Tunable Mechanical Strength Research Articles

3D Micro‐Nano Hierarchical Constructs Enabling Transmural Ingrowth of Adventitia Improves the “Fallout endothelialization” of Vascular Grafts

AbstractImproving transmural ingrowth of adventitia is believed to promote luminal endothelialization during host remodeling of the vascular graft. However, fabricating vascular grafts with opening microstructures favoring cell ingrowth and tunable mechanical strength warranting clinical safety remains challenging. In this study, an ultrathin nanofibrous lumen stented with a highly porous tube is fabricated to acquire a harmonious balance between mechanical stability and the requisite openness for effective cell recruitment. In vitro examination reveals clinically feasible mechanical bridging of the rabbit carotid artery, such vascular graft with 3D micro‐nano hierarchical structures (3D‐MnHCs) enable fast and sufficient cell ingrowth, including transmural angiogenesis and muscular remodeling by myofibroblasts. Harnessing an integrated spatial transcriptomics approach and angiogenesis inhibition experiments, unprecedented insights revealing the positive roles of vascularized adventitia on “Fallout” endothelialization are provided. To conclude, 3D‐MnHCs offer a“concept of proof” for balancing adequate cell ingrowth and clinically applicable strength and degrading rates, therefore introducing a novel perspective for small caliber arterial regeneration.

Cytocompatible Hydrogels with Tunable Mechanical Strength and Adjustable Swelling Properties through Photo-Cross-Linking of Poly(vinylphosphonates).

Herein, the synthesis, characterization, and application of a novel synthetic hydrogel based on the photoinitiated cross-linking of poly(vinylphosphonates) is presented. First, statistical copolymers with adjustable ratios of the monomers diallyl vinylphosphonate (DAlVP) and diethyl vinylphosphonate (DEVP), as well as different molecular weights, were obtained via rare earth metal-mediated group-transfer polymerization (REM-GTP) while maintaining narrow polydispersities. The copolymers were cross-linked by applying photoinitiated thiol-ene click chemistry (λ = 365 nm). The network formation was monitored via oscillatory rheology coupled with UV-irradiation, revealing the high spatiotemporal control of the reaction. Moreover, the equilibrium storage moduli of poly(vinylphosphonate)-based hydrogels increased with a growing number of DAlVP units and upon application of a different cross-linker, which was additionally confirmed by nanoindentation experiments. In contrast, the water uptake of hydrogels decreased with higher DAlVP amounts in the corresponding hydrogels due to lower chain mobility and an overall increase in the hydrophobicity of the samples. Upon successful functionalization of P(DEVP-stat-DAlVP) copolymers with sodium 3-mercaptopropane-1-sulfonate, as indicated via 1H DOSY NMR, the respective cross-linked materials displayed a remarkable increase in the water uptake; thus, presenting highly hydrophilic gels with an apparent interplay between water uptake, cross-linking density, and functionalization degree. Finally, the purified hydrogels showed cytocompatibility and enabled cell adhesion of human umbilical artery smooth muscle cells (HUASMCs) after direct seeding. The materials further allowed the adhesion and growth of an endothelial layer, triggered no pro-inflammatory response as evidenced by cytokine release of M0 macrophages, and exhibited antibacterial properties toward S. aureus and E. coli.

CoFe Oxides-Coated 2D Black Phosphorus for Flame-Retardant Nanocoatings with Tunable Mechanical Strength and Efficient Elimination of Toxic Gases.

2D black phosphorus (BP) degrades irreversibly into phosphate compounds under ambient conditions, which limits its application in a variety of fields. In this study, by coating amorphous ferric-cobalt oxides (CoFeO)on BP nanosheets, a multifunctional CoFeO@2D BP is successfully developed that effectively inhibited combustion and catalyzed CO oxidation to eliminate toxic gases. Strong affinity between transition-metal cations and BP allowed the uniform growth of amorphous ferric‒cobalt oxides on the BP surface, which effectively prevented the spontaneous degradation of 2D BP. By combining CoFeO@2D BP with gelatin and kosmotropic salts, the as-obtained nanocoatings are used for surface treatment of flammable polyurethane foam (PU). Kosmotropic ions induced strong hydrophobic interactions and bundling within the gelatin chains which significantly enhanced the mechanical performance of the PU. BP accelerates the carbonization of gelatin to inhibit the combustion of PU, and CoFe oxides, which act as true active centers to accelerate the oxidation of CO, effectively inhibiting the production of harmful gas. The release rate of CO decreases by 73% and the limiting oxygen index (LOI) increases from 17% to ≈32% during PU combustion. The developed novel 2D material opens the way for multifunctional coatings with integrated durability, flame retardancy, and high smoke suppression efficiency.

Glucose Oxidase-Coated Calcium Peroxide Nanoparticles as an Innovative Catalyst for In Situ H2O2-Releasing Hydrogels.

In situ forming and hydrogen peroxide (H2O2)-releasing hydrogels have been considered as attractive matrices for various biomedical applications. Particularly, horseradish peroxidase (HRP)-catalyzed crosslinking reaction serves efficient method to create in situ forming hydrogels due to its advantageous features, such as mild reaction conditions, rapid gelation rate, tunable mechanical strength, and excellent biocompatibility. Herein, a novel HRP-crosslinked hydrogel system is reported that can produce H2O2 in situ for long-term applications, using glucose oxidase-coated calcium peroxide nanoparticles (CaO2@GOx NPs). In this system, CaO2 gradually produced H2O2 to support the HRP-mediated hydrogelation, while GOx further catalyzed the oxidation of glucose for in situ H2O2 generation. As the hydrogel is formed rapidly is expected and the H2O2 release behavior is prolonged up to 10 days. Interestingly, hydrogels formed by HRP/CaO2@GOx-mediated crosslinking reaction provided a favorable 3D microenvironment to support the viability and proliferation of fibroblasts, compared to that of hydrogels formed by either HRP/H2O2 or HRP/CaO2/GOx-mediated crosslinking reaction. Furthermore, HRP/CaO2@GOx-crosslinked hydrogel enhanced the angiogenic activities of endothelial cells, which is demonstrated by the in vitro tube formation test and in ovo chicken chorioallantoic membrane model. Therefore, HRP/CaO2@GOx-catalyzed hydrogels is suggested as potential in situ H2O2-releasing materials for a wide range of biomedical applications.

A hydrogel based on Fe(II)-GMP demonstrates tunable emission, self-healing mechanical strength and Fenton chemistry-mediated notable antibacterial properties.

Supramolecular hydrogels serve as an excellent platform to enable in situ reactive oxygen species (ROS) generation while maintaining controlled localized conditions, thereby mitigating cytotoxicity. Herein, we demonstrate hydrogel formation using guanosine-5'-monophosphate (GMP) with tetra(4-carboxylphenyl) ethylene (1) to exhibit aggregation-induced emission (AIE) and tunable mechanical strength in the presence of divalent metal ions such as Ca2+, Mg2+, and Fe2+. The addition of divalent metal ions leads to structural transformation in the metallogels (M-1GMP). Furthermore, the incorporation of Fe2+ ions into the hydrogel (Fe-1GMP) promotes the Fenton reaction that could be upregulated upon adding ascorbic acid (AA), demonstrating antibacterial efficacy via ROS generation. In vitro studies on AA-loaded Fe-1GMP demonstrate excellent bacterial killing efficacy against E. coli, S. aureus and vancomycin-resistant enterococci (VRE) strains. Finally, in vivo studies involving topical administration of Fe-1GMP to Balb/c mice with skin infections further suggest the potential antibacterial efficacy of the hydrogel. Taken together, the hydrogel with its unique combination of mechanical tunability, ROS generation capability and antibacterial efficacy can be used for biomedical applications, particularly in wound healing and infection control.

In situ biomineralization reinforcing anisotropic nanocellulose scaffolds for guiding the differentiation of bone marrow-derived mesenchymal stem cells

Nanocellulose (NC) is a promising biopolymer for various biomedical applications owing to its biocompatibility and low toxicity. However, it faces challenges in tissue engineering (TE) applications due to the inconsistency of the microenvironment within the NC-based scaffolds with target tissues, including anisotropy microstructure and biomechanics. To address this challenge, a facile swelling-induced nanofiber alignment and a novel in situ biomineralization reinforcement strategies were developed for the preparation of NC-based scaffolds with tunable anisotropic structure and mechanical strength for guiding the differentiation of bone marrow-derived mesenchymal stem cells for potential TE application. The bacterial cellulose (BC) and cellulose nanofibrils (CNFs) based scaffolds with tunable swelling anisotropic index in the range of 10–100 could be prepared by controlling the swelling medium. The in situ biomineralization efficiently reinforced the scaffolds with 2–4 times and 10–20 times modulus increasement for BC and CNFs, respectively. The scaffolds with higher mechanical strength were superior in supporting cell growth and proliferation, suggesting the potential application in TE application. This work demonstrated the feasibility of the proposed strategy in the preparation of scaffolds with mechanical anisotropy to induce cells-directed differentiation for TE applications.

Co-Assembly of Soft and Hard Nanoparticles into Macroscopic Colloidal Composites with Tailored Mechanical Property and Processability.

Colloidal composites, translating the great potential of nanoscale building bricks into macroscopic dimensions, have emerged as an appealing candidate for new materials with applications in optics, energy storage, and biomedicines. However, it remains a key challenge to bridge the size regimes from nanoscopic colloidal particles to macroscale composites possessing mechanical robustness. Herein, a bottom-up approach is demonstrated to manufacture colloidal composites with customized macroscopic forms by virtue of the co-assembly of nanosized soft polymeric micelles and hard inorganic nanoparticles. Upon association, the hairy micellar corona can bind with the hard nanoparticles, linking individual hard constituents together in a soft-hard alternating manner to form a collective entity. This permits the integration of block copolymer micelles with controlled amounts of hard nanoparticles into macroscopic colloidal composites featuring diverse internal microstructures. The resultant composites showed tunable microscale mechanical strength in a range of 90-270MPa and macroscale mechanical strength in a range of 7-42MPa for compression and 2-24MPa for bending. Notably, the incorporation of soft polymeric micelles also imparts time- and temperature-dependent dynamic deformability and versatile capacity to the resulting composites, allowing their application in the low-temperature plastic processing for functional fused silica glass.

A slicing and path generation method for 3D printing of periodic surface structure

Periodic surface (PS) model holds enormous potential in the field of lightweight, heat management, and biomedical implants. To achieve tunable mechanical strength and high surface area versus volume (SA/V) ratio, it is imperative to achieve solid representation of the PS models. However, because of the complex inner structure, converting the surface model to solid model with uniform thickness remains a major challenge. In the meantime, the most pervasive practice to achieve tunable wall thickness is by offsetting the contour with a constant value or setting a constant value difference between two implicit functions. However, these existing approaches cannot guarantee uniform wall thickness. In this paper, a novel method is proposed to define an adjacent implicit surface with a uniform offset distance to the original. By repeatedly generating implicit surfaces with uniform distance from each other, the solid representation of the PS model with uniform thickness can be achieved. Meanwhile, a new slicing method allowing for the slicing without stereolithography (STL) file is developed to slice the implicit surfaces and generate the printing path so that the accumulation of slicing errors introduced by meshing steps can be avoided. By slicing each implicit surface separately, the corresponding G-code file is generated. This developed method is demonstrated by fabricating typical PS with fused filament 3D printing.

Tongue-inspired gelatin/poly(acrylate-co-acrylamide)-Fe3+ organic hydrogel with tunable mechanical, electrical, and sensory properties

Conductive hydrogels have emerged as one of the most promising candidates for the next generation of wearable soft electronics. However, they face limitations during practical implementation owing to their unbalanced overall properties. In this study, we present a dynamic cross-linked gelatin/poly(acrylic acid-co-acrylamide) (GxPyFez) hydrogel with tunable mechanical strength, self-healing, freezing resistance, electrical conductivity, and high sensitivity, which was prepared by incorporating Fe3+ ions. The hydrogel was prepared based on the tongue, in which gelatin/poly(acrylic acid-co-acrylamide) and Fe3+ ions mimic the connective tissue and receptor cells of the human tongue. The synergistic effect of reversible crosslinking, along with the modulation of rigid and flexible components enabled tunable flexible structures that exhibit excellent mechanical properties such as elongation at break (569 %) and toughness (8.82 MJ m−3). Notably, the G2P3Fe0.1 hydrogel exhibited remarkable self-healing ability, even at room temperature, while maintaining a good freezing resistance. Furthermore, the G2P3Fe0.1 demonstrated fast response characteristics along with a high sensitivity (GF = 2.75). Consequently, it could be assembled into sensors capable of effectively detecting various movements of the human body; it serves as an electronic skin that responds to diverse external stimuli and monitors underwater motion signals. This study provides new insights into the design of conductive hydrogels with tunable overall properties that can be modified to suit specific application scenarios.

Hydrogen Bonds Reinforced Ionogels with High Sensitivity and Stable Autonomous Adhesion as Versatile Ionic Skins.

Flexible wearable sensors have demonstrated enormous potential in various fields such as human health monitoring, soft robotics, and motion detection. Among them, sensors based on ionogels have garnered significant attention due to their wide range of applications. However, the fabrication of ionogels with high sensitivity and stable autonomous adhesion remains a challenge, thereby limiting their potential applications. Herein, we present an advanced ionogel (PACG-MBAA) with exceptional performances based on multiple hydrogen bonds, which is fabricated through one-step radical polymerization of N-acryloylglycine (ACG) in 1-ethyl-3-methylimidazolium ethyl sulfate (EMIES) in the presence of N,N'-methylenebis(acrylamide) (MBAA). Compared with the ionogel (PAA-MBAA) formed by polymerization of acrylic acid (AA) in EMIES, the resulting ionogel exhibits tunable mechanical strength (35-130 kPa) and Young's modulus comparable to human skin (60-70 kPa) owing to the multiple hydrogen bonds formation. Importantly, they demonstrate stable autonomous adhesion to various substrates and good self-healing capabilities. Furthermore, the ionogel-based sensor shows high sensitivity (with a gauge factor up to 6.16 in the tensile range of 300-700%), enabling the detection of both gross and subtle movements in daily human activities. By integration of the International Morse code, the ionogel-based sensor enables the encryption, decryption, and transmission of information, thus expanding its application prospects.

An interfacial host-guest inclusion complex regulated supramolecular nanocomposite hydrogel showing tunable mechanical strength, self-healing, strain sensitivity and NIR responsiveness.

The development of supramolecular nanocomposite hydrogels with good mechanical properties and multifunctional characteristics remains challenging. The reinforced role of interfacial weak interactions is important for the mechanical properties of nanocomposite hydrogels. Here, a dynamic host-guest inclusion complex from the host molecule CB[7] and guest units was employed to prepare Fe3O4 hybrid supramolecular nanocomposite hydrogels. The results show that the as-obtained hydrogel with a porous structure was prepared. The CB[7]-modified Fe3O4 (Fe3O4@CB[7]) nanoparticles severed as a cross-linker for fabricating the hydrogel's network. By changing the Fe3O4@CB[7] content, their tensile stress ranged from 0.102 to 0.403 MPa and their compression stress ranged (70% compression strain) from 0.059 to 0.775 MPa. By changing the guest units, their tensile stress ranged from 0.3 MPa to 0.403 MPa. The self-healing efficiency of the hydrogels was 99% after 48 h at room temperature. The as-obtained hydrogels with strain sensitivity can be applied for detecting the movement of an elbow and finger. The supramolecular hydrogel exhibits NIR responsiveness, self-healing, injectability, tunable mechanical strength and conductive ability, and can be used in flexible electronics.

A 3D-Printed Cuttlefish Bone Elastomeric Sponge Rapidly Controlling Noncompressible Hemorrhage.

Developing a self-expanding hemostatic sponge with high blood absorption and rapid shape recovery for noncompressible hemorrhage remains a challenge. In this study, a 3D-printed cuttlefish bone elastomeric sponge (CBES) is fabricated, which combined ordered channels and porous structures, presented tunable mechanical strength, and shape memory potentials. The incorporation of cuttlefish bone powder (CBp) plays key roles in concentrating blood components, promoting aggregation of red blood cells and platelets, and activating platelets, which makes CBES show enhanced hemostatic performance compared with commercial gelatin sponges in vivo. Moreover, CBES promotes more histiocytic infiltration and neovascularization in the early stage of degradation than gelatin sponges, which is conducive to the regeneration and repair of injured tissue. To conclude, CBp loaded 3D-printed elastomeric sponges can promote coagulation, present the potential to guide tissue healing, and broaden the hemostatic application of traditional Chinese medicine.

Enzyme-mediated fabrication of nanocomposite hydrogel microneedles for tunable mechanical strength and controllable transdermal efficiency

Microneedles (MNs) are increasingly used in transdermal drug delivery due to high bioavailability, simple operation, and improved patient compliance. However, further clinical applications are hindered by unsatisfactory mechanical strength and uncontrolled drug release. Herein, an enzyme-mediated approach is reported for the fabrication of nanocomposite hydrogel-based MNs with tunable mechanical strength and controllable transdermal efficiency. As a proof-of-concept, tetrakis(1-methyl-4-pyridinio)porphyrin (TMPyP) was chosen as a model drug for photodynamic therapy of melanoma. TMPyP-loaded PLGA nanoparticles (NP/TMPyP) served as an inner phase of MNs for controlled release of photosensitizers, and enzyme-mediated hyaluronic acid-tyramine (HAT) hydrogels served as an external phase for optimizing the mechanical strength of MNs. By changing the concentration of HRP and H2O2, three types of MNs were fabricated for transdermal delivery of TMPyP, which demonstrated different cross-linking densities and various mechanical strength. Among the three MNs, the HAT-Medium@NP/TMPyP-MN with a medium mechanical strength exhibited the highest values of transdermal efficiency in vitro and the longest retention time in vivo. As compared to pure TMPyP and TMPyP-loaded nanoparticles, the HAT-Medium@NP/TMPyP-MN demonstrated higher anticancer efficacy in both melanoma A375 cells and a xenografted tumor mouse model. Therefore, the enzyme-mediated nanocomposite hydrogel MNs show great promise in the transdermal delivery of therapeutic drugs with enhanced performance. Statement of SignificanceThis study reports an enzyme-mediated approach for the fabrication of photodynamically-active microneedles (HAT@NP/TMPyP-MNs) with tunable mechanical strength and controllable transdermal efficiency. On one hand, HAT hydrogels that bear different cross-linking densities, facilitate tunable mechanical strength and optimized transdermal performances of MNs; on the other hand, NP/TMPyP and HAT network contribute to sustained release of photosensitizers. Comparing to other formulation (i.e., NP/TMPyP or TMPyP), the HAT-Medium@NP/TMPyP-MN exhibited excelling anticancer efficacy in photodynamic therapy in vitro and in vivo. We believe that the combination of enzyme-mediated polymeric cross-linking and slow-releasing nano-vehicles in a single nanocomposite platform provides a versatile approach for the fabrication of MNs with enhanced therapeutic efficacy, which holds great promise in the transdermal delivery of various therapeutic drugs in future.

Continuous Stereolithography 3D Printing of Multi-Network Hydrogels in Triply Periodic Minimal Structures With Tunable Mechanical Strength for Energy Absorption

Abstract This work presents a fast additive manufacturing (AM) protocol for fabricating multi-network hydrogels. A gas-permeable PDMS (polydimethylsiloxane) film creates a polymerization-inhibition zone, enabling continuous stereolithography (SLA) 3D printing of hydrogels. The fabricated multi-bonding network integrates rigid covalent bonding and tough ionic bonding, allowing effective tuning of elastic modulus and strength for various loading conditions. The 3D-printed triply periodic minimal structures (TPMS) hydrogels exhibit high compressibility with up to 80% recoverable strain. Additionally, dried TPMS hydrogels display novel energy/impact absorption properties. By comparing uniform and gradient TPMS hydrogels, we analyze their energy/impact absorption capability of the 3D-printed specimens. We use finite element analysis (FEA) simulation studies to reveal the anisotropy and quasi-isotropy behavior of the TPMS structures, providing insights for designing and controlling TPMS structures for energy absorption. Our findings suggest that gradient TPMS hydrogels are preferable energy absorbers with potential applications in impact resistance and absorption.

Reconstruction of Cellulose Intermolecular Interactions from Hydrogen Bonds to Dynamic Covalent Networks Enables a Thermo-processable Cellulosic Plastic with Tunable Strength and Toughness.

Its excellent renewability and biodegradability make cellulose an attractive resource to prepare fossil-based plastic alternatives. However, cellulose itself exhibits strong intermolecular hydrogen bond (H-bond) interactions, significantly restricting the mobility of cellulose chains, thus leading to poor thermo-processing performance. Here, we reconstructed the intermolecular interactions of cellulose chains via replacing the original H-bonds with dynamic covalent bonds. By this, cellulose can be easily thermo-processed into a cellulosic plastic under mild conditions (70 °C). Through adjusting the chemical structure of dynamic covalent networks, the cellulosic plastic shows tunable mechanical strength (3.0-33.5 MPa) and toughness (43-321 kJ m-2). The cellulosic plastic also exhibits excellent resistance to water, organic solvent, acid solution, alkali solution, and high temperature (>400 °C). Moreover, it owns good chemical and biological degradability and recyclability. This work provides an effective method to develop high-performance cellulosic plastics for fossil-based plastic substitution.

Bilayer nonwovens using natural rubber, poly(lactic acid) and bactericidal nanoparticles for wound dressings

Wound healing poses a significant challenge in healthcare, impacting not only on patients' quality of life but also placing a substantial financial burden on healthcare systems. Bilayer nonwovens have emerged as a promising solution for wound dressings due to their porous morphology, providing a high surface area for cellular adhesion and growth, and their permeability, allowing proper oxygen and fluid exchange to promote wound healing. When bactericide materials are added to the formulation, they can decrease or prevent infection caused by microorganisms, further aiding the healing process. Solution blow spinning is an appealing technique for creating bilayer nonwovens as it can produce high yields at a low cost. Yet, even though natural rubber boasts a well-established safety record in biomaterials, it remains an underexplored candidate for generating micro-nanofibrous structures. In this study, solution blow spinning was employed to fabricate bilayer composite nonwovens for wound dressing materials. The material architecture consisted of a bottom layer composed of a blend of natural rubber, poly(lactic acid) (PLA), and polyethylene glycol in the respective proportion of 2:1:3 w/w and a top layer composed of PLA and ZnO nanoparticles added in concentrations of 1%, 2.5%, and 5% based on the PLA mass of this layer. The top layer was further functionalized with Ag nanoparticles through spraying. The obtained materials demonstrated satisfactory hydrophobicity for cellular adhesion in the bottom layer, ranging from 51.95° to 92.20° of water sessile drop contact angle, and tunable mechanical strength, which could be controlled by varying the content of ZnO nanoparticles. Additionally, the material showed antimicrobial properties due to the presence of added Ag nanoparticles, able to inhibit E. coli, S. enterica serovar Typhimurium, and S. aureus by direct contact. Besides, the nonwoven prevented the passage of microorganisms due to the pore size of the structure. Overall, the unique properties of the developed material, such as its low cost, ease of production, and remarkable wound-healing properties, make it a promising candidate for wound dressing applications.

Electrospun compliant heparinized elastic vascular graft for improving the patency after implantation

The low patency rate after artificial blood vessel replacement is mainly due to the ineffective use of anticoagulant factors and the mismatch of mechanical compliance after transplantation. Electrospun nanofibers with biomimetic extracellular matrix three-dimensional structure and tunable mechanical strength are excellent carriers for heparin. In this work, we have designed and synthesized a series of biodegradable poly(ester-ether-urethane)ureas (BEPU), following compound with optimized constant concentration of heparin by homogeneous emulsion blending, then spun into the hybrid BEPU/heparin nanofibers tubular graft for replacing rats' abdominal aorta in situ for comprehensive performance evaluation. The results in vitro demonstrated that the electrospun L-PEUUH (LDI-based PEUU with heparin) vascular graft was of regular microstructure, optimum surface wettability, matched mechanical properties, reliable cytocompatibility, and strongest endothelialization in situ. Replacement of resected abdominal artery with the L-PEUUH vascular graft in rat showed that the graft was capable of homogeneous hybrid heparin and significantly promoted the stabilization of vascular endothelial cells (VECs) and vascular smooth muscle cells (VSMCs), as well as stabilizing the blood microenvironment. This research demonstrates the L-PEUUH vascular graft with substantial patency, indicating their potential for injured vascular healing.

Dynamic ionic crosslinking, graft polyethylene glycol-based polymeric phase change materials networks with ultrahigh latent heat efficiency and recycling ability

Polymeric polyethylene glycol (PEG)-based phase change materials (PCMs) present the intrinsic shape-stable essence, tunable phase change properties and mechanical strength, yet most of polymeric PCMs present a relatively low latent heat density (<120 J/g) and efficiency (<0.7), non-recycling ability resulting from the covalent crosslinking structure. Herein, the graft PCMs (GPCMs) with graft PEG side chains were synthesized via the dynamic ionic crosslinking reaction of carboxyl-functionalized graft PEGs and citric acid as the carboxyl co-donors with divalent zinc cations. The phase change and rheological properties of the GPCMs can be readily tuned by the length of PEG side chains and the loading content of citric acid. The highest latent heat density and efficiency of the GPCMs reach up to 155.0 J/g and ∼1, respectively, resulting from the synergistic effect of the ionic bonding and graft PEG side chains. The GPCMs present the shape-stable solid-solid phase transition behavior, high thermal reliability and stability, photothermal properties by compositing carbon black and excellent solvent-induced dissolving ability resulting from the nature of dynamic ionic crosslinking. The design of dynamic ionic crosslinking GPCMs structure will provide a robust, versatile access to the combination of high latent heat density and efficiency, high mechanical strength, recycling ability in a single organic PCMs.

Tough and Transparent Photonic Hydrogel Nanocomposites for Display, Sensing, and Actuation Applications

Thermosensitive hydrogels with periodic dielectric structures displaying tunable structural color by temperature stimuli have attracted much research interest recently. However, reported thermosensitive photonic hydrogels either using the poly(N-isopropylacrylamide) (PNIPAM) bulk hydrogel as the responsive matrix or using PNIPAM microgels as the photonic building blocks have poor mechanical strength. Moreover, the expensive and time-consuming preparation process also limits their further application. In this work, a different strategy for preparing PNIPAM-based photonic hydrogel nanocomposite films with strong mechanical strength is proposed by incorporating a PNIPAM microgel film with the polyacrylamide (PAM) hydrogel. The preparation process is simple but efficient, and the obtained nanocomposite films have tunable mechanical strength by changing the crosslinking degree of the PAM hydrogels. More interestingly, the structural color of the nanocomposite films can be retained up to 80 °C (at least), much higher than those of previously reported PNIPAM-based photonic materials. In addition to being thermochromic, the film is sensitive to humidity, and the structural color-changing process is similar to the molting process of cicadas. Furthermore, the nanocomposite films have synchronous shape deformations and color changes and can be used as color-tunable soft actuators. The microgel film-capped photonic hydrogels provide a new strategy for the preparation of thermoresponsive photonic hydrogels and structural color-tunable actuators.

Injectable hydrogels of enzyme-catalyzed cross-linked tyramine-modified gelatin for drug delivery

Enzymatically catalyzed cross-linking is a hydrogel fabrication method that generally is considered to have lower cytotoxicity than traditional chemical cross-linking methods. In order to optimize the properties of injectable hydrogels and expand their applications, an enzyme-catalyzed cross-linked injectable hydrogel was designed. The tyramine-modified gelatin (G-T) was formed into a stable injectable hydrogel by the combination of horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) catalysis. 1H NMR spectroscopy was used to demonstrate the successful modification of gelatin by tyramine. The surface morphology of the prepared hydrogels was characterized jointly by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Rheological tests demonstrated the tunable mechanical strength, formation kinetics, shear thinning and good self-recovery properties of the hydrogels. In addition, the hydrogels can be formed into various shapes by injection. The hydrogel network structure is complex and interlaced, as such it is suitable to encapsulate drugs for controlled release. The drug release from the prepared hydrogels followed the Peppas–Sahlin model and belonged to Fickian diffusion. This study constructed injectable hydrogels through the enzyme-catalyzed cross-linking of modified gelatin and applied the hydrogels for drug release, which is expected to expand the application in biomedical fields.