Gels, Volume 10, Issue 7 (July 2024) – 18 articles

Phosphorous (P) is one the most important elements in several biological cycles, and is a fundamental component of soil, plants and living organisms. P has a low mobility and is quickly adsorbed on clayey soils, limiting its availability and absorption by plants. Here, biodegradable hydrogels based on Cassava starch crosslinked with citric acid (CA) were made and loaded with KH₂PO₄ and phosphorite to promote the slow release of phosphorus, the storing of water, and the reduction in P requirements during fertilization operations. Crosslinking as a function of CA concentrations was investigated by ATR-FTIR and TGA. The water absorption capacity (WAC) and P release, under different humic acid concentration regimens, were studied by in vitro tests. It is concluded that hydrogel formed from 10% w/w of CA showed the lowest WAC because of a high crosslinking degree. Hydrogel containing 10% w/w of phosphorite was shown to be useful to encouraging the slow release of P, its release behavior being fitted to the Higuchi kinetics model. In addition, P release increased as humic acid contents were increased. These findings suggest that these hydrogels could be used for encouraging P slow release during crop production. Full article

Articular cartilage is an avascular tissue with very limited capacity of self-regeneration. Trauma or injury-related defects, inflammation, or aging in articular cartilage can induce progressive degenerative joint diseases such as osteoarthritis. There are significant clinical demands for the development of effective therapeutic approaches to promote articular cartilage repair or regeneration. The current treatment modalities used for the repair of cartilage lesions mainly include cell-based therapy, small molecules, surgical approaches, and tissue engineering. However, these approaches remain unsatisfactory. With the advent of three-dimensional (3D) bioprinting technology, tissue engineering provides an opportunity to repair articular cartilage defects or degeneration through the construction of organized, living structures composed of biomaterials, chondrogenic cells, and bioactive factors. The bioprinted cartilage-like structures can mimic native articular cartilage, as opposed to traditional approaches, by allowing excellent control of chondrogenic cell distribution and the modulation of biomechanical and biochemical properties with high precision. This review focuses on various hydrogels, including natural and synthetic hydrogels, and their current developments as bioinks in 3D bioprinting for cartilage tissue engineering. In addition, the challenges and prospects of these hydrogels in cartilage tissue engineering applications are also discussed. Full article

Injectable hydrogels show great promise for bone tissue engineering applications due to their high biocompatibility and drug delivery capabilities. The bone defects in osteoporosis are usually characterized by an oxidative and inflammatory microenvironment that impairs the regeneration capability of bone tissues. To attenuate the reactive oxygen species (ROS) and promote bone regeneration, an anti-oxidative hydrogel with osteogenic capacity was developed in this study. The poorly water soluble, natural antioxidant, resveratrol, was encapsulated in thiolated Pluronic F-127 micelles with over 50-times-enhanced solubility. The injectable hydrogel was facilely formed because of the new thioester bond between the free thiol group in modified F-127 and the arylate group in hyaluronic acid (HA)–acrylate. The resveratrol-loaded hydrogel showed good viscoelastic properties and in vitro stability and was cyto-compatible with bone-marrow-derived mesenchymal stem cells (BMSCs). The hydrogel allowed for a sustained release of resveratrol for at least two weeks and effectively enhanced the osteogenic differentiation of BMSCs by the up-regulation of osteogenic markers, including ALP, OCN, RUNX-2, and COL1. Moreover, the hydrogel exhibited anti-oxidative and anti-inflammatory abilities through the scavenging of intracellular ROS in RAW264.7 cells and inhibiting the gene expression and secretion of pro-inflammatory cytokines TNF-α and IL-1β under LPS exposure. In summary, the results suggest that our multifunctional hydrogel loaded with resveratrol bearing osteogenic, anti-oxidative, and anti-inflammatory actions is easily prepared and represents a promising resveratrol delivery platform for the repair of osteoporotic bone defects. Full article

This study describes the development of hydrogel formulations with ionic crosslinking capacity and photocatalytic characteristics. The objective of this research is to provide an effective, accessible, “green”, and facile route for the decontamination of chemical warfare agents (CWAs, namely the blistering agent—mustard gas/sulfur mustard (HD)) from contaminated surfaces, by decomposition and entrapment of CWAs and their degradation products inside the hydrogel films generated “on-site”. The decontamination of the notorious warfare agent HD was successfully achieved through a dual hydrolytic–photocatalytic degradation process. Subsequently, the post-decontamination residues were encapsulated within a hydrogel membrane film produced via an ionic crosslinking mechanism. Polyvinyl alcohol (PVA) and sodium alginate (ALG) are the primary constituents of the decontaminating formulations. These polymeric components were chosen for this application due to their cost-effectiveness, versatility, and their ability to form hydrogen bonds, facilitating hydrogel formation. In the presence of divalent metallic ions, ALG undergoes ionic crosslinking, resulting in rapid gelation. This facilitated prompt PVA-ALG film curing and allowed for immediate decontamination of targeted surfaces. Additionally, bentonite nanoclay, titanium nanoparticles, and a tetrasulfonated nickel phthalocyanine (NiPc) derivative were incorporated into the formulations to enhance absorption capacity, improve mechanical properties, and confer photocatalytic activity to the hydrogels obtained via Zn²⁺—mediated ionic crosslinking. The resulting hydrogels underwent characterization using a variety of analytical techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscometry, and mechanical analysis (shear, tensile, and compression tests), as well as swelling investigations, to establish the optimal formulations for CWA decontamination applications. The introduction of the fillers led to an increase in the maximum strain up to 0.14 MPa (maximum tensile resistance) and 0.39 MPa (maximum compressive stress). The UV-Vis characterization of the hydrogels allowed the determination of the band-gap value and absorption domain. A gas chromatography–mass spectrometry assay was employed to evaluate the decontamination efficacy for a chemical warfare agent (sulfur mustard—HD) and confirmed that the ionic crosslinked hydrogel films achieved decontamination efficiencies of up to 92.3%. Furthermore, the presence of the photocatalytic species can facilitate the degradation of up to 90% of the HD removed from the surface and entrapped inside the hydrogel matrix, which renders the post-decontamination residue significantly less dangerous. Full article

A comprehensive study was performed on the supramolecular ordering and optical properties of thin nanostructured glycerohydrogel sol-gel plates based on chitosan L- and D-aspartate and their individual components in the X-ray, UV, visible, and IR ranges. Our comparative analysis of chiroptical characteristics, optical collimated transmittance, the average cosine of the scattering angle, microrelief and surface asymmetry, and the level of structuring shows a significant influence of the wavelength range of electromagnetic radiation and the enantiomeric form of aspartic acid on the functional characteristics of the sol-gel materials. At the macrolevel of the supramolecular organization, a complex topography of the surface layer and a dense amorphous–crystalline ordering of polymeric substances were revealed, while at the nanolevel, there were two forms of voluminous scattering domains: nanospheres with diameters of 60–120 nm (L-) and 45–55 nm (D-), anisometric particles of lengths within ~100–160 (L-) and ~85–125 nm (D-), and widths within ~10–20 (L-) and ~20–30 nm (D-). The effect of optical clearing on glass coated with a thin layer of chitosan L-(D-)aspartate in the near-UV region was discovered (observed for the first time for chitosan-based materials). The resulting nanocomposite shape-stable glycerohydrogels seem promising for sensorics and photonics. Full article

Motivated by the enormous potential of hydrogels in regenerative medicine, new biocompatible gelatin-based hybrid hydrogels were developed through a green process using poly(ethylene glycol) diglycidyl ether as a cross-linking agent, adding carrageenan and chitosan polysaccharides to the network to better mimic the hybrid composition of native extracellular matrix. Overall, the hydrogels show suitable structural stability, high porosity and pore interconnectivity, good swellability, and finally, biocompatibility. Their mechanical behavior, investigated by tensile and compression tests, appears to be characterized by nonlinear elasticity with high compliance values, fast stress-relaxation, and good strain reversibility with no sign of mechanical failure for compressive loading–unloading cycles at relatively high deformation levels of 50%. Degradation tests confirm the hydrogel bioresorbability by gradual hydrolysis, during which the structural integrity of both materials is maintained, while their mechanical behavior becomes more and more compliant. Human Umbilical Cord-derived Mesenchymal Stem Cells (hUC-MSCs) were used to test the hydrogels as potential carriers for cell delivery in tissue engineering. hUC-MSCs cultured inside the hydrogels show a homogenous distribution and maintain their growth and viability for at least 21 days of culture, with an increasing proliferation trend. Hence, this study contributes to a further understanding of the potential use of hybrid hydrogels and hUC-MSCs for a wide range of biomedical applications, particularly in soft tissue engineering. Full article

The objective of this study was to develop a food 3D printing gel and investigate the effects of whey protein isolate (WPI), sodium alginate (SA), and water-bath heating time on the 3D printing performance of the gel. Initially, the influence of these three factors on the rheological properties of the gel was examined to determine the suitable formulation ranges for 3D printing. Subsequently, the formulation was optimized using response surface methodology, and texture analysis, scanning electron microscopy (SEM), and Fourier-transform infrared (FTIR) spectroscopy were conducted. The rheological results indicated that gels with WPI concentrations of 6–7 g, SA concentrations of 0.8–1.2 g, and water-bath heating times of 10–12 min exhibited lower yield stress and better self-supporting properties. The optimized formulation, determined through response surface methodology, consisted of 1.2 g SA, 6.5 g WPI, and a heating time of 12 min. This optimized formulation demonstrated enhanced extrusion capability and superior printing performance. SEM analysis revealed that the optimized gel possessed good mechanical strength, and FTIR spectroscopy confirmed the successful composite formation of the gel. Overall, the results indicate that the optimized gel formulation can be successfully printed and exhibits excellent 3D printing performance. Full article

Hydrogels based on biocompatible polysaccharides with biological activity that can slowly release an active principle at the wound site represent promising alternatives to traditional wound dressing materials. In this respect, new hydrogels based on curdlan derivative with 2-hydroxypropyl dimethyl octyl ammonium groups (QCurd) and native curdlan (Curd) were obtained at room temperature by covalent cross-linking using a diepoxy cross-linking agent. The chemical structure of the QCurd/Curd hydrogels was investigated by Fourier transform infrared spectroscopy (FTIR) spectroscopy. Scanning electron microscopy (SEM) revealed well-defined regulated pores with an average diameter between 50 and 75 μm, and hydrophobic micro-domains of about 5 μm on the pore walls. The high swelling rate (21–24 g_water/g_hydrogel) and low elastic modulus values (7–14 kPa) make them ideal for medical applications as wound dressings. To evaluate the possible use of the curdlan-based hydrogels as active dressings, the loading capacity and release kinetics of diclofenac, taken as a model drug, were studied under simulated physiological skin conditions. Several mathematical models have been applied to evaluate drug transport processes and to calculate the diffusion coefficients. The prepared QCurd/Curd hydrogels were found to have good antibacterial properties, showing a bacteriostatic effect after 48 h against S. aureus, MRSA, E. coli, and P. aeruginosa. The retarded drug delivery and antimicrobial properties of the new hydrogels support our hypothesis that they are candidates for the manufacture of wound dressings. Full article

Functional articular cartilage regeneration remains an unmet medical challenge, increasing the interest for innovative biomaterial-based tissue engineering (TE) strategies. Hydrogels, 3D macromolecular networks with hydrophilic groups, present articular cartilage-like features such as high water content and load-bearing capacity. In this study, 3D porous polyethylene glycol diacrylate (PEGDA) hydrogels were fabricated combining the gas foaming technique and a UV-based crosslinking strategy. The 3D porous PEGDA hydrogels were characterized in terms of their physical, structural and mechanical properties. Our results showed that the size of the hydrogel pores can be modulated by varying the initiator concentration. In vitro cytotoxicity tests showed that 3D porous PEGDA hydrogels presented high biocompatibility both with human chondrocytes and osteoblast-like cells. Importantly, the 3D porous PEGDA hydrogels supported the viability and chondrogenic differentiation of human bone marrow-derived mesenchymal stem/stromal cell (hBM-MSC)-based spheroids as demonstrated by the positive staining of typical cartilage extracellular matrix (ECM) (glycosaminoglycans (GAGs)) and upregulation of chondrogenesis marker genes. Overall, the produced 3D porous PEGDA hydrogels presented cartilage-like mechanical properties and supported MSC spheroid chondrogenesis, highlighting their potential as suitable scaffolds for cartilage TE or disease modelling strategies. Full article

Numerous studies report on chitosan hydrogels in different forms, such as films, porous structures, nanoparticles, and microspheres, for biomedical applications; however, this study concentrates on their modifications with different crosslinking agents and observes their effects on drug loading and releasing capacities. Linear chitosan, along with chitosans crosslinked with two major crosslinkers, i.e., genipin and disulfide, are used to formulate three different hydrogel systems. The crosslinking process is heavily impacted by temperature and pH conditions. Three different drugs, i.e., thymoquinone, gefitinib, and erlotinib, are loaded to the hydrogels in de-ionized water solutions and released in phosphate-buffered solutions; thus, a total of nine combinations are studied and analyzed for their drug loading and releasing capabilities with ultraviolet–visible (UV–Vis) spectroscopy. This study finds that thymoquinone shows the lowest loading efficacy compared to the two other drugs in all three systems. Gefitinib shows stable loading and releasing regardless of crosslinking system, and the genipin-crosslinked system shows stable loading and releasing with all three drug molecules. These experimental results agree well with the findings of our previously published results conducted with molecular dynamics simulations. Full article

In this work, the effect of sonication on the molecular characteristics of polyacrylic acid (Carbopol^® Ultrez 10), as well as on its rheological behavior in aqueous dispersions and microgels, was analyzed for the first time by rheometry, weight-average molecular weight (M_w) measurements via static light scattering (SLS), Fourier transform infrared (FTIR) spectroscopy and confocal microscopy. For this, the precursor dispersion and the microgels containing 0.25 wt.% of Ultrez 10 were sonicated in a commercial ultrasound bath at constant power and at different times. The main rheological properties of the microgel, namely, shear modulus, yield stress and viscosity, all decreased with increasing sonication time, while the microgel’s Herschel–Bulkley (H-B) behavior, without thixotropy, was preserved. Also, M_w of Ultrez 10 decreased up to almost one-third (109,212 g/mol) of its original value (300,860 g/mol) after 180 min of sonication. These results evidence a softening of the gel microstructure, which results from the reduction in the M_w of polyacrylic acid with sonication time. Separately, FTIR measurements show that sonication produces scission in the C-C links of the Carbopol^® backbone, which results in chains with the same chemistry but lower molecular weight. Finally, confocal microscopy observations revealed a diminution of the size of the microsponge domains and more free solvent with sonication time, which is reflected in a less compact and softer microstructure. The present results indicate that both the microstructure and the rheological behavior of Carbopol^® microgels, in particular, and complex fluids, in general, may be manipulated or tailored by systematic high-power ultrasonication. Full article

Hydrogels are materials made of crosslinked 3D networks of hydrophilic polymer chains that can absorb and retain significant amounts of water due to their hydrophilic structure without being dissolved. In relation to alternative biomaterials, hydrogels offer increased biocompatibility and biodegradability, giving them distinct advantages. Thus, hydrogel platforms are considered to have the potential for the development of biomedical applications. In this study, the main objective was the development of hybrid hydrogels to act as a drug delivery platform. These hydrogels were made from chitosan (CH) and type A gelatin (G), two natural polymers that provide a supportive environment for cellular attachment, viability, and growth, thanks to their unique properties. Particularly, the use of gelatins for drug delivery systems provides biodegradability, biocompatibility, and non-toxicity, which are excellent properties to be used in the human body. However, gelatins have some limitations, such as thermal instability and poor mechanical properties. In order to improve those properties, the aim of this work was the development and characterization of hybrid hydrogels with different ratios of CH–G (100–0, 75–25, 50–50, 25–75, 0–100). Hydrogels were characterized through multiple techniques, including Fourier transform infrared (FTIR) spectroscopy, rheological and microstructural studies, among others. Moreover, a model hydrophilic drug molecule (tetracycline) was incorporated to evaluate the feasibility of this platform to sustain the release of hydrophilic drugs, by being tested in a solution of Phosphate Buffer Solution at a pH of 7.2 and at 37 °C. The results revealed that the synergy between chitosan and type A gelatin improved the mechanical properties as well as the thermal stability of it, revealing that the best ratios of the biopolymers are 50–50 CH–G and 75–25 CH–G. Thereby, these systems were evaluated in a controlled release of tetracycline, showing a controlled drug delivery of 6 h and highlighting their promising application as a platform for controlled drug release. Full article

With the emphasis placed by society on environmental resources, current petroleum-based packaging in the food industry can no longer meet people’s needs. However, new active packaging technologies have emerged, such as proteins, polysaccharides, and lipids, in which proteins are widely used for their outstanding gel film-forming properties. Most of the current literature focuses on research applications of single protein-based films. In this paper, we review the novel protein-based packaging technologies that have been used in recent years to categorize different proteins, including plant proteins (soybean protein isolate, zein, gluten protein) and animal proteins (whey protein isolate, casein, collagen, gelatin). The advances that have recently been made in protein-based active packaging technology can be understood by describing protein sources, gel properties, molding principles, and applied research. This paper presents the current problems and prospects of active packaging technology, provides new ideas for the development of new types of packaging and the expansion of gel applications in the future, and promotes the development and innovation of environmentally friendly food packaging. Full article

To reduce the risk of the adsorption of granular activated carbon in the gastrointestinal tract, we successfully produced a hollow-type spherical bacterial cellulose (HSBC) gel containing activated carbon with a particle size of 6 μm. In this study, the aim of which was to develop an effective formulation, we evaluated the stability of activated-carbon-encapsulating HSBC gels under various pH conditions. Activated-carbon-encapsulating HSBC gels (ACEGs) retained the activated carbon without leaking when subjected to agitation in acidic or basic environments. The saturated adsorption amount, calculated using the Langmuir adsorption isotherm, was affected by the target adsorbate and pH conditions. These results indicate that ACEGs can adsorb uremic toxins and their precursors similarly to conventional uremic toxin adsorbents while preventing direct contact between the encapsulated activated carbon and the gastrointestinal tract. Compared to powdered activated carbon, the ACEG is less likely to be adsorbed in the gastrointestinal tract. Therefore, the proposed ACEG is a promising new formulation that will contribute to the treatment of renal failure and improve patients’ compliance with medication. Full article

Plasticized polyvinyl chloride (PVC) gel has large deformation under an applied external electrical field and high driving stability in air and is a candidate artificial muscle material for manufacturing a flexible actuator. A porous PVC gel actuator consists of a mesh positive pole, a planar negative pole, and a PVC gel core layer. The current casting method is only suitable for manufacturing simple 2D structures, and it is difficult to produce multilayer porous structures. This study investigated the feasibility of a 3D-printed carbon nanotube-doped silicone electrode for manufacturing multilayer porous PVC gel artificial muscle. Carbon nanotube-doped silicone (CNT-PDMS) composite inks were developed for printing electrode layers of PVC gel artificial muscles. The parameters for the printing plane and mesh electrodes were explored theoretically and experimentally. We produced a CNT-PDMS electrode and PVC gel via integrated printing to manufacture multilayer porous PVC artificial muscle and verified its good performance. Full article

The preparation of conducting polymer aerogels is an effective strategy to produce innovative materials with enhanced physicochemical properties. Herein, polypyrrole (PPy) aerogels were oxidatively prepared in the presence of tannic acid (TA) with different concentrations (2.5, 5, and 10% mole ratio to pyrrole monomer) under freezing conditions. Nanofibrillated cellulose (NFC) was added during the PPy/TA synthesis to enhance mechanical stability. The effect of TA concentration on the aerogels’ morphology, conductivity, thermal stability, and adsorption capacity was investigated. The conductivity of 9.6 ± 1.7 S cm⁻¹ was achieved for PPy/TA prepared with 2.5% TA, which decreased to 0.07 ± 0.01 S cm⁻¹ when 10% TA was used. PPy/TA aerogels have shown high efficacy in removing Cr(VI) ions from aqueous solutions. Adsorption experiments revealed that all the aerogels follow pseudo-second-order kinetics. PPy/TA prepared with NFC has a maximum adsorption capacity of 549.5 mg g⁻¹. Full article

Hydrogels, composed of hydrophilic homopolymer or copolymer networks, have structures similar to natural living tissues, making them ideal for applications in drug delivery, tissue engineering, and biosensors. Since Wichterle and Lim first synthesized hydrogels in 1960, extensive research has led to various types with unique features. Responsive hydrogels, which undergo reversible structural changes when exposed to stimuli like temperature, pH, or specific molecules, are particularly promising. Temperature-sensitive hydrogels, which mimic biological processes, are the most studied, with poly(N-isopropylacrylamide) (PNIPAm) being prominent due to its lower critical solution temperature of around 32 °C. Additionally, pH-responsive hydrogels, composed of polyelectrolytes, change their structure in response to pH variations. Despite their potential, conventional hydrogels often lack mechanical strength. The double-network (DN) hydrogel approach, introduced by Gong in 2003, significantly enhanced mechanical properties, leading to innovations like shape-deformable DN hydrogels, organic/inorganic composites, and flexible display devices. These advancements highlight the potential of hydrogels in diverse fields requiring precise and adaptable material performance. In this review, we focus on advancements in the field of responsive acrylamide-based hydrogels with IPN structures, emphasizing the recent research on DN hydrogels. Full article