Search Results (462)

Modulating the physical crosslink architecture of gelatin methacryloyl (GelMA) hydrogels without altering total polymer concentration or introducing exogenous components remains a central challenge in biomaterial design. Here, we present a source blending strategy in which porcine skin gelatin (PG) and salmon skin gelatin (SG), two gelatins with markedly different proline and hydroxyproline contents, are combined at seven compositional ratios (PG weight fractions 0–1.0) and subsequently functionalized to GelMA under standardized conditions (8% v/v methacrylic anhydride, 60 °C, 3 h). Near-complete degrees of substitution (95–98%) were achieved across all formulations, as confirmed by both TNBS and ¹H-NMR analyses. In the parent gelatin mixtures, increasing PG fraction progressively increased viscosity, elastic modulus (G′), gelation temperature (Tgel), and compression modulus at 4 °C, with DSC revealing independent SG (0–15 °C) and PG (20–40 °C) endothermic transitions that suggest partial hindrance of PG triple-helix formation by high SG fractions. These composition-dependent trends were preserved after functionalization to GelMA, albeit with attenuated physical crosslinking due to steric impairment by the methacrylate groups. Photocrosslinked GelMA hydrogels fabricated after pre-incubation at 4 °C exhibited systematically higher compression moduli and lower swelling degrees with increasing PG content, demonstrating that the PG/SG ratio provides an effective means for independently tuning hydrogel mechanics and mesh architecture. In vitro release assays using Rhodamine 6G further demonstrated that pre-incubation at 4 °C prior to photocrosslinking effectively modulates transport kinetics in SG-PG GelMA hydrogels. This strategy delayed characteristic release times and constrained Weibull shape parameters to the anomalous-transport regime (0.75 < β < 1), where diffusion is governed by network chain relaxation. This effect was most pronounced in the 0.4SG:0.6PG formulation, where lower SG content permitted unhindered triple-helix formation, as corroborated by DSC and compression studies. Ultimately, adjusting the pre-incubation temperature and gelatin source combination provides a straightforward, processing-additive-free strategy to achieve programmable release profiles via controlled matrix tortuosity. Full article

Objectives: To address the critical limitations of current formulations that fail to simultaneously resolve indomethacin’s poor water solubility, susceptibility to gastric acid hydrolysis, and difficulty in balancing rapid onset with long-term sustained release, this study prepared solid dispersions via anti-solvent freeze-drying to improve drug dissolution, constructed oral buccoadhesive bilayer controlled-release tablets using direct powder compression, and elucidated the intrinsic relationships among polymer gel properties, swelling-erosion behavior, tablet integrity maintenance, and drug release mechanisms. Methods: Solid dispersions (SDs) were prepared by anti-solvent freeze-drying. Bilayer tablets (25 mg IND/tablet, 12.5 mg/layer) were fabricated via direct powder compression after optimizing disintegrants and polymer matrices. In vitro dissolution, surface pH, adhesion time, and adhesion strength were evaluated. Results: SDs enhanced dissolution by at least 30-fold in water and 2.4-fold at pH 6.8 within 2 h versus pure drug. Optimized bilayer tablets achieved 45% drug release at 20 min and 80% sustained release over 8 h, with surface pH of 6.8 ± 0.1, adhesion time of 8.3 ± 0.1 h, and adhesion strength of 57 ± 0.13 g. Conclusions: The physicochemical properties of polymeric excipients are critical for balancing drug release and mucoadhesion in buccal tablets. To achieve ideal controlled-release effects, in addition to focusing on the swelling and erosion characteristics of matrix-based tablets, the ability to maintain tablet integrity during dynamic dissolution must be further investigated, which is an essential factor for ensuring precisely modulated drug release. Meanwhile, when employing solid dispersions as solubilizing intermediates to prepare controlled-release formulations, the gelling properties of polymers in each formulation component should be fully considered to avoid incomplete disintegration and insufficient release at the initial dissolution stage. Full article

Scaffolds designed for mechanically demanding soft tissue engineering applications should integrate mechanical support, efficient mass transfer, and good cellular compatibility. This work presents a one-pot method based on “radical-free click chemistry + carbodiimide coupling” to produce a double-network (DN) PEG–alginate cryogel. The PEG network is formed by a Michael addition reaction between thiol-based crosslinker and 8-arm PEG-acrylate. The second network is covalently crosslinked through EDC/NHS-mediated coupling of carboxyl groups in alginate and adipic acid dihydrazide (AAD). The subsequent freezing and gelation of the gel precursor at sub-zero temperatures results in an ice templated cryogel with an interconnected macroporous network. These cryogels demonstrate high elasticity, compressive modulus and rapid swelling equilibrium in aqueous environments, as well as controlled degradation under physiological conditions. Compared to the classical Ca²⁺ ion crosslinking systems, the covalent linking of the alginate in the double-network cryogel shows advantages in mechanical and structural stability. In addition, it is cell-compatible and allows culture of mesenchymal stem cells (MSCs) with homogeneous infiltration. Furthermore, the double-network cryogels supports chondrogenic differentiation of MSCs upon treatment with chondrogenic media or macrophage-conditioned media for a short period of time. These results indicate that crosslinking chemistry and polymer composition can be used to modulate the balance between mechanical performance and degradation behavior, while maintaining cytocompatibility and an interconnected macroporous network, thereby providing a scaffold design strategy for applications that require coordinated mechanical support and mass transfer, such as cartilage-related tissue engineering. Full article

Gelatin functionalized with methacrylate (GelMA), norbornene (GelNB), and phenol (GelPH) has been studied as a precursor for crosslinkable biomaterials in tissue engineering. Cytocompatibility is usually assessed post-hydrogel formation, but cells briefly encounter soluble precursors during preparation and residual functional groups that may remain post-gelation. However, the biological effects of these uncrosslinked derivatives remain poorly understood. This study systematically investigated the impact of functional group chemistry on cellular responses under uncrosslinking conditions. Four cell lines, including fibroblasts (BALB/3T3), cervical cancer cells (HeLa), mesenchymal stem cells (UE7T-13), and neuronal cells (PC-12), were exposed to soluble GelMA, GelNB, and GelPH at matched polymer concentrations and degrees of functionalization (~50%). The results showed no overt cytotoxicity. The detectable differences were subtle and strongly cell type-dependent. HeLa and PC-12 cells showed no clear differences from untreated controls in most parameters. BALB/3T3 fibroblasts showed mainly GelMA-associated differences in mitochondrial activity, proliferation, and morphology. In the UE7T-13 cells, GelMA-treated cells showed the largest deviations from controls across the readouts examined, including mitochondrial activity, cell area, phenotype-related gene expression, and some osteogenic markers, while GelPH was intermediate and GelNB was comparable to controls. These findings underscore the importance of considering residual precursor effects in gelatin-based biomaterial design. Full article

A critical challenge in coalbed methane (CBM) extraction is the severe formation damage induced by conventional foam fracturing fluids, primarily through polymer retention and hydrogen bond disruption within the microporous matrix. This study presents a molecularly engineered, low-damage foam fracturing fluid that leverages synergistic nanoparticle–surfactant interactions to construct a robust interfacial pseudo-gel network, thereby decoupling effective fracture stimulation from adverse geochemical damage. The primary novelties of this work are threefold: (i) establishing a direct, quantitative cause-and-effect relationship between molecular interfacial architecture and reservoir protection, (ii) proposing a comprehensive “interfacial control” design paradigm that engineers viscoelasticity at the gas–liquid interface rather than through bulk polymer gelation, and (iii) demonstrating the complete decoupling of foam stability from formation damage in a polymer-free system. A systematic optimization methodology was employed: initial foaming agents were screened via the Waring Blender method, evaluating foam volume, half-life, and a derived comprehensive index; subsequently, synergistic binary surfactant mixtures and foam stabilizers were assessed to formulate the final systems. An optimized formulation, designated Foam System I (0.5 wt.% fluorosurfactant FK + 0.5 wt.% nano-silica RX + 2.0 wt.% KCl), demonstrated exceptional foam quality (Γ = 77.1 ± 1.5%) and kinetic stability (T₁/₂ > 350 s). Rheological characterization confirmed shear-thinning behavior conforming to the Herschel–Bulkley model (n = 0.38–0.42, R² > 0.98) and a structural recovery of 92.5 ± 2.1%—comparable to crosslinked polymer gels but achieved without any bulk viscosifier. Core flood analyses revealed that Foam System I induced a permeability damage of only 12.75 ± 1.8%, representing a 55–75% reduction compared to polyethylene glycol (PEG)-stabilized reference fluids (28.36–51.91%). X-ray photoelectron spectroscopy (XPS) correlated this enhanced reservoir compatibility with an 18.0 ± 2.0% suppression of oxygen-containing functional group adsorption, attributed to the steric hindrance conferred by the fluorinated hydrophobic moieties. This work establishes an “interfacial control” paradigm wherein gel-like stabilization for proppant transport is achieved via interfacial viscoelasticity rather than bulk polymer gelation, thereby directly addressing the critical imperative to harmonize fracture conductivity with reservoir protection in unconventional energy development. The findings are validated for shallow CBM reservoir conditions (25–35 °C), with extension to higher-temperature formations identified as a priority for future investigation. Full article

To address the poor temperature resistance of conventional gel breakers, the uncontrollable gel-breaking time, and the risk of secondary reservoir damage during temporary plugging of fractured formations with polymer gels, a high-temperature-resistant double-shell encapsulated gel breaker, UF-EC/SA, was prepared using oil-phase phase separation combined with in situ polymerization. In this material, urea-formaldehyde resin (UF) served as the outer shell, ethyl cellulose (EC) as the inner shell, and sulfamic acid (SA) as the core. Unlike conventional single-shell persulfate or directly added acid breakers, this double shell design integrates a thermally resistant UF barrier, a diffusion-controlling EC layer, and an acid core to delay premature gel degradation while enabling subsequent cleanup. The physical structure and sustained-release behavior of the capsules were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), and conductivity measurements. The compatibility between the encapsulated breaker and the polymer gel, as well as the effects of salinity and breaker dosage on the rheological properties of the gel, were investigated. The regulatory effects of temperature and capsule dosage on gel-breaking performance were studied in detail. In addition, high-temperature/high-pressure displacement experiments were conducted to evaluate the temporary plugging performance of the gel containing the encapsulated breaker in fractured cores and packed-sand tubes. The results showed that the prepared capsules had good sphericity and a dense shell structure, with an encapsulation efficiency of 76.7%. The capsules exhibited temperature resistance up to 150 °C and favorable sustained-release characteristics. The UF-EC/SA breaker showed good compatibility with the polymer gel and did not inhibit gelation within the temperature range of 80–150 °C or at dosages of 0–16 wt.%. The gel maintained good mechanical strength even in highly mineralized brines. At 150 °C and a capsule dosage of 16 wt.%, the gel was completely broken within 2.5 d; the residue concentration was only 351 mg/L, and the residue size was mainly distributed within 100–500 μm. The high-temperature/high-pressure displacement tests demonstrated that the gel containing 16 wt.% capsules achieved a maximum breakthrough pressure of 5.16 MPa in a 3 mm wedge-shaped fracture core, and the pressure remained stable for 5 d. After gel breaking, the residue could be readily flowed back, indicating excellent synergy between temporary plugging and subsequent gel breaking. Therefore, the UF-EC/SA encapsulated breaker provides a new technical option for efficient gel breaking in high-temperature fractured formations. Full article

With an increased number of chronic wounds and accidents worldwide, the need for advanced wound care approaches has been urgent. In this regard, sprayable hydrogel dressings have emerged as an innovative biomaterial due to their unique rheological properties, minimally invasive operation capabilities, excellent adaptability to irregular surfaces, and in situ rapid gelation. This review focused on elaborating the main materials used to construct sprayable hydrogels, including natural polymers and synthetic polymers, and discussing their respective molecular structures, physicochemical properties, advantages, and challenges in formulation design. This review also explored the properties of sprayable hydrogels, including sprayability, adhesion performance, mechanical strength, moisture absorption, breathability, biocompatibility, and degradability. The mechanisms of their controllable gelation through chemical crosslinking and physical crosslinking strategies were analyzed. Subsequently, the applications of sprayable hydrogels in wound areas, including diabetic wounds, infected wounds, postoperative adhesions, burn wounds, and joint wounds, were comprehensively reviewed. The challenges and future developments in wound healing were clarified to provide valuable references for promoting interdisciplinary research and the clinical translation of sprayable hydrogels. Full article

This study examines the influence of scale effects on the thermomechanical and structural performance of chemically cured, glass-fibre-reinforced polyester composites. Two reinforcement architectures—plain 0/90° fabric and biaxial fabric—were analysed to assess differences in resin flow, curing behaviour, and mechanical characteristics. Differential Scanning Calorimetry (DSC) was employed to characterise cross-linking kinetics at 15 °C, 19 °C, and 25 °C, demonstrating that higher cure temperatures markedly accelerate gelation and cross-linking. Composite plates were manufactured by Light Resin Transfer Moulding (L-RTM), and static tensile tests were conducted in accordance with PN-EN ISO 527-4. The results confirm that reinforcement architecture strongly affects processability and mechanical performance. The 0/90° fabric provided superior resin permeability and shorter infusion times, whereas the biaxial fabric required higher injection pressure and exhibited longer curing duration. Statistical analysis based on Weibull’s brittle strength theory verified the presence of scale effects: larger specimens displayed lower nominal strength due to a higher probability of internal flaws. Multiple regression modelling further revealed relationships between geometric and mechanical parameters: maximum (destructive) stress, Rm, was the dominant factor influencing both specimen thickness and number of layers, while deformation at maximum stress (εm) primarily determined specimen length. These findings highlight the necessity of accounting for size-dependent behaviour when designing and testing polymer composites. Considering scale effects enables more reliable extrapolation from laboratory-scale tests to full-scale components, thereby improving predictability and structural reliability in engineering applications. Full article

Silk fibroin (SF)–polyphenol systems have emerged as a versatile class of gels and hydrogels in which supramolecular interactions and dynamic crosslinking regulate network formation, responsiveness, and multifunctional performance. Polyphenols interact with SF through hydrogen bonding, hydrophobic interactions, π–π stacking, metal coordination, and covalent crosslinking, thereby modulating conformational transitions, gelation behavior, structural stability, and interfacial functionality. These interaction mechanisms enable the development of SF–polyphenol gel systems with tunable mechanical properties, wet adhesion, antioxidant activity, self-healing capability, and stimuli responsiveness. This review summarizes recent advances in SF–polyphenol gels and hydrogels, with particular emphasis on molecular interaction mechanisms, gelation and fabrication strategies, responsive behaviors, and structure–property relationships. Representative preparation approaches, including solution blending, electrospinning, impregnation–adsorption, enzymatic crosslinking, metal–phenolic coordination, and photo-initiated processing, are systematically discussed in relation to their effects on network architecture and functional output. The responsive behaviors of these systems under pH, redox, electrical, thermal, and optical stimuli are also analyzed from the perspective of dynamic gel networks and adaptive material design. Emerging applications of SF–polyphenol gels in bioadhesives, delivery platforms, flexible bioelectronics, wound-related materials, and sustainable functional systems are highlighted. Current limitations associated with polyphenol instability, formulation sensitivity, reproducibility, and scale-up are critically discussed, together with future opportunities for predictive design of gel-based natural polymer systems. This review provides a comprehensive framework for understanding SF–polyphenol gelation and for guiding the development of next-generation multifunctional gels and hydrogels. Full article

Chlorogenic acid (CGA) is a natural polyphenol with various biological activities, but its poor stability and premature release in the gastrointestinal tract limit oral application. Herein, a pH-responsive bilayer hydrogel based on sodium alginate (SA) and carboxymethyl cellulose (CMC) was developed to enhance the gastrointestinal stability and controlled release of CGA. CGA-loaded SA hydrogels were prepared via Ca²⁺-induced ionotropic gelation, followed by CMC coating to form a bilayer structure. The SA/CMC hydrogels showed a drug loading capacity of 15.2–16.7% and pH-dependent swelling behavior. In vitro release studies revealed that the bilayer hydrogel suppressed CGA release in simulated gastric fluid (pH 1.2), with a cumulative release of approximately 30%, while enabling sustained release in simulated intestinal fluid (pH 6.8), reaching about 70% within 10 h. Release kinetics indicated that CGA release was controlled by Fickian diffusion under acidic conditions and by a diffusion-polymer relaxation mechanism under intestinal conditions. Moreover, encapsulation in the SA/CMC hydrogel improved the thermal, light, and pH stability of CGA while maintaining its antioxidant activity and biocompatibility. These results indicate that SA/CMC bilayer hydrogels provide a promising strategy for stabilized gastrointestinal delivery of chlorogenic acid. Full article

Polymer gel profile control technology can effectively modify water flow channels in water-flooded oil reservoirs and enhance oil recovery. However, most polymer gel systems exhibit poor performance, such as low strength, not suitable for high-temperature and high-salinity reservoir conditions, leading to ineffective water shutoff. To address this challenge in complex formations of high-temperature, high-salinity fractured reservoirs, a temperature- and salt-tolerant polymer gel system with delayed crosslinking was developed based on the concept of slow hydrogen-bond crosslinking. Laboratory evaluations demonstrated that a gel system formulated with 0.4 wt% HPAM and 0.2 wt% PEI (HPAM/PEI) achieved a gel strength grade of G index. Even at 100 °C or a salinity of 200,000 ppm, the HPAM/PEI system maintained a gel strength grade of F, indicating excellent temperature resistance and shear stability. The slow hydrogen-bond crosslinking mechanism endowed the system with delayed gelation characteristics. Sandpack and core flooding experiments confirmed that the HPAM/PEI system could form high-strength gels in situ with low polymer retention. After treatment, the permeability of the core was reduced by over 99%, and the effective blocking duration exceeded 12 months. This study provides a theoretical foundation for applying the HPAM/PEI gel system in deep profile control and water shutoff in high-temperature and high-salinity reservoirs. Full article

Corneal defects are a major cause of vision loss and require rapid, biocompatible, and effective sealing methods to restore ocular integrity and prevent infection. Current clinical adhesives, such as cyanoacrylate and fibrin glue, are limited by problems such as poor biocompatibility and inadequate stability. This study presents the design and evaluation of a fast-curable polymer bioadhesive hydrogel, a corneal glue formulated for efficient sealing of corneal defects. Hydrogels were synthesized from natural and synthetic polymers, including polyvinyl alcohol (PVA), sodium alginate (SA), and carboxymethyl cellulose (CMC), optimized for rapid gelation (~45 s), robust adhesion (~15 kPa), and mechanical strength (tensile strength ~0.35 MPa and storage modulus G′ indicating strong elastic behavior). Physicochemical and rheological properties, including swelling behavior and optical transparency (>90% transmittance across 400–700 nm), were characterized, including gelation time, swelling behavior, and mechanical strength. In vitro biocompatibility was assessed using human corneal epithelial cells to evaluate cytotoxicity and cell adhesion. Ex vivo studies on human cadaveric corneas with full-thickness defects measured adhesive strength and sealing efficacy through burst pressure (~38 mmHg) and leakage tests, with comparisons to commercial fibrin and cyanoacrylate adhesives. The optimized corneal glue exhibited fast curing, robust adhesion, high water retention with minimal swelling, favorable viscoelastic properties, and excellent cytocompatibility effectively sealing corneal defects in ex vivo models. These results highlight its potential as a promising fast-curable bioadhesive for corneal wound repair and ocular surface restoration. Full article

Low-molecular-weight gelators (LMWGs) have attracted growing attention as versatile alternatives to conventional polymeric thickeners and gelators, owing to their ability to form three-dimensional fibrillar networks through non-covalent self-assembly and to undergo reversible sol–gel transitions in response to external stimuli. Among the various stimuli that can be exploited, pH represents a particularly attractive trigger given its direct relevance to biological and physiological environments. This review focuses on three categories of pH-responsive LMWGs that have shown notable progress over the past decade yet remain relatively underexplored in the literature. First, N-oxide-type hydrogelators are discussed, with emphasis on amide amine oxide-based surfactants and pyridine-N-oxide frameworks. The pH-dependent protonation of the N-oxide moiety modulates intermolecular hydrogen bonding, thereby governing self-assembly and gel formation. The structural versatility of these gelators enables rational tuning of aggregate morphology and confers clear pH and temperature responsiveness. Second, recent advances in phenylboronic acid-based LMWGs are highlighted. Although boronic acid derivatives have long been studied as dynamic crosslinking units in polymeric hydrogels, 3-isobutoxyphenylboronic acid was recently identified as the first example of phenylboronic acid functioning as an LMWG, in which gelation is driven primarily by hydrogen bonding and pH responsiveness is exploited for stimuli-triggered gel disruption rather than gel formation. Third, pH-responsive orthogonal self-assembly systems are reviewed. Representative examples include multicomponent hybrid hydrogels combining pH-activated LMWGs with polymer gelators for controlled drug release, pH-triggered self-sorting of two LMWGs without any polymeric component, and bio-based orthogonal hydrogels composed of a glucolipid LMWG and cellulose nanocrystals. For each system, both advantages and remaining limitations are critically assessed. Collectively, this review aims to provide a timely overview of emerging trends in pH-responsive LMWG research and to offer perspectives on the rational design of next-generation stimuli-responsive soft materials. Full article

Hydrogels constructed from natural biomacromolecules with multifunctional properties, such as improved mechanical strength, ionic stability, biocompatibility, and ionic conductivity, are highly desirable for advanced food and biomedical applications, yet remain challenging to design. Although alginate is one of the most widely used hydrogel-forming polysaccharides due to its biocompatibility and gelation ability, its intrinsic limitations often hinder the development of hydrogels with fully optimized performance. This review provides a systematic comparison of alginate-based composite hydrogels formed with complementary biopolymers, including whey proteins, gelatin, pectin, starch, and chitosan, focusing on their synergistic effects on structural, mechanical, and functional properties. Recent studies are critically analyzed to elucidate how polymer–polymer interactions influence gel network formation, environmental ionic stability, and encapsulation performance. Particular attention is given to fabrication strategies and formulation parameters that enhance the immobilization and controlled release of probiotics, vitamins, polyphenols, and other bioactive compounds. By integrating current knowledge on structure–function relationships and processing approaches, this review offers practical design guidelines for the development of multifunctional alginate-based hydrogel systems for applications in functional foods and nutraceutical delivery. Full article

Hydrogels have emerged as promising functional materials for improving water management and nutrient delivery in agriculture, particularly under conditions of increasing water scarcity and declining soil fertility. However, most commercially available superabsorbent hydrogels are based on petroleum-derived polymers, raising concerns regarding their persistence in soils, potential microplastic formation and long-term environmental impact. In response, significant research efforts are being directed toward the development of biodegradable hydrogels derived from renewable biopolymers. This review provides a critical overview of recent advances in hydrogel systems designed for agricultural applications, with a particular focus on biopolymer-based materials. First, the current landscape of hydrogel technologies used as soil conditioners and controlled-release systems for agrochemicals is contextualized, highlighting the limitations of conventional synthetic hydrogels. Subsequently, the main classes of natural polymers explored for hydrogel fabrication, including polysaccharides (e.g., chitosan, alginate, cellulose and starch) and proteins (e.g., gelatin, keratin and soy protein), are analyzed in terms of raw material sources, gelation mechanisms and structure–property relationships. Their performance in key agricultural functions, such as water retention, controlled nutrient release, soil conditioning and enhancement of plant growth, is also discussed. Finally, the review identifies major challenges that currently hinder large-scale implementation, including mechanical stability, degradation behavior in complex soil environments, nutrient release control and economic scalability. By integrating recent progress and outlining emerging research directions, this work aims to support the rational design of next-generation biodegradable hydrogels capable of contributing to sustainable agriculture and circular bioeconomy strategies. Full article