly reinforce the polymeric matrix and enhance resilience, but also exhibit low-energy-dissipating features under stress conditions, simultaneously benefiting for low-hysteresis properties. These aggregates can also promote toughness and subsequent anti-fatigue properties in response to external cyclic mechanical stimuli. More importantly, these ionogels are presented as a model system to elucidate the underlying mechanism of the low hysteresis and fatigue resistance. Based on these findings, it is further demonstrated that the supramolecular low-hysteresis strategy is universal.

Non-equilibrium-Growing Aesthetic Ionic Skin for Fingertip-Like Strain-Undisturbed Tactile Sensation and Texture Recognition.

Humans use periodically ridged fingertips to precisely perceive the characteristics of objects via ion-based fast- and slow-adaptive mechanotransduction. However, designing artificial ionic skins with fingertip-like tactile capabilities remains challenging because of the contradiction between structural compliance and pressure sensing accuracy (e.g., anti-interference from stretch and texture recognition). Inspired by the formation and modulus-contrast hierarchical structure of fingertips, an aesthetic ionic skin grown from a non-equilibrium Liesegang patterning process is introduced. This ionic skin with periodic stiff ridges embedded in a soft hydrogel matrix enables strain-undisturbed triboelectric dynamic pressure sensing as well as vibrotactile texture recognition. By coupling with another piezoresistive ionogel, an artificial tactile sensory system is further fabricated as a soft robotic skin to mimic the simultaneous fast- and slow-adaptive multimodal sensations of fingers in grasping actions. This approach may inspire the future design of high-performance ionic tactile sensors for intelligent applications in soft robotics and prosthetics.

Aqueous spinning of robust, self-healable, and crack-resistant hydrogel microfibers enabled by hydrogen bond nanoconfinement.

Robust damage-tolerant hydrogel fibers with high strength, crack resistance, and self-healing properties are indispensable for their long-term uses in soft machines and robots as load-bearing and actuating elements. However, current hydrogel fibers with inherent homogeneous structure are generally vulnerable to defects and cracks and thus local mechanical failure readily occurs across fiber normal. Here, inspired by spider spinning, we introduce a facile, energy-efficient aqueous pultrusion spinning process to continuously produce stiff yet extensible hydrogel microfibers at ambient conditions. The resulting microfibers are not only crack-insensitive but also rapidly heal the cracks in 30 s by moisture, owing to their structural nanoconfinement with hydrogen bond clusters embedded in an ionically complexed hygroscopic matrix. Moreover, the nanoconfined structure is highly energy-dissipating, moisture-sensitive but stable in water, leading to excellent damping and supercontraction properties. This work creates opportunities for the sustainable spinning of robust hydrogel-based fibrous materials towards diverse intelligent applications.

Highly Damping and Self-Healable Ionic Elastomer from Dynamic Phase Separation of Sticky Fluorinated Polymers.

Shock-induced low-frequency vibration damage is extremely harmful to bionic soft robots and machines that may incur the malfunction of fragile electronic elements. However, current skin-like self-healable ionic elastomers as the artificial sensing and protecting layer still lack the ability to dampen vibrations, due to their almost opposite design for molecular frictions to material's elasticity. Inspired by the two-phase structure of adipose tissue (the natural damping skin layer), here, a highly damping ionic elastomer with energy-dissipating nanophases embedded in an elastic matrix is introduced, which is formed by polymerization-induced dynamic phase separation of sticky fluorinated copolymers in the presence of lithium salts. Such a supramolecular design decouples the elastic and damping functions into two distinct phases, and thus reconciles a few intriguing properties including ionic conductivity, high stretchability, softness, strain-stiffening, elastic recovery, room-temperature self-healability, recyclability, and most importantly, record-high damping capacity at the human motion frequency range (loss factor tan δ > 1 at 0.1-50 Hz). This study opens the door for the artificial syntheses of high-performance damping ionic skins with robust sensing and protective applications in soft electronics and robotics.