The control of major bleeding in accidents or clinical settings is a critical area that needs to be developed in the current medical field. Cryogel sponges have excellent hemostasis and wound healing potential due to its high porosity and water absorption. Here, a composite sponge (HH-MnBGs+) of natural polymer and positively charged Mn-doped bioactive glass nanofibers (MnBGs+) was prepared. The main body of sponge is composed of hyaluronic acid (HA) and hydroxypropyl chitosan (HPCS). The directional channels are constructed through directional freezing method and they can absorb water more quickly through capillary action. MnBGs+ were prepared by electrospinning methods and quaternized with silane coupling agents and adsorbed onto the surface of the channels through electrostatic interactions to facilitate rapid contact between them and blood or tissue. These multifunctional nanofibers adsorbed in the channel can respond to the external environment in a timely manner and achieve multifunctionality in antibacterial, anti-inflammatory, hemostatic, and healing promotion. When blood flowed into the channel, red blood cells (RBCs) and platelets were adsorbed on the surface of channel and form the artificial thrombus. Moreover, MnBGs+ can effectively alleviate inflammation and promote wound healing by removing reactive oxygen species (ROS) and accelerating angiogenesis. Thus, HH-MnBGs+ sponge has a great potential for application in non-compression hemostasis and wound healing.
Lipopolysaccharide (LPS) is recognized as a promising candidate for immunotherapy due to its potent immunogenic properties. However, this strong immunogenicity necessitates precise and protective delivery strategies to ensure safe and effective application. In this study, an ultrasonic probe-fabricated nanocapsule was first developed. Owing to the hydrophobic barrier provided by the system, LPS covalently linked methyl acrylated hyaluronic acid (HAMA-LPS) based surfactant-free emulsion polymerization occurred exclusively at the interface of monomer vesicles, resulting in the formation of a hollow-structured nanocapsule. This structure not only protected the immunogenic LPS from oxidative damage in free radical polymerization but also enabled the in situ loading of the hydrophobic photosensitizer chlorin e6 (Ce6). The prepared nanocapsules achieved a 1.53% loading rate of Ce6 and could effectively generate ROS under laser irradiation and undergo acid/enzyme-responsive release. Following cellular uptake by tumor cells, the nanocapsule underwent degradation mediated by hyaluronidase, leading to the release of LPS-Ce6. Subsequently, LPS-Ce6 anchored onto the tumor cell membrane via hydrophobic interactions and exerted photodynamic therapy upon laser irradiation. This therapeutic strategy elicited a robust immune response. On the one hand, photodynamic therapy compromised cell membrane integrity, thereby promoting the release of damage-associated molecular patterns. More importantly, the membrane-anchored LPS-Ce6 acted as an in situ antitumor vaccine, providing a focal point for monocyte and macrophage recruitment, while inducing macrophage polarization toward the M1 phenotype and stimulating the secretion of various antitumor cytokines. Both in vitro and in vivo experimental results demonstrated that the nanocapsule effectively inhibited tumor growth and generated a significant antitumor immune response.
This study established a visible-light initiated inverse emulsion photopolymerization system for synthesizing polyacrylamide (PAM) microspheres under green LED irradiation. By systematically regulating emulsification parameters (surfactant ratio, oil/water ratio) and polymerization conditions (irradiation time, irradiation power), stable water-in-oil (W/O) emulsions were achieved. Optimal emulsion stability was observed at a hydrophilic-lipophilic balance (HLB) value of 7.2 and an oil/water ratio of 85
Diabetic wound healing remains a critical clinical challenge due to persistent oxidative stress, recurrent infections, and dysregulated inflammation within the wound microenvironment. Consequently, it is desirable to develop advanced dressings capable of microenvironment-adaptive therapy to simultaneously address these pathological conditions. Herein, an innovative guanosine (G4)-stabilized lipoic acid (LA)-based supramolecular hydrogel integrating LA and G4 is fabricated through a one-step assembly. This design pioneers a dynamic stabilization strategy wherein the G4 network’s multivalent hydrogen bonds prevent reverse ring-opening depolymerization of polylipoic acid (PolyLA) while enabling on-demand reversible disulfide reconfiguration, thereby overcoming the stability-depolymerization imbalance in conventional LA-based hydrogels. Furthermore, by modulating the content of LA, two types of hydrogels including injectable hydrogels and patch hydrogels are developed tailored for meeting different clinical applications. Both in vitro and in vivo studies demonstrate that these hydrogels exhibit multiple responsiveness, potent reactive oxygen species (ROS) scavenging capacity, significant anti-inflammatory activity, and antibacterial properties, thereby facilitating the healing of diabetic wounds. This innovative approach not only addresses the inherent instability of LA-based hydrogels but also establishes an effective responsive therapeutic platform for chronic wound management. Statement of Significance A newly developed approach addresses the reverse ring-opening depopolymerization of polylipoic acid by employing a guanosine supramolecular network for stabilization. The guanosine network provides robust stabilization while exhibiting multi-stimuli responsiveness, enabling a controllable reverse depolymerization of polylipoic acid that surpasses conventional unidirectional strategies. Importantly, the synthesis conditions for the guanosine network and polylipoic acid are nearly identical, as both require an alkaline pH and elevated temperature. This compatibility allows direct hydrogel formation through a simple process of mixing, heating, and cooling. The resulting hydrogel capitalizes on the inherent biological activities of both lipoic acid and guanosine, demonstrating potent antioxidant and antimicrobial properties alongside multi-stimuli responsiveness for diabetic wound management.
Food colorants are widely developed and used in food processing. However, synthetic colorants that are not effectively utilized are discharged with industrial wastewater, posing a threat to the ecological environment. It is crucial to develop green and efficient preparation methods and design high-capacity adsorbents. In this work, a rapid preparation strategy with zero-solvent-emission enabled a significant decrease in gelation time (10 s) for the synthesis of PAD/QC aerogel beads, using diallyldimethylammonium chloride (DMDAAC) and acrylamide (AM) as functional monomers with quaternized chitosan (QC) as an interpenetrating polymer network (IPN). The physicochemical properties of the aerogel beads were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Zeta-potential, Raman spectroscopy, and thermogravimetric analysis (TGA). The PAD/QC aerogel beads exhibited good adsorption capability toward Sunset Yellow (SY), reaching a maximum of 142.75 mg & sdot;g- 1. Adsorption kinetics, adsorption isotherms, and molecular dynamics (MD) simulations were employed to elucidate the adsorption mechanism. The CCK-8 and live/dead cell staining assays confirmed their excellent biocompatibility. For the adsorption of SY in commercial beverages, the removal rate of PAD/QC aerogel beads was 80.69%, making it an effective adsorbent for the removal of food colorants.
During photopolymerization, the large molecular size and complex entanglement of the products may result in the physical encapsulation of the photosensitizers within the polymer matrix, potentially influencing material properties and introducing additional optical activity, which can alter the material properties in product performance and even introduce unwanted additional optical activity. In contrast, in fields such as photodynamic therapy, organic synthesis, and wastewater treatment, the retention of photosensitizers within the products can provide sustained reactive functionality. ZnPC and ZnTTP exhibit excellent photochemical activity due to their unique rigid structures and closed-shell configurations. In this work, these two zinc-coordinated photosensitizers were employed in TEOA/DPI-assisted systems for photopolymerization. The photopolymerization mechanisms of ZnPC- and ZnTTP-based initiating systems were elucidated through double bond conversion, cyclic voltammetry, and electron paramagnetic resonance analyses. Furthermore, the singlet oxygen production efficiencies of the two compounds were measured, which confirmed the hypothesis that ZnPC and ZnTTP were retained within the products, and provided two possible products with potential as photosensitizers.
Exosomes as a unique drug delivery system provide a new choice for tumor therapy. However, the in vitro functionalization of exosomes and the process of circulating drug delivery can easily cause exosome degradation and drug loss, thus reducing the efficiency of drug delivery. In this work, based on the endocyto-fusion-exocytosis pathway of exosome formation, a multifunctional hyaluronic acid nanogel loaded with the antiangiogenic drug vatalanib and the near-infrared photothermal agent indocyanine green (ICG) was designed. Lysosome escape and photothermal therapy were combined to promote exosome production. Hyaluronic acid nanogels were endocytosed by tumor cells with CD44 mediation, forming intracellular vesicle-coated nanogels, which were subsequently degraded by hyaluronidase with high expression in tumor cells. Anti-angiogenic signals in intracellular vesicles were then delivered to vascular endothelial cells by exosomes through membrane fusion and exocytosis, which inhibited tumor angiogenesis to prevent tumor proliferation and metastasis. Cell experiments and tumor models demonstrate that our therapeutic strategy can achieve effective tumor inhibition.
Internal bleeding has always been a major cause of human death in clinical or battlefield settings. In this study, a cryogel sponge was prepared by freezing method, it can effectively stop bleeding by concentrating blood, efficiently adsorbing red blood cells and platelets. Cryogels have excellent anti-swelling performance and avoid the problem of further wound expansion caused by swelling. Hyaluronic acid and hydroxypropyl chitosan are the main bodies of cryogel, and dopamine is grafted onto the side chain of hyaluronic acid through a one pot method to cope with oxidative stress and shorten the process flow. Quaternary chitosan is intercalated into the polymer network and provides abundant positive charges. Cryogel shows high positive electricity in acidic environment (17.10 mV, pH = 5.0), which benefits cryogel to adsorb red blood cells and platelets and to resist bacterial infection. On this basis, bioactive glass is added into the cryogel to further promote coagulation and wound healing. Cryogel can be repeatedly compressed (40.3 kPa) and significantly reduce the amount of bleeding, resulting in an 81.9 % decrease in the amount of bleeding compared with blank group in vivo hemostasis experiment. Moreover, cryogel could effectively inhibit inflammatory reaction and promote wound healing.
Deep burn wounds present significant challenges to rapid healing due to their complex microenvironment, characterized by multiple bacterial infections, excessive oxidative stress and blocked angiogenesis. Herein, a skin-inspired biogel/nanofiber composite dressing composed of gelatin-based biogel and electrospun nanofiber membrane co-loaded with asiaticoside (AS) and ZnO is designed and prepared for regulating the wound microenvironment to accelerate deep burn wound healing. Sodium pyrrolidone carboxylate (PCA-Na) as a natural moisturizing factor is introduced into the gelatin solution to prepare a skin-inspired biogel with strong tissue adhesion, high mechanical strength and good water retention capacity. The sustained release of AS and zinc ions (Zn2+) co-loaded into nanofibers promotes antibacterial activity, anti-inflammatory effects, angiogenesis and collagen deposition. The composite dressing exhibits excellent adhesion to red blood cells and platelets, hemocompatibility and cytocompatibility. Furthermore, it also presents remarkable rapid hemostasis capability with the hemostatic time greatly shortened to 35 s and the blood loss significantly reduced to 71 mg. Notably, it can significantly shorten the healing time of deep burn wound to 17 days by rapidly absorbing wound exudate, promoting collagen deposition and new blood vessels regeneration. Consequently, the composite dressing represents a promising sustained co-delivery system for accelerating burn wound healing.
To overcome the inherent mechanical limitations of polysaccharide hydrogels for dye adsorption, we developed dual-network hydrogel microspheres via efficient one-step droplet photopolymerization initiated by green LED. The primary network was photopolymerized from sodium acrylate monomers and ethylene glycol dimethacrylate cross-linker, while the secondary network formed through Schiff base conjugation between oxidized chondroitin sulfate and carboxymethyl chitosan. Systematic characterization (FTIR, TGA, SEM, XPS) confirmed the hydrogels' structural and thermal properties. Key operational parameters including contact time, temperature, initial MG concentration, pH, and ionic strength were optimized. At room temperature, adsorption equilibrium was achieved within 3 h, following pseudo-second-order kinetics. The adsorption capacity is 806.51 mg/g and fitted the Langmuir isotherm model. Electrostatic interactions dominated the adsorption mechanism, as verified by pH and ionic strength experiments. After five adsorption-desorption cycles, MG removal efficiency remained more than 80 %.
Metal-organic framework (MOF) materials are recognized as outstanding templates for preparing porous metal oxides used as gas-sensitive materials. Here, a facile synthesis strategy is proposed to prepare Pt-Co3O4@ZnO hollow porous nanofibers with MOF-on-MOF structure and noble metal for gas-sensing applications. Sensors fabricated with this unique nanomaterial show fast response, low detection limit (LOD), high selectivity, and good stability to H2S gas. Notably, the gas response of the sensor with Pt-Co3O4/ZnO nanofibers is three times that for the sensor with Co3O4/ZnO, and the optimal operating temperature is reduced by 125 degrees C. Furthermore, the gas-sensing mechanism is proposed in detail, and theoretical calculations based on the first principles further reveal the performance enhancement of Pt-Co3O4/ZnO nanofibers to H2S. This study offers a strategy for fabricating noble metal-dropping dual MOFs-based nanofibers with abundant pores and high surface area for high-performance gas-sensing applications.
Hemodialysis catheters are prone to catheter-related complications due to their rough surface microstructure and poor lubrication, yet clinical solutions remain limited. This study developed a facile three-dimensional semi-interpenetrating polymer network (semi-IPN) hydrogel coating based on sulfobetaine methacrylate (SBMA) and polyvinyl alcohol (PVA) for surface lubrication of hemodialysis catheters. The hydrogel coating was characterized via Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Swelling tests, shear resistance assays, and hemolysis experiments confirmed its structural stability and blood compatibility. Hydrophilicity and lubricity were validated through water contact angle measurements and friction coefficient analyses. Anti-bacterial adhesion, anti-platelet adhesion, and ex vivo circulation experiments demonstrated its anti-infective and anticoagulant capabilities. This study proposes a novel functional coating strategy to reduce catheter-related complications in hemodialysis, offering significant potential for clinical translation.
With the rapid development of industry, water pollution has become one of the important problems that harm the ecological environment and human health. The extensive use and random discharge of dyes have caused serious damage to water resources. Hydrogel bead is a promising material for dye adsorption due to its advantages of rich functional groups and high specific surface area. Here, acrylic acid sodium salt (AAS) and 2acrylamide-2-methylpropanesulfonic acid (AMPS) as monomers, N,N'-Methylene-bis-acrylamide (MBA) as crosslinking agent, sodium alginate (SA) as semi-interpenetrating network component, laponite as nano-clay additive, and single 2 ',4 ',5 ',7 ' -tetrabromofluorescein disodium salt (EY)/ Triethanolamine (TEOA)/ diphenyl iodonium hexafluorophosphate (DPI) as green light polymerization initiating system were combined to prepare composite hydrogel beads within 10 s under green LED irradiation. The composite hydrogels were characterized by infrared spectroscopy (FTIR), thermogravimetric analyzer (TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The addition of sodium alginate and laponite can improve the mechanical properties of hydrogel beads. In the adsorption study of malachite green, the influence of time, temperature, dye concentration, pH, ionic strength, and other factors on the adsorption effect were investigated. The adsorption process was consistent with the second-order kinetic process and Langmuir adsorption. At room temperature, the highest adsorption capacity of the hydrogel beads for malachite green reached 829.63 mg/g. The PAAS-SL hydrogel beads maintained a high adsorption effect in the pH range (3-10), and the capacity reached 575.0 mg /g at pH 3, which had a good ability to resist low pH. In the adsorption-desorption experiments, the removal rate of PAAS-SL hydrogel beads for MG is still more than 80 % after 5 cycles. Our research provides a promising strategy for the efficient and rapid preparation of hydrogel beads with excellent properties.
The safety and performance of lithium-ion batteries (LIBs) are closely related to the separator. Commercial polyolefin separators hinder electrochemical performance and may result in safety issues at high temperatures due to insufficient thermal stability and electrolyte wettability. In this work, a polyimide (PI)/metal-organic framework-5 (MOF-5) composite separator was prepared via in situ polymerization and electrospinning. The tensile strength of the PI/MOF-5 composite membrane was superior to that of the PI membrane by 104%. The outstanding flame retardancy of the PI/MOF-5 composite separator significantly enhances the safety of lithium-ion batteries, especially in high-temperature environments. The PI/MOF-5 separator demonstrated a high number of lithium-ion transferences (t Li + = 0.79). The cell using the PI/MOF-5 separator exhibited excellent cycling performance, with an initial discharge capacity of 174.7 mA h/g at a current density of 0.5 C, which is 140.8 and 46.6% higher than that of the LIB coin cell with a polypropylene (PP) separator and PI separator, respectively. After 200 cycles at a current density of 0.5 C, the specific discharge capacity of the battery using the PI/MOF-5 separator still maintained 89.02% of the initial specific discharge capacity, which is higher than that of the PP and PI separators. Consequently, the outstanding properties of the PI/MOF-5 composite separator indicate its potential in high-performance lithium-ion batteries.
Photopolymerization is a convenient method for preparing nanogels. However, the retention of photoinitiators within the nanogels can potentially be cytotoxic and cause additional fluorescence interference in visualization process. To address this issue, chlorophyll hyaluronic acid nanogels (HAChlgel) were prepared through a chlorophyll-photoinitiated approach. The resulting HAChlgel effectively retained the chlorophyll photoinitiator internally and utilized its versatile photoactivity as a photosensitizer in photodynamic therapy. HAChlgel could provide exogenous oxygen supply and undergo self-promoted photodynamic therapy, which confirmed by oxygen probe and ROS generation assay. Notably, under tumor acidic conditions, HAChlgel exhibited a tendency to release Mg2+, which enhanced the synergistic therapeutic effect. Through the targeting effect induced by hyaluronic acid, HAchlgel aggregates in the tumor area, and executes self-promoting photodynamic therapy.
Hollow polymer nanoparticles have garnered significant attention in sensing, catalysis, and biomedical applications due to their unique structural properties. To develop a novel synthetic approach of dual-responsive hollow nanoparticles, a visible-light-initiated photopolymerization strategy under green LED irradiation was established. First, monodisperse poly(methyl methacrylate) (PMMA) nanoparticles were synthesized via dispersion photopolymerization. These nanoparticles served as seeds for subsequent seed photopolymerization, enabling the formation of raspberry-like core-shell structures with different sizes and surface morphologies by adding different dosages of secondary stimuli-responsive monomers N-isopropylacrylamide (NIPAM) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). Finally, solvent etching was employed to remove the PMMA seeds, producing hollow polymer nanoparticles with controllable temperature and pH responsiveness.
Uncontrolled bleeding of wound is one of the main causes of death, and wound often has bacterial infection and inflammation to hinder wound healing. In this study, natural polyphenol procyanidin was added to gelatin and quaternized chitosan, and a pure natural sponge (GQ2O) was prepared by mechanical stirring, crosslinking and freeze-drying. The macroporous structure of GQ2O was formed by natural soybean lecithin as blowing agent combined with mechanical stirring, and the three-dimensional network structure was crosslinked by Genipin. The use of natural compounds avoids the toxicity of traditional chemical blowing agents and crosslinkers. GQ2O has excellent water absorption ability (2060.1 %), suitable mechanical property (28.1 kPa), biodegradability, biocompatibility, antibacterial and antioxidant properties, and shows rapid hemostasis and accelerate wound healing performances in vivo. In the rat liver injury model, the bleeding time and blood loss of GQ2O were significantly lower than those in gauze group, commercial hemostatic gelatin sponge group and blank group. In the rat back full-thickness skin defect model, the wound inflammation was significantly relieved by GQ2O treatment, and the wound healing rate reached 98.9 % on the 14th day. Therefore, GQ2O has great potential for rapid hemostasis and promoting wound healing.
Lipoic acid-based hydrogels are considered promising candidates for wound dressings due to their antioxidant properties. However, their practical application has been hindered by complex and time-consuming fabrication methods. To address this limitation, a novel oscillation-driven strategy was developed for the rapid and energy-efficient preparation of lipoic acid@polyethyleneimine-x-poly (ethylene glycol) diacrylate-y-protocatechualdehyde-z (LA@PEIx-GyAz) hydrogels. In detail, the polymerization of lipoic acid (LA) is initiated by polyethyleneimine (PEI) to form polylipoic acid (PolyLA), which is stabilized by poly (ethylene glycol) diacrylate (PEGDA) and protocatechualdehyde (PA). Gelation was completed within minutes without requiring external thermal or photoactivation. Additionally, a controlled reverse closed-loop depolymerization process was employed to optimize the hydrogel's mechanical properties, producing a soft and adhesive material suitable for tissue application. In this system, a three-dimensional scaffold was formed by PolyLA, while liberated LA monomers served as bioactive components. Our experimental results demonstrate that the LA@PEIx-GyAz hydrogel not only exhibits superior skin adhesion, with an average strength of 23.45 ± 1.78 kPa, but also effectively alleviates oxidative stress and presents antibacterial performance. Moreover, the hydrogel shows a promoting effect on wound healing in a rat model.
The treatment of chronic diabetic wounds faces considerable challenges owing to complex environments in the wound bed, such as chronic inflammation, excessive reactive oxygen species (ROS), impaired extracellular matrix (ECM) and bacterial infection. Current strategies, including bandages, hydrogel dressings and medical devices, that focus solely on a few pathological features have limited success. Herein, a fast self-gelling polyacrylic acid (PAA) derivative/madecassoside (MA) particulate dressing with anti-inflammatory, antioxidative, collagen deposition-promoting and intrinsic antibacterial properties is developed to simultaneously regulate the wound microenvironment and promote tissue regeneration in infected diabetic wounds. The incorporation of N-[Tris(hydroxymethyl)methyl]acrylamides (THMA), a small molecule compound that has three hydroxy groups clustered together, into the PAA backbone confers the copolymer with self-gelation, robust wet tissue adhesion and a strong capacity to load MA via multiple hydrogen bonding. The developed dual-component particulate dressing effectively regulated macrophage polarization towards the anti-inflammatory phenotype, and displayed potent antibacterial activity against both Gram-positive S. aureus (99.2 %) and Gram-negative E. coli (90.8 %) at a dose of 8 mg mL-1. Further, the dressing obviously accelerated the healing of full-thickness skin wounds compared with commercial fibrin glue in a S. aureus-infected diabetic mouse model. This multifunctional PAA-based wound dressing is potentially valuable for clinical applications towards diabetic foot ulcers, pressure ulcers and other conditions of acute or chronic wounds.
A key challenge in multifunctional injectable wound dressings is the lack of integration between the appropriate mechanical strength, the effects of antibacterial, antioxidant and pro-healing properties. In this study, a pioneering research has been designed with the polymerization between oxidized dextran (ODex) and carboxymethyl chitosan (CMCS) to develop a double cross-linked injectable hydrogel (OD/CM/BP@Bai). This hierarchical structure combines a physically entangled network (providing immediate mechanical integrity) and a dynamic covalent network (enabling self-healing and injectability), resulting in a composite hydrogel with a storage modulus (G') approximately twenty times higher than that of single-network ODex pre-gel. Innovatively, black phosphorus nanosheets (BPNS) were incorporated as dual-functional elements, acting concurrently as photothermal conversion agents and nanoscale drug reservoirs. Through π-π stacking interactions, a high drug loading rate of 5.6 % was achieved for the hydrophobic drug baicalein (Bai). Incorporation of the nanoparticles further enhanced the overall mechanical properties of the hydrogel. Under near-infrared (NIR) irradiation, the hydrogel enabled synergistic and on-demand therapy. The photothermal effect not only directly eradicated bacteria but also triggered rapid Bai release. Through the synergistic interaction of functional components (CMCS/Bai/BPNS), a responsive hydrogel integrating antibacterial, anti-inflammatory, and pro-regenerative performances was constructed, which provides an innovative solution for wound treatment.