Reversible Cross-linking Research Articles

3D Printing of Interpenetrating Network Flexible Hydrogels with Enhancement of Adhesiveness.

3D printing of hydrogels has been widely explored for the rapid fabrication of complex soft structures and devices. However, using 3D printing to customize hydrogels with both adequate adhesiveness and toughness remains a fundamental challenge. Here, we demonstrate mussel-inspired (polydopamine) PDA hydrogel through the incorporation of a classical double network (2-acrylamido-2-methylpropanesulfonic acid) PAMPS/(polyacrylamide) PAAm to achieve simultaneously tailored adhesiveness, toughness, and biocompatibility and validate the 3D printability of such a hydrogel into customized architectures. The strategy of combining PDA with PAMPS/PAAm hydrogels leads to favorable adhesion on either hydrophilic or hydrophobic surfaces. The hydrogel also shows excellent flexibility, which is attributed to the reversible cross-linking of PDA and PAMPS, together with the long-chain PAAm cross-linking network. Among them, the reversible cross-linking of PDA and PAMPS is capable of dissipating mechanical energy under deformation. Meanwhile, the long-chain PAAm network contributes to maintaining a high deformation capability. We establish a theoretical framework to quantify the contribution of the interpenetrating networks to the overall toughness of the hydrogel, which also provides guidance for the rational design of materials with the desired properties. Our work manifests a new paradigm of printing adhesive, tough, and biocompatible interpenetrating network hydrogels to meet the requirements of broad potential applications in biomedical engineering, soft robotics, and intelligent and superabsorbent devices.

Dynamically Cross-Linked Granular Hydrogels for 3D Printing and Therapeutic Delivery.

Granular hydrogels have recently emerged as promising biomaterials for tissue engineering and 3D-printing applications, addressing the limitations of bulk hydrogels while exhibiting desirable properties such as injectability and high porosity. However, their structural stability can be improved with post-injection interparticle cross-linking. In this study, we developed granular hydrogels with interparticle cross-linking through reversible and dynamic covalent bonds. We fragmented photo-cross-linked bulk hydrogels to produce aldehyde or hydrazide-functionalized microgels using chondroitin sulfate. Mixing these microgels facilitated interparticle cross-linking through reversible hydrazone bonds, providing shear-thinning and self-healing properties for injectability and 3D printing. The resulting granular hydrogels displayed high mechanical stability without the need for secondary cross-linking. Furthermore, the porosity and sustained release of growth factors from these hydrogels synergistically enhanced cell recruitment. Our study highlights the potential of reversible interparticle cross-linking for designing injectable and 3D printable therapeutic delivery scaffolds using granular hydrogels. Overall, our study highlights the potential of reversible interparticle cross-linking to improve the structural stability of granular hydrogels, making them an effective biomaterial for use in tissue engineering and 3D-printing applications.

Electrically and thermally healable nanocomposites via one-step Diels-Alder reaction on carbon nanotubes

Carbon nanotubes (CNTs) were directly employed as reactive fillers in furan-pendant polyketones via the Diels-Alder (DA) reaction. CNTs and furan groups function as dienophile and diene, respectively, forming a reversible crosslinking network. Here, pristine CNTs not only serve as crosslinking agents, but also improve the thermal and electrical conductivity. The DA covalent linkage was confirmed by IR, TGA, DSC, elemental analysis and dispersion tests. This one-step approach offers a facile route to synthesize reversibly crosslinked thermoset polymer nanocomposites. The rigidity of the nanocomposites could be controlled through the number of furan groups in order to achieve distinct properties. The nanocomposites demonstrated dynamic temperature-dependent behavior due to the retro Diels-Alder reaction. Cyclic tests via rheology showed good reversibility below 120 °C. However, an irreversible increase of modulus was observed at higher temperatures, which is possibly attributed to a side reaction. At filler loadings above 5%, both electrical and thermal self-healing tests showed good results. The Diels-Alder reaction between CNTs and furan-pendant polymers opens up a new possibility of directly employing fillers in the polymer matrix without any prior modifications. It is also possible to use other fillers with diene/dienophile properties in future reversible polymer nanocomposites.

Photodegradable Non‐Drying Hydrogel Substrates for Liquid Metal Based Sustainable Soft‐Matter Electronics

AbstractThe increasing interest in disposable electronics such as wearable patches, e‐textiles, and smart packaging, warns emergence of another man‐made disaster. A paradigm shift toward a more sustainable future through the development of soft material architectures that are robust and durable, but also degradable by external stimuli is proposed. Hydrogels, a class of soft polymers with exceptional properties, and high water content are rarely used as substrates, mainly due to lack of ink‐adhesion and rapid dehydration. Herein, photodegradable hydrogels are tailor‐made that are nondrying, robust, adhesive to ink, and permit triggerable degradation, making them suitable substrates for sustainable electronics. These hydrogels are prepared by reversible ionic crosslinking between sodium alginate and divalent cations (Ca2+) and light‐responsive crosslinking of poly(acrylamide) (PAAm) chains through synthesized ortho‐nitrobenzyl (ONB)‐based crosslinkers. By displacing the water molecules in the hydrogels by immersion in glycerol, the drying problem and printability of conductive ink are addressed. It is demonstrated that digital printing of a liquid metal (LM)‐based stretchable ink over the developed substrate, shows several body‐worn printed wearable sensors, and demonstrates their degradation and recycling of the expensive metals. This work lays the foundation for the use of hydrogels as promising substrates for the next generation of environmentally friendly electronics.

Photoradical-Mediated Catalyst-Independent Protein Cross-Link with Unusual Fluorescence Properties.

Photo-actively modified natural amino acids have served as lucrative probes for precise mapping of the dynamics, interaction networks, and turnover of cytosolic proteins both in vivo and ex vivo. In our attempts to extend the utility of photoreactive reporters to map the molecular characteristics of vital membrane proteins, we carried out site-selective incorporation of 7-fluoro-indole in the human mitochondrial outer membrane protein VDAC2 (voltage-dependent anion channel isoform 2), with the aim of generating Trp-Phe/Tyr cross-links. Prolonged irradiation at 282 nm provided us with a surprisingly unusual fluorophore that displayed sizably red-shifted excitation (λex-max =280 nm→360 nm) and emission (λem-max =330 nm→430 nm) spectra that was reversible with organic solvents. By measuring the kinetics of the photo-activated cross-linking with a library of hVDAC2 variants, we demonstrate that formation of this unusual fluorophore is kinetically retarded, independent of tryptophan, and is site-specific. Using other membrane (Tom40 and Sam50) and cytosolic (MscR and DNA Pol I) proteins, we additionally show that formation of this fluorophore is protein-independent. Our findings reveal the photoradical-mediated accumulation of reversible tyrosine cross-links, with unusual fluorescent properties. Our findings have immediate applications in protein biochemistry and UV-mediated protein aggregation and cellular damage, opening avenues for formulating therapeutics that prolong cell viability in humans.

Thermally Reversible Cross-Linking of Recyclable Polyamide Materials Based on Schiff Base and Diels-Alder Reactions.

Recyclability of cross-link polymer materials is essential to alleviate environmental pollution caused by discarded or damaged polymers. Herein, a facile method for producing recyclable polyamide materials is developed. Linear polymer chains are constructed by Schiff base reaction between glutaraldehyde (GD) and furandiamine (FD). The linear polymer chains are crosslinked by bismaleimide (BM) to give rise to polyamide material, named GF-BMs. The resulting GF-BMs polyamide material possesses strong tensile strength (78MPa) and good solvent resistance from room temperature to 135 °C. Especially, the thermally reversible Diels-Alder covalent bonds and dynamic imine bonds in the polymer network have a synergistic effect on fast-reprocessing, self-healing, and recyclability, which provides a new idea for recyclable materials.

Acoustodynamic Covalent Materials Engineering for the Remote Control of Physical Properties Inside Materials.

Advances in vat-photopolymerization (VP) three-dimensional printing (3DP) technology enable the production of highly precise 3D objects. However, it has been a major challenge to create dynamic functionalities and to manipulate the physical properties of the inherently insoluble and infusible crosslinked material generated from VP-3DP without reproduction. Here, we report the fabrication of light- and high-intensity focused ultrasound (HIFU)-responsive crosslinked polymeric materials linked with hexaarylbiimidazole (HABI) in polymer chains based on VP-3DP. Although the photochemistry of HABI produces triphenylimidazolyl radicals (TPIRs) during the process of VP-3DP, the orthogonality of the photochemistry of HABI and photopolymerization enables the introduction of reversible crosslinks derived from HABIs in the resulting 3D printed objects. While photostimulation cleaves a covalent bond between two imidazoles in HABI to generate TPIRs only near the surface of the 3D printed objects, HIFU triggers cleavage in the interior of materials. In addition, HIFU travels beyond an obstacle to induce a response of HABI-embedded crosslinked polymers, which cannot be attainable with photostimulation. The present system would be beneficial for tuning the physical properties and recycling of various polymeric materials, but it will also open the door for pinpoint modification, healing, and reshaping of materials when coupled to various dynamic covalent materials. This article is protected by copyright. All rights reserved.

A large deformation model for quasi-static to high strain rate response of a rate-stiffening soft polymer

Polyborosiloxane (PBS) is an important rate-stiffening soft polymer with dynamic, reversible crosslinks used in applications ranging from self-healing sensing and actuation to body and structural protection. Its highly rate-dependent response, especially for impact-mitigating structures, is important. However, the large strain response of PBS has not been characterized over quasi-static to high strain rates. Currently, there are no constitutive models that can predict the strongly rate-dependent large-deformation elastic-viscoplastic response of PBS. To address this gap, we have developed a microstructural physics motivated constitutive model for PBS, similar soft polymers and polymer gels with dynamic crosslinks to predict their large strain, non-linear loading–unloading, and significantly rate-dependent response. We have conducted compression experiments on PBS up to true strains of ∼125% and over a wide strain rate range of 10−3 s−1 to 103 s−1. The proposed semi-physical model fairly accurately captures the response of PBS over six decades of strain rates. We propose boron–oxygen coordinate-bond dynamic crosslinks with macroscopic relaxation timescale τ≈3 s and temporary entanglement lockups at high strain rates acting as crosslinks with τ≈0.0005 s as the two types of crosslink network mechanisms in PBS. We have outlined a numerical update procedure to evaluate the convolution-like time integrals arising from dynamic crosslink kinetics. Experiments involving three-dimensional inhomogeneous deformations were used to verify the predictive capabilities of our model and its finite element implementation. The modeling framework can be adopted for other dynamically crosslinked rate-stiffening soft polymers and polymer gels that are microstructurally similar to PBS.

Flexible and recoverable ion-conductive hydrogels with cross-linked triple network for highly sensitive wearable Motion-monitoring sensors

The practical applications of hydrogel-based sensors are limited by their low mechanical strength, insufficient sensitivity and machining difficulties caused by electrically conductive fillers. It is of great practical importance for facile preparation of hydrogel sensor combined with excellent mechanical properties and conductive sensitivity. In this work, a series of ion-conductive hybrid hydrogels based on in-situ polymerized polyacrylamide with double and triple network structures have been fabricated via both chemical and physical cross-linking. The triple network structured hydrogels achieve the tensile strength of 2.105 MPa and compression strength of 57.56 MPa, which are much higher than those of hydrogels with double network due to the established energy dissipation gradient. The reversible non-covalent cross-linking in the network also leads a relatively fast recovery in tensile cycle tests and double compression tests, enabling the excellent stability of strain sensing in the durability test. The hydrogels show the tensile resistance sensitivity factor of 0.9352 at 0–120% strain and a high pressure sensitivity factor of 5.134 kPa−1 with the pressure ranged from 0 to 6 kPa. The hydrogels are also assembled as flexible sensors for human motion monitoring, and the signals of motions can be distinguished by different resistance variation values and certain curve shape, showing the potential of applications on flexible device and human-machine interface.

Synergistic chondrogenesis promotion and arthroscopic articular cartilage restoration via injectable dual-drug-loaded sulfated hyaluronic acid hydrogel for stem cell therapy

Bone marrow stem cells (BMSCs)-loaded injectable hydrogels are promising vehicles for the restoration of articular cartilage defect (ACD), while was limited with insufficient chondrogenic capacity and poor maintenance of chondrogenic phenotype. Herein, we reported a dual-drug delivering sulfated hyaluronic acid (SHA) hydrogel with injectable capacity to promote ACD repairment. Two precursor solutions were initial prepared: the HA-CHO-SO3 solution loaded with Kartogenin (KGN), β-cyclodextrin-CHO (β-CD-CHO) and BMSCs, and the HA-NHNH2-SO3 loaded with transforming growth factor β1 (TGF-β1) and BMSCs. The HA-CHO-SO3 could adsorb TGF-β1 through sulfonic acid group, and β-CD-CHO could preabsorb KGN through a hydrophobic cavity on β-CD. The aldehyde group on β-CD-CHO could react directly with the acylhydrazide to load KGN onto the HA-NHNH2-SO3 network. The mixture of two solutions resulted in the formation of a SHA@KGN/TGF-β1 hydrogel through reversible dynamic Schiff-based cross-linking between hydrazide and aldehyde groups. The SHA@KGN/TGF-β1 hydrogel had the benefits of injectability, rapid gelation, self-healing, and firm adhesion to the host tissue due to the reaction between the amine group on the host tissue and the aldehyde group on the SHA. Additionally, it could simultaneously load both TGF-β1 and KGN through electrostatic reaction and host-guest reaction, respectively, providing sustained release kinetics for both drugs. The dual-loaded drugs in the SHA@KGN/TGF-β1 hydrogel could synergistically enhance chondrogenic differentiation and suppress the hypertrophy of BMSCs, effectively promoting cartilage regeneration at both in vitro and in vivo circumstance. The one-step construction of this hydrogel system via mixing injection endowed facile arthroscopic ACD restoration and may significantly promote clinical application.

A facile bioorthogonal chemistry-based reversible to irreversible strategy to surmount the dilemma between injectability and stability of hyaluronic acid hydrogels

Injectable and stable hydrogels have great promise for clinical applications. Fine-tuning the injectability and the stability of the hydrogels at different stages has been challenging due to the limited number of coupling reactions. A distinct “reversible to irreversible” concept using a thiazolidine-based bioorthogonal reaction between 1,2-aminothiols and aldehydes in physiological conditions to surmount the dilemma between injectability and stability is presented for the first time. Upon mixing aqueous solutions of aldehyde-functionalized hyaluronic acid (SA-HA) and cysteine-capped ethylenediamine (DI-Cys), SA-HA/DI-Cys hydrogels formed through reversible hemithioacetal crosslinking within 2 min. The reversible kinetic intermediate facilitated thiol-triggered gel-to-sol transition, shear-thinning and injectability of the SA-HA/DI-Cys hydrogel but then converted to the irreversible thermodynamic network after injection, thereby permitting the resulting gel with improved stability. As compared to the Schiff base hydrogels, the hydrogels generated from this simple, yet effective concept awarded improved protection to the embedded mesenchymal stem cells and fibroblast during injection, retained the cells homogeneously within the gel, and allowed them further proliferation in vitro and in vivo. There is potential for the proposed approach of “reversible to irreversible” based on thiazolidine chemistry to be applied as a general coupling technique for developing injectable and stable hydrogels for biomedical applications.

Reversible cross-linking of gelatin by a disulphide-containing bis-succinimide for tunable degradation and release.

Generally, gelatin was irreversibly cross-linked by chemical reagents to improve its water-resistance. However, few chemical reagents meet both the requirements of high cross-inking efficiency and tunable degradation. Here a reversible cross-linker, disulphide-containing bis-succinimide, was synthesized and used to control the cross-linking and degradation of edible gelatin film. Mixture of the gelatin and cross-linker for 120min generated gelatin films that could preserve their morphology in 37 ℃ warm water for above 40days. The gelatin film changed its microstructure from net to tightness after the cross-linking, thus facilitating the embedding of the targeted molecule into the gelatin material. The degradation of the cross-linked gelatin film and the release of its inclusion could be controlled by biocompatible glutathione. This work provides a good method for preparing modified gelatin with promising water-resistance, good biocompatibility, and tunable degradation for food/biomedical engineering applications.

Natural Rubber Composites Using Hydrothermally Carbonized Hardwood Waste Biomass as a Partial Reinforcing Filler-Part II: Mechanical, Thermal and Ageing (Chemical) Properties.

Natural rubber composites were reinforced by the co-fillers 'hydrochar' (HC), obtained by hydrothermal carbonization of hardwood sawdust and commercial carbon black (CB). The content of the combined fillers was kept constant while their ratio was varied. The aim was to test the suitability of HC as a partial filler in natural rubber. Due to its larger particle size and hence smaller specific surface area, large amounts of HC reduced the crosslinking density in the composites. On the other hand, due to its unsaturated organic character, HC was found to display interesting chemical effects: if it was used as the exclusive filler component, it displayed a very strong anti-oxidizing effect, which greatly stabilized the rubber composite against oxidative crosslinking (and hence embrittlement). HC also affected the vulcanization kinetics in different ways, depending on the HC/CB ratio. Composites with HC/CB ratios 20/30 and 10/40 displayed interesting chemical stabilization in combination with fairly good mechanical properties. The performed analyses included vulcanization kinetics, tensile properties, determination of density of permanent and reversible crosslinking in dry and swollen states, chemical stability tests including TGA, thermo-oxidative aging tests in air at 180 °C, simulated weathering in real use conditions ('Florida test'), and thermo-mechanical analyses of degraded samples. Generally, the results indicate that HC could be a promising filler material due to its specific reactivity.

Preparation and Properties of Self-Cross-Linking Hydrogels Based on Chitosan Derivatives and Oxidized Sodium Alginate.

A self-cross-linking and biocompatible hydrogel has wide application potential in the field of tissue engineering. In this work, an easily available, biodegradable, and resilient hydrogel was prepared using a self-cross-linking method. This hydrogel was composed of N-2-hydroxypropyl trimethyl ammonium chloride chitosan (HACC) and oxidized sodium alginate (OSA). A stable and reversible cross-linking network was formed by the Schiff base self-cross-linked and hydrogen bonding. The addition of a shielding agent (NaCl) may weaken the intense electrostatic effect between HACC and OSA and solve the problem of flocculation caused by the rapid formation of ionic bonds, which provided an extended time for the Schiff base self-cross-linked reaction for forming a homogeneous hydrogel. Interestingly, the shortest time for the formation of the HACC/OSA hydrogel was within 74 s and the hydrogel had a uniform porous structure and enhanced mechanical properties. The HACC/OSA hydrogel withstood large compression deformation due to improved elasticity. What's more, this hydrogel possessed favorable swelling property, biodegradation, and water retention. The HACC/OSA hydrogels have great antibacterial properties against Staphylococcus aureus and Escherichia coli and demonstrated good cytocompatibility as well. The HACC/OSA hydrogels have a good sustained release effect on rhodamine (model drug). Thus, the obtained self-cross-linked HACC/OSA hydrogels in this study have potential applications in the field of biomedical carriers.

Covalent Adaptable Polymethacrylate Networks by Hydrazide Crosslinking Via Isosorbide Levulinate Side Groups.

Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resulting covalent adaptable network contains acylhydrazone bonds cleavable under acidic conditions, thereby providing reversibility. In the present work, we regioselectively prepare a novel isosorbide monomethacrylate with a pendant levulinoyl group via a two-step biocatalytic synthesis. Subsequently, a series of copolymers with different contents of the levulinic isosorbide monomer and methyl methacrylate are prepared by radical polymerization. Using dihydrazides, these linear copolymers are then crosslinked via reaction with the ketone groups in the levulinic side chains. Compared to the linear prepolymers, the crosslinked networks exhibit enhanced glass transition temperatures and thermal stability, up to 170 and 286 °C, respectively. Moreover, the dynamic covalent acylhydrazone bonds are efficiently and selectively cleaved under acidic conditions to retrieve the linear polymethacrylates. We next show that recovered polymers can again be crosslinked with adipic dihydrazide, thus demonstrating the circularity of the materials. Consequently, we envision that these novel levulinic isosorbide-based dynamic polymethacrylate networks have great potential in the field of recyclable and reusable biobased thermoset polymers.

Synthesis and Excision Repair of Site-Specific 3'-End DNA-Histone Cross-Links Derived from Abasic Sites.

Histones catalyze the DNA strand incision at apurinic/apyrimidinic (AP) sites accompanied by formation of reversible but long-lived DNA-protein cross-links (DPCs) at 3'-DNA termini within single-strand breaks. These DPCs need to be removed because 3'-hydroxyl is required for gap-filling DNA repair synthesis but are challenging to study because of their reversible nature. Here we report a chemical approach to synthesize stable and site-specific 3'-histone-DPCs and their repair by three nucleases, human AP endonuclease 1, tyrosyl-DNA phosphodiesterase 1, and three-prime repair exonuclease 1. Our method employs oxime ligation to install an alkyne to 3'-DNA terminus, genetic incorporation of an azidohomoalanine to histone H4 at a defined position, and click reaction to conjugate DNA to H4 site-specifically. Using these model DPC substrates, we demonstrated that the DPC repair efficiency is highly affected by the local protein environment, and prior DPC proteolysis facilitates the repair.

Facile synthesis of highly stretchable, tough and photodegradable hydrogels.

Recently we reported highly stretchable and tough hydrogels that are photodegradable on-demand (Materials Today Bio, 15, 100 325, 2022). Unfortunately, the preparation procedure was complex due to the hydrophobic nature of the photocrosslinkers. Herein, we report a simple method to prepare photodegradable double-network (DN) hydrogels that exhibit high stretchability, toughness and biocompatibility. We synthesized hydrophilic ortho-nitrobenzyl (ONB) crosslinkers with incorporating different poly(ethylene glycol) (PEG) backbones (600, 1000, and 2000g⋅mol-1 ). These photodegradable DN hydrogels were prepared by the irreversible crosslinking of chains by using such ONB crosslinkers, and the reversible ionic crosslinking between sodium alginate and divalent cations (Ca2+ ). Remarkable mechanical properties are obtained by combining ionic and covalent crosslinking and their synergistic effect, and by reducing the length of the PEG backbone. We also demonstrate the rapid on-demand degradation of these hydrogels by using cytocompatible light wavelength (λ = 365nm) that degrades the photosensitive ONB units. We have successfully used these hydrogels as skin-worn sensors for monitoring human respiration and physical activities. A combination of excellent mechanical properties, facile fabrication, and on-demand degradation holds promise for their application as the next generation of substrates or active sensors eco-friendly for bioelectronics, biosensors, wearable computing, and stretchable electronics. This article is protected by copyright. All rights reserved.

Gelation Time of Network-Forming Polymer Solutions with Reversible Cross-Link Junctions of Variable Multiplicity.

The gelation time tg necessary for a solution of functional (associating) molecules to reach its gel point after a temperature jump, or a sudden concentration change, is theoretically calculated on the basis of the kinetic equation for the stepwise cross-linking reaction as a function of the concentration, temperature, functionality f of the molecules, and multiplicity k of the cross-link junctions. It is shown that quite generally tg can be decomposed into the product of the relaxation time tR and a thermodynamic factor Q. They are functions of a single scaled concentration x≡λ(T)ϕ, where λ(T) is the association constant and ϕ is the concentration. Therefore, the superposition principle holds with λ(T) as a shift factor of the concentration. Additionally, they all depend on the rate constants of the cross-link reaction, and hence it is possible to estimate these microscopic parameters from macroscopic measurements of tg. The thermodynamic factor Q is shown to depend on the quench depth. It generates a singularity of logarithmic divergence as the temperature (concentration) approaches the equilibrium gel point, while the relaxation time tR changes continuously across it. Gelation time tg obeys a power law tg-1∼xn in the high concentration region, whose power index n is related to the multiplicity of the cross-links. The retardation effect on the gelation time due to the reversibility of the cross-linking is explicitly calculated for some specific models of cross-linking to find the rate-controlling steps in order for the minimization of the gelation time to be easier in the gel processing. For a micellar cross-linking covering a wide range of the multiplicity, as seen in hydrophobically-modified water-soluble polymers, tR is shown to obey a formula similar to the Aniansson-Wall law.

Coacervation-Mediated Cytocompatible Formation of Supramolecular Hydrogels with Self-Evolving Macropores for 3D Multicellular Spheroid Culture.

Coacervation driven liquid-liquid phase separation of biopolymers has aroused considerable attention for diverse applications, especially for the construction of microstructured polymeric materials. Herein, a coacervate-to-hydrogel transition strategy is developed to create macroporous hydrogels (MPH), whichare formed via the coacervation process of supramolecular assemblies (SA) built by the host-guest complexation between γ-cyclodextrin and anthracene dimer. The weak and reversible supramolecular crosslinks endow the SA with liquid-like rheological properties, which facilitate the formation of SA-derived macroporous coacervates and the subsequent transition to MPH (pore size ≈ 100µm). The excellent structural dynamics (derived from SA) and the cytocompatible void-forming process of MPH can better accommodate the dramatic volumetric expansion associated with colony growth of encapsulated multicellular spheroids compared with the non-porous static hydrogel with similar initial mechanical properties. The findings of this work not only provide valuable guidance to the design of biomaterials with self-evolving structures but also present a promising strategy for 3D multicellular spheroid culture and other diverse biomedical applications.

A Transparent, and Self-Healable Strain-Sensor E-Skin Based on Polyurethane Membrane with Silver Nanowires

Electronic skin (E-skin) is increasingly utilized in modern society, yet current E-skin technology suffers from issues, such as opacity, hardness, and fragility. To address these challenges, a novel E-skin was developed using polyurethane (PU) as the matrix material and silver nanowires (AgNWs) as the sensing material. By leveraging the small degree of microphase separation and lack of crystallization in the PU, combined with the appropriate length–diameter ratio of the AgNWs, the resulting E-skin exhibited a visible light transmittance of 75%. The E-skin also showed excellent self-healing properties (83.63% efficiency in the third repair) and mechanical properties (with almost no degradation after 60 tensile cycles) due to the reversible dynamic cross-linking network within the PU. The synergistic effect of PU and AgNWs resulted in exceptional sensing performance for the E-skin, with a gauge factor of 46 (when ε = 10%). Moreover, the E-skin demonstrated signal stability during human joint motion monitoring and successfully identified different movement states, highlighting its potential for diverse applications. This research presents a simple yet effective approach for producing transparent, durable, and stable E-skin.