Mechanically skin-like and water-resistant self-healing bioelastomer for high-tension wound healing.

The biomedical application of self-healing materials in wet or (under)water environments is quite challenging because the insulation and dissociation effects of water molecules significantly reduce the reconstruction of material-interface interactions. Rapid closure with uniform tension of high-tension wounds is often difficult, leading to further deterioration and scarring. Herein, a new type of thermosetting water-resistant self-healing bioelastomer (WRSHE) was designed by synergistically incorporating a stable polyglycerol sebacate (PGS) covalent crosslinking network and triple hybrid dynamic networks consisting of reversible disulfide metathesis (SS), and dimethylglyoxime urethane (Dou) and hydrogen bonds. And a resveratrol-loaded WRSHE (Res@WRSHE) was developed by a swelling, absorption, and crosslinked network locking strategy. WRSHEs exhibited skin-like mechanical properties in terms of nonlinear modulus behavior, biomimetic softness, high stretchability, and good elasticity, and they also achieved ultrafast and highly efficient self-healing in various liquid environments. For wound-healing applications of high-tension full-thickness skin defects, the convenient surface assembly by self-healing of WRSHEs provides uniform contraction stress to facilitate tight closure. Moreover, Res@WRSHEs gradually release resveratrol, which helps inflammatory response reduction, promotes blood vessel regeneration, and accelerates wound repair.

Biomimetic Non-ergodic Aging by Dynamic-to-covalent Transitions in Physical Hydrogels.

Hydrogels are soft materials engineered to suit a multitude of applications that exploit their tunable mechanochemical properties. Dynamic hydrogels employing noncovalent, physically cross-linked networks dominated by either enthalpic or entropic interactions enable unique rheological and stimuli-responsive characteristics. In contrast to enthalpy-driven interactions that soften with increasing temperature, entropic interactions result in largely temperature-independent mechanical properties. By engineering interfacial polymer-particle interactions, we can induce a dynamic-to-covalent transition in entropic hydrogels that leads to biomimetic non-ergodic aging in the microstructure without altering the network mesh size. This transition is tuned by varying temperature and formulation conditions such as pH, which allows for multivalent tunability in properties. These hydrogels can thus be designed to exhibit either temperature-independent metastable dynamic cross-linking or time-dependent stiffening based on formulation and storage conditions, all while maintaining structural features critical for controlling mass transport, akin to many biological tissues. Such robust materials with versatile and adaptable properties can be utilized in applications such as wildfire suppression, surgical adhesives, and depot-forming injectable drug delivery systems.

Self-healing, antioxidant, and antibacterial Bletilla striata polysaccharide-tannic acid dual dynamic crosslinked hydrogels for tissue adhesion and rapid hemostasis.

Biomaterials capable of achieving effective sealing and hemostasis at moist wounds are in high demand in the clinical management of acute hemorrhage. Bletilla striata polysaccharide (BSP), a natural polysaccharide renowned for its hemostatic properties, holds promising applications in biomedical fields. In this study, a dual-dynamic-bonds crosslinked hydrogel was synthesized via a facile one-pot method utilizing poly(vinyl alcohol) (PVA)-borax as a matrix system, followed by the incorporation of BSP and tannic acid (TA). Chemical borate ester bonds formed around borax, coupled with multiple physical hydrogen bonds between BSP and other components, enhanced the mechanical properties and rapid self-healing capabilities. The catechol moieties in TA endowed the hydrogel with excellent adhesive strength of 30.2 kPa on the surface of wet tissues and facilitated easy removal without residue. Benefiting from the synergistic effect of TA and the preservation of the intrinsic properties of BSP, the hydrogel exhibited outstanding biocompatibility, antibacterial, and antioxidant properties. Moreover, it effectively halted acute bleeding within 31.3 s, resulting in blood loss of 15.6 % of that of the untreated group. As a superior hemostatic adhesive, the hydrogel in this study is poised to offer a novel solution for addressing future acute hemorrhage, wound healing, and other biomedical applications.

Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages.

A novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B-O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3-based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π-π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions. Significantly, the CPOFs can be synthesized on a gram-scale using cost-effective monomers. In addition, the numerous acidic sites endow the CPOFs with high NH3 capacity, surpassing most porous organic materials and commercial materials.

Interfacial self-healing polymer electrolytes for Long-Cycle silicon anodes in High-Performance solid-state lithium batteries.

For all-solid-state lithium-ion batteries (ASSLIBs), silicon (Si) stands out as an appealing anodes material due to its high energy density and improved safety compared to lithium metal. However, the substantial volume changes during cycling result in poor solid-state physical contact and electrolyte-electrode interface issues, leading to unsatisfactory electrochemical performance. In this study, we employed in-situ polymerization to construct an integrated Si anodes/self-healing polymer electrolyte for ASSLIBs. The polymer chain reorganization stems from numerous dynamic bonds in the constructed self-healing dynamic supermolecular elastomer electrolyte (SHDSE) molecular structure. Notably, SHDSE also serves as a Si anodes binder with enhanced adhesive capability. As a result, the well-structured Li|SHDSE|Si-SHDSE cell generates subtle electrolyte-electrode interface contacts at the molecular level, which can offer a continuous and stable Li+ transport pathway, reduce Si particle displacement, and mitigate electrode volume expansion. This further enhances cyclic stability (>500 cycles with 68.1 % capacity retention and >99.8 % Coulombic efficiency). More practically, the 2.0 Ah wave-shaped Si||LiCoO2 soft-pack battery with in-situ cured SHDSE exhibits strongly stabilized electrochemical performance (1.68 Ah after 700 cycles, 86.2 % capacity retention) in spite of a high operating temperatures up to 100 °C and in various bending tests. This represents a groundbreaking report in flexible solid-state soft-pack batteries containing Si anodes.

Dynamic-Bond-Mediated Chain Reptation Enhances Energy Dissipation of Elastomers.

Vibrations with various frequencies in daily life and industry can cause health hazards and fatigue failure of critical structures, which requires the development of elastomers with high energy dissipation at desired frequencies. Current strategies relying on tuning characteristic relaxation time of polymer chains are mostly qualitative empirical methods, and it is difficult to precisely control damping performances. Here, we report a general strategy for constructing dynamic crosslinked polymer fluid gels that provide controllable ultrahigh energy dissipation. This is realized by dynamic-bond-mediated chain reptation of polymer fluids in a crosslinked network, where the characteristic time of chain reptation is dominated by the presence of well-defined dissociation time of dynamic bonds and almost independent of their molar mass. Using prototypical supramolecular polydimethylsiloxane elastomers, we demonstrate that dynamic crosslinked polymer fluid gels exhibit a controllable ultrahigh damping performance at desired frequencies (10-2~102 Hz), exceeding that of typical state-of-the-art silicone damping materials. Their shock absorption is over 300 % higher than that of commercial silicone rubber under the same impact force.

Multifunctional fish-skin collagen-based hydrogel sealant with dual-dynamic-bond cross-linked for rapid hemostasis and accelerated wound healing.

Collagen (COL) is the most widespread functional protein. Designing and developing dual-dynamic-bond cross-linked COL adhesive hydrogel sealants with multifunctional is highly advantageous for achieving a superior wound closure effect and hemostasis. In this study, we developed hybrid hydrogels consisting of fish-skin COL, oxidized sodium alginate (OSA), borax and polyvinyl alcohol (PVA) to enhance full-thickness wound healing. The hydrogels were furnished with first-rate self-healing capabilities through the dual-dynamic-bond cross-linking of dynamic Schiff base bonds (COL-OSA) and diol boric acid bonds (OSA-borax) with reversible breakage and re-formation. Moreover, the incorporation of PVA stimulated the formation of hydrogen bonds in the system, bolstering the stability of the hydrogel framework. The prepared hydrogel manifests self-healing, injectability, multifunctional adhesiveness and biodegradability. In vivo assessment of the hemostatic capacity of COSP20 hydrogel was superior to gauze both in the mice liver injury model and mice tail amputation model. In addition, a full-thickness skin wound model in mice revealed that the COSP20 hydrogel facilitated faster wound closure by accelerating reepithelialization, COL deposition and angiogenesis. These findings illustrate the potential of hybrid fish-skin COL-based hydrogels to enhance wound healing and promote rapid tissue repair, and provide new possibilities for the effective utilization of marine fishery resources.

3D Printing of Self-Healing Materials.

This review article presents a comprehensive overview of the latest advances in the field of 3D printable structures with self-healing properties. Three-dimensional printing (3DP) is a versatile technology that enables the rapid manufacturing of complex geometric structures with precision and functionality not previously attainable. However, the application of 3DP technology is still limited by the availability of materials with customizable properties specifically designed for additive manufacturing. The addition of self-healing properties within 3D printed objects is of high interest as it can improve the performance and lifespan of structural components, and even enable the mimicking of living tissues for biomedical applications, such as organs printing. The review will discuss and analyze the most relevant results reported in recent years in the development of self-healing polymeric materials that can be processed via 3D printing. After introducing the chemical and physical self-healing mechanism that can be exploited, the literature review here reported will focus in particular on printability and repairing performances. At last, actual perspective and possible development field will be critically discussed.

The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se-Se/Te-Te Bonds.

We report thermochromism in crystals of diphenyl diselenide (dpdSe) and diphenyl ditelluride (dpdTe), which is at variance with the commonly known mechanisms of thermochromism in molecular crystals. Variable temperature neutron diffraction studies indicated no conformational change, tautomerization or phase transition between 100 K and 295 K. High-pressure crystallography studies indicated no associated piezochromism in dpdSe and dpdTe crystals. The evolution of the crystal structures and their electronic band structure with pressure and temperature reveal the contributions of intramolecular and intermolecular factors towards the origin of thermochromism-especially the intermolecular Se⋅⋅⋅Se and Te⋅⋅⋅Te chalcogen bonds and torsional modes of vibrations around the dynamic Se-Se and Te-Te bonds. Further, a co-crystal of dpdSe with iodine (dpdSe-I2 ) and an alloy crystal of dpdSe and dpdTe implied a predominantly intramolecular origin of the observed thermochromism associated with vibronic coupling.

Fabrication of versatile poly(xylitol sebacate)-co-poly(ethylene glycol) hydrogels through multifunctional crosslinkers and dynamic bonds for wound healing.

Poly(polyol sebacate) (PPS) polymer family has been recognized as promising biomaterials for biomedical applications with their characteristics of easy production, elasticity, biodegradation, and cytocompatibility. Poly(xylitol sebacate)-co-poly(ethylene glycol) (PXS-co-PEG) has been developed to fabricate PPS-based hydrogels; however, current PXS-co-PEG hydrogels presented limited properties and functions due to the limitations of the crosslinkers and crosslinking chemistry used in the hydrogel formation. Here, we fabricate a new type of PXS-co-PEG hydrogels through the use of multifunctional crosslinkers as well as dynamic bonds. In our design, polyethyleneimine-polydopamine (PEI-PDA) macromers are utilized to crosslink aldehyde-functionalized PXS-co-PEG (APP) through imine bonds and hydrogen bonds. PEI-PDA/APP hydrogels present multiple functional properties (e.g., fluorescent, elastomeric, biodegradable, self-healing, bioadhesive, antioxidant, and antibacterial behaviors). These properties of PEI-PDA/APP hydrogels can be fine-tuned by changing the PDA grafting degrees in the PEI-PDA crosslinkers. Most importantly, PEI-PDA/APP hydrogels are considered promising wound dressings to promote tissue remodeling and prevent bacterial infection in vivo. Taken together, PEI-PDA/APP hydrogels have been demonstrated as versatile biomaterials to provide multiple tailorable properties and desirable functions to expand the utility of PPS-based hydrogels for advanced biomedical applications. STATEMENT OF SIGNIFICANCE: Various strategies have been developed to fabricate poly(polyol sebacate) (PPS)-based hydrogels. However, current PPS-based hydrogels present limited properties and functions due to the limitations of the crosslinkers and crosslinking chemistry used in the hydrogel formation. This work describes that co-engineering crosslinkers and interfacial crosslinking is a promising approach to synthesizing a new type of poly(xylitol sebacate)-co-poly(ethylene glycol) (PXS-co-PEG) hydrogels as multifunctional hydrogels to expand the utility of PPS-based hydrogels for advanced biomedical applications. The fabricated hydrogels present multiple functional properties (e.g., fluorescent, biodegradable, elastomeric, self-healing, bioadhesive, antioxidative, and antibacterial), and these properties can be fine-tuned by the defined crosslinkers. The fabricated hydrogels are also used as promising wound dressing biomaterials to exhibit promoted tissue remodeling and prevent bacterial infection in vivo.

Fabrication of triple-crosslinked gelatin/alginate hydrogels for controlled release applications.

Hydrogels have been demonstrated as smart drug carriers to recognize the tumor microenvironment for cancer treatment, where the dynamic crosslinks in the hydrogel network contribute to the stimuli-responsive features but also result in poor stability and weak mechanical property of the hydrogels. Here, phenylboronic acid-grafted polyethyleneimine (PBA-PEI)-modified gelatin (PPG) was synthesized to crosslink alginate dialdehyde (ADA) through imine bonds and boronate ester bonds, and then calcium ions (Ca2+) were added to introduce the third calcium-carboxylate crosslinking in the network to form the triple-crosslinked PPG/ADA-Ca2+ hydrogels. Given the three types of dynamic bonds in the network, PPG/ADA-Ca2+ hydrogels possessed a self-healing manner, stimuli-responsiveness, and better mechanical properties compared to single- or double-crosslinked hydrogels. The controlled release capability of PPG/ADA-Ca2+ hydrogels was also demonstrated, showing the encapsulated molecules can be rapidly released from the hydrogel network in the presence of hydrogen peroxide while the release rate can be slowed down at acidic pH. Furthermore, PPG/ADA-Ca2+ hydrogels presented selected cytotoxicity and drug delivery to cancer cells due to the regulated degradation by the cellular microenvironment. Taken together, PPG/ADA-Ca2+ hydrogels have been demonstrated as promising biomaterials with multiple desirable properties and dynamic features to perform controlled molecule release for biomedical applications.

Multiple Dynamic Bonds-Driven Integrated Cathode/Polymer Electrolyte for Stable All-Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries (LMBs) are considered as the promising higher-energy and improved-safety energy-storage systems. Nevertheless, the electrolyte-electrodes interfacial issues due to the limited solid physical contact lead to discontinuous interfacial charge transport and large interfacial resistance, thereby suffering from unsatisfactory electrochemical performance. Herein, we construct an integrated cathode/polymer electrolyte for all-solid-state LMBs under the action of polymer chains exchange and recombination originating from multiple dynamic bonds in our well-designed dynamic supramolecular ionic conductive elastomers (DSICE) molecular structure. The DSICE acts as polymer electrolytes with excellent electrochemical performance and mechanical properties, achieving the ultrathin pure polymer electrolyte thickness (12 µm). Notably, the DSICE also functions as lithium iron phosphate (LiFePO4 , LFP) cathode binders with enhanced adhesive capability. Such well-constructed Li|DSICE|LFP-DSICE cells generate delicate electrolyte-electrodes interfacial contact at the molecular level, providing continuous Li+ transport pathways and promoting uniform Li+ deposition, further delivering superior long-term charge/discharge stability (>600 cycles, Coulombic efficiency, >99.8 %) and high capacity retention (80 % after 400 cycles). More practically, the Li|DSICE|LFP-DSICE pouch cells show stable electrochemical performance, excellent flexibility and safety under abusive tests.

Body Armor-Inspired Double-Wrapped Binder with High Energy Dispersion for a Stable SiOx Anode.

The high specific capacity and relatively low volume expansion of silicon suboxide (SiOx) highlight its potential as one of the most promising anode materials for lithium-ion batteries. Nevertheless, the traditional binder of polyacrylic acid (PAA) still cannot adapt to enormous stress during the repeated volume expansion/contraction owing to its intrinsic rigid backbone. Inspired by the "soft and hard composite body armor", we herein design a double-wrapped binder consisting of PAA with a high internal Young's modulus (hard part) and polyurethane (DOU) with a low external Young's modulus (soft part). When the SiOx particle expands during lithiation, the rigid PAA firstly accommodates the volume change to dissipate most of the inner stress, and the elastic DOU with triple dynamic bonds serves as a buffer layer to absorb the residual stress via the breakage/formation of dynamic bonds. By optimizing the PAA/DOU ratio, the SiOx anode can maintain the integrity during long-term cycling and deliver a relatively high reversible capacity of 1064.1 mAh g-1 with a preeminent capacity retention of 83.7% at 0.5C after 300 cycles. Such a double-wrapped binder can provide a novel design strategy for multicomponent functional polymer binders toward high-performance SiOx anodes.

High-Performance Multi-Dynamic Bond Cross-Linked Hydrogel with Spatiotemporal siRNA Delivery for Gene-Cell Combination Therapy of Intervertebral Disc Degeneration.

Chronic inflammatory diseases, such as intervertebral disc degeneration (IVDD), which affect the lives of hundreds of millions of people, still lack effective and precise treatments. In this study, a novel hydrogel system with many extraordinary properties is developed for gene-cell combination therapy of IVDD. Phenylboronic acid-modified G5 PAMAM (G5-PBA) is first synthesized, and therapeutic siRNA silencing the expression of P65 mixed with G5-PBA (siRNA@G5-PBA) is then embedded into the hydrogel (siRNA@G5-PBA@Gel) based on multi-dynamic bonds including acyl hydrazone bonds, imine linkage, π-π stacking, and hydrogen bonding interactions. Local and acidic inflammatory microenvironment-responsive gene-drug release can achieve spatiotemporal regulation of gene expression. In addition, gene-drug release from the hydrogel can be sustained for more than 28 days in vitro and in vivo, greatly inhibiting the secretion of inflammatory factors and the subsequent degeneration of nucleus pulposus (NP) cells induced by lipopolysaccharide (LPS). Through prolonged inhibition of the P65/NLRP3 signaling pathway, the siRNA@G5-PBA@Gel is verified to relieve inflammatory storms, which can significantly enhance the regeneration of IVD when combined with cell therapy. Overall, this study proposes an innovative system for gene-cell combination therapy and a precise and minimally invasive treatment method for IVD regeneration.

Tough, Photoluminescent, Self-Healing Waterborne Polyurethane Elastomers Resulting from Synergistic Action of Multiple Dynamic Bonds.

Polymers that integrate multiple functions into one system broaden the application range of materials, but it remains a great challenge to obtain polymer materials with simultaneously high strength, high toughness, and high self-healing rate. In this work, we prepared waterborne polyurethane (WPU) elastomers using Schiff bases containing disulfide and acylhydrazone bonds (PD) as chain extenders. Acylhydrazone forming a hydrogen bond not only acts as a physical cross-linking point, which promotes the microphase separation of polyurethane to increase the thermal stability, tensile strength, and toughness of the elastomer, but also serves as a "clip" to integrate various dynamic bonds together to synergistically reduce the activation energy of the polymer chain movement and endow the molecular chain with faster fluidity. Therefore, WPU-PD exhibits excellent mechanical properties at room temperature, such as a tensile strength and a fracture energy of 25.91 MPa and 121.66 kJ m-2, respectively, and a high self-healing efficiency of 93.7% in a short time under moderate heating conditions. In addition, the photoluminescence property of WPU-PD enables us to track its self-healing process by monitoring change of the fluorescence intensity at the cracks, which helps to avoid the accumulation of cracks and improve the reliability of the elastomer. This self-healing polyurethane has a great potential application value in optical anticounterfeiting, flexible electronics devices, functional automobile protective films, and so on.

Engineering the viscoelasticity of gelatin methacryloyl (GelMA) hydrogels via small "dynamic bridges" to regulate BMSC behaviors for osteochondral regeneration.

The dynamic extracellular matrix (ECM) constantly affects the behaviors of cells. To mimic the dynamics of ECM with controllable stiffness and energy dissipation, this study proposes a strategy in which a small molecule, 3,4-dihydroxybenzaldehyde (DB), was used as fast "dynamic bridges'' to construct viscoelastic gelatin methacryloyl (GelMA)-based hydrogels. The storage modulus and loss modulus of hydrogels were independently adjusted by the covalent crosslinking density and by the number of dynamic bonds. The hydrogels exhibited self-healing property, injectability, excellent adhesion and mechanical properties. Moreover, the in vitro results revealed that the viscous dissipation of hydrogels favored the spreading, proliferation, osteogenesis and chondrogenesis of bone marrow mesenchymal stem cells (BMSCs), but suppressed their adipogenesis. RNA-sequencing and immunofluorescence suggested that the viscous dissipation of hydrogels activated Yes-associated protein (YAP) by stabilizing integrin ß1, and further promoted nuclear translocation of smad2/3 and ß-catenin to enhance chondrogenesis and osteogenesis. As a result, the viscoelastic GelMA hydrogels with highest loss modulus showed best effect in cartilage and subchondral bone repair. Taken together, findings from this study reveal an effective strategy to fabricate viscoelastic hydrogels for modulating the interactions between cells and dynamic ECM to promote tissue regeneration.

Tuning interfacial microstructure of alginate-based amphiphile by dynamic bonding for stabilizing Pickering emulsion.

Polysaccharide-based soft colloidal particles mediated by the dynamic bonding-engineered interfacial self-assembly can regulate the properties of oil-water interfacial films, availing the stability of emulsions under a wide pH range. The amphiphilic phenylboronic alginate soft colloidal particles (Alg-PBA) were designed to stabilize pH-responsive Pickering emulsions (PEs). Combining stability analysis with quartz crystal microbalance and dissipation monitoring (QCM-D), the microstructure and viscoelasticity of Alg-PBA at the oil-water interface were determined. The results showed that PEs stabilized by Alg-PBA due to a thicker and stronger viscoelastic interface film induced by BO bonds and hydrogen bonds. The structure-function relationship of the Alg-PBA emulsifier driven by dynamic bonds was further elaborated at multiple scales by laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Meanwhile, the microstructure of aerogels templated by emulsion could be tuned by adjusting dynamic bonds, which provides a new idea for polysaccharide soft material engineering.

Ultrasonic-Excited Ultrafast Seamless Integration of Heterostructured Liquid Crystalline Elastomers for Multi-responsive Soft Actuators.

Multicomponent/heterostructured liquid crystalline elastomers (LCEs) have recently garnered extensive attention for the design of soft robots with high dexterity and flexibility. However, the reported integration strategies of LCEs seriously suffer from high welding temperature, long processing time, and poor joint quality. Herein, the high-efficiency seamless ultrasonic welding (UW) of reprogrammable silver nanowire-LCE composites (AgNW-LCEs) have been realized without any auxiliary reagents based on the dynamic silver-disulfide coordination interactions. The elaborate combination of silver-disulfide coordination interactions and UW technology establishes an effective double-network welding mechanism of AgNWs and dynamic LC networks due to the high-frequency vibration at the welding interface. During the UW process, monolithic AgNW-LCEs can be integrated into heterostructured actuators at room temperature for 0.68 s. Furthermore, the welded AgNW-LCEs demonstrate an exceptional strain healing efficiency of ∼100%, a stress healing efficiency of ∼85%, and a maintained orientation of the LC alignment. Taking advantage of the high-efficiency UW technology, the heterostructured AgNW-LCE actuators with different LC alignments or LC monomers have been successfully implemented for a multi-degree-of-freedom soft robotic arm and a time-modulated flower-mimic actuator. This work provides an efficient approach toward the development of multi-responsive entirely soft actuators based on smart polymers.

Reversible Molecular Capture and Release in Microfluidics by Host-Guest Interactions in Hydrogel Microdots.

The integration of microscopic hydrogels with high specific surface area and physically reactive groups into microfluidic systems for selective molecular interactions is attracting increasing attention. Herein, the reversible capture and release of molecules through host-guest interactions of hydrogel dots in a microfluidic device is reported, which translates the supramolecular chemistry to the microscale conditions under continuous flow. Polyacrylamide (PAAm) hydrogel arrays with grafted ß-cyclodextrin (ß-CD)  modified poly(2-methyl-2-oxazoline) (CD-PMOXA) chains are fabricated by photopolymerization and integrated into a polydimethylsiloxane (PDMS)-on-glass chip. The ß-CD/adamantane (ß-CD/Ada) host-guest complex is confirmed by two dimensional Nuclear Overhauser Effect Spectroscopy NMR (2D NOESY NMR) prior to transfer to microfluidics. Ada-modified molecules are successfully captured by host-guest interaction formed between the CD-PMOXA grafted chains in the hydrogel network and the guest molecule in the solution. Furthermore, the captured molecules are released by perfusing free ß-CD with higher binding affinity than those grafted in the hydrogel array. A small guest molecule adamantane-fluorescein-isothiocyanate (Ada-FITC) and a macromolecular guest molecule (Ada-PMOXA-Cyanine 5 (Cy5)) are separately captured and released for three times with a release ratio up to 46% and 92%, respectively. The reproducible capture and release of functional molecules with different sizes demonstrates the stability of this hydrogel system in microfluidics and will provide an opportunity for future applications.

Double Modification of Poly(urethane-urea): Toward Healable, Tear-Resistant, and Mechanically Robust Elastomers for Strain Sensors.

Polyurethane elastomers with mechanical robustness, tear resistance, and healing efficiency hold great potential in wearable sensors and soft robots. However, achieving excellent mechanical properties and healable capability simultaneously remains highly desirable but exclusive. Herein, we propose a straightforward procedure for double modification of poly(urethane-urea) (PUU) via thiolactone chemistry, and two different dynamic cross-linking bonds (disulfide linkages and Zn2+/imidazole coordination) are successively incorporated into the side chain of PUU, producing double cross-linking elastomers (PUU-I/Zn-S). The synergy between disulfide linkages and Zn2+/imidazole coordination forms a robust and dynamic network, endowing PUU-I/Zn-S with excellent mechanical and healing properties. The tensile stress, elongation at break, and toughness of the resultant elastomer can reach 44.06 MPa, 1000%, and 181.93 MJ m-3, respectively. Meanwhile, PUU-I/Zn-S exhibits outstanding tearing resistance with a tearing energy of 42.1 kJ m-2. The PUU-I/Zn-S can restore its mechanical robustness after self-healing at room temperature (25 ± 2 °C) or 60 °C and even maintain 91% of its original tensile strength after reprocessing two times. Additionally, PUU-I/Zn-S-based strain sensors are fabricated by introducing conductive nanofillers and demonstrate remarkable sensing capability to diverse human body motions. This work demonstrates a simple and feasible method for the postfunctionalization and enhancement of polyurethane and provides some insights into reconciling the traditional contradictory properties of mechanical robustness and healing efficiency.