Enhancing Alginate Hydrogels as Possible Wound-Healing Patches: The Synergistic Impact of Reduced Graphene Oxide and Tannins on Mechanical and Adhesive Properties.

Hydrogels are three-dimensional crosslinked materials known for their ability to absorb water, exhibit high flexibility, their biodegradability and biocompatibility, and their ability to mimic properties of different tissues in the body. However, their application is limited by inherent deficiencies in their mechanical properties. To address this issue, reduced graphene oxide (rGO) and tannins (TA) were incorporated into alginate hydrogels (Alg) to evaluate the impact of the concentration of these nanomaterials on mechanical and adhesive, as well as cytotoxicity and wound-healing properties. Tensile mechanical tests demonstrated improvements in tensile strength, elastic modulus, and toughness upon the incorporation of rGO and TA. Additionally, the inclusion of these materials allowed for a greater energy dissipation during continuous charge-discharge cycles. However, the samples did not exhibit self-recovery under environmental conditions. Adhesion was evaluated on pig skin, revealing that higher concentrations of rGO led to enhanced adhesion, while the concentration of TA did not significantly affect this property. Moreover, adhesion remained consistent after 10 adhesion cycles, and the contact time before the separation between the material and the surface did not affect this property. The materials were not cytotoxic and promoted healing in human fibroblast-model cells. Thus, an Alg/rGO/TA hydrogel with enhanced mechanical, adhesive, and wound-healing properties was successfully developed.

Design and Study of Novel Composites Based on EPDM Rubber Containing Bismuth (III) Oxide and Graphene Nanoplatelets for Gamma Radiation Shielding.

The mechanical, thermal and gamma radiation attenuation properties of ethylene-propylene-diene monomer (EPDM)-based composites containing graphene nanoplatelets (GNs) and bismuth (III) oxide nanoparticles (B) were investigated. The use of polyethylene glycol (PEG) as a compatibilizer to improve the dispersion of the fillers was also investigated. The results showed that the combined use of these fillers resulted in a drastic increase in mechanical properties, reaching 123% and 83% of tensile strength and elongation at break, respectively, compared to those of EPDM. In contrast, the addition of PEG to composites containing EPDM GNs and B resulted in composites with lower values of mechanical properties compared to the EPDM/B/GN-based composite. However, the presence of PEG leads to obtaining a composite (EPDM/B/GNP) with a mass attenuation coefficient to gamma radiation (137Cs, 662 keV) superior to that composite without PEG. In addition, the composite EPDM, B and PEG exhibited an elongation at break 153% superior to unfilled EPDM. Moreover, the binary filler system consisting of 100 phr of bismuth (III) oxide and 10 phr of GN leads to reaching 61% of the linear damping coefficient of the EPDM composite compared to that value of the unfilled EPDM. The study of the morphology and the state of filler dispersion in the polymer matrix, obtained using scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively, provides a useful background for understanding the factors affecting the gamma radiation attenuation properties. Finally, the results also indicated that by adjusting the formulation, it is possible to tune the mechanical and thermal properties of EPDM composites reinforced with bismuth oxide and graphene nanoplatelets.

Interactions of variants of human apolipoprotein A-I with biopolymeric model matrices. Effect of collagen and heparin.

BACKGROUND: The extracellular matrix (ECM) is a complex tridimensional scaffold that actively participates in physiological and pathological events. The objective of this study was to test whether structural proteins of the ECM and glycosaminoglycans (GAGs) may favor the retention of human apolipoprotein A-I (apoA-I) variants associated with amyloidosis and atherosclerosis. METHODS: Biopolymeric matrices containing collagen type I (Col, a main macromolecular component of the ECM) with or without heparin (Hep, a model of GAGs) were constructed and characterized, and used to compare the binding of apoA-I having the native sequence (Wt) or Arg173Pro, a natural variant inducing cardiac amyloidosis. Protein binding was observed by fluorescence microscopy and unbound proteins quantified by a colorimetric assay. RESULTS: Both, Wt and Arg173Pro bound to the scaffolds containing Col, but the presence of Hep diminished the binding efficiency. Col-Hep matrices retained Arg173Pro more than the Wt. The retained protein was only partially removed from the matrices with saline solutions, indicating that electrostatic interactions may occur but are not the main driving force. Using in addition thermodynamic molecular simulations and size exclusion chromatography approaches, we suggest that the binding of apoA-I variants to the biopolymeric matrices is driven by many low affinity interactions. CONCLUSIONS: Under this scenario Col-Hep scaffolds contribute to the binding of Arg173Pro, as a cooperative platform which could modify the native protein conformation affecting protein folding. GENERAL SIGNIFICANCE: We show that the composition of the ECM is key to the protein retention, and well characterized biosynthetic matrices offer an invaluable in vitro model to mimic the hallmark of pathologies with interstitial infiltration such as cardiac amyloidosis.

Cells immersed in collagen matrices show a decrease in plasma membrane fluidity as the matrix stiffness increases.

Cells are constantly adapting to maintain their identity in response to the surrounding media's temporal and spatial heterogeneity. The plasma membrane, which participates in the transduction of external signals, plays a crucial role in this adaptation. Studies suggest that nano and micrometer areas with different fluidities at the plasma membrane change their distribution in response to external mechanical signals. However, investigations linking fluidity domains with mechanical stimuli, specifically matrix stiffness, are still in progress. This report tests the hypothesis that the stiffness of the extracellular matrix can modify the equilibrium of areas with different order in the plasma membrane, resulting in changes in overall membrane fluidity distribution. We studied the effect of matrix stiffness on the distribution of membrane lipid domains in NIH-3 T3 cells immersed in matrices of varying concentrations of collagen type I, for 24 or 72 h. The stiffness and viscoelastic properties of the collagen matrices were characterized by rheometry, fiber sizes were measured by Scanning Electron Microscopy (SEM) and the volume occupied by the fibers by second harmonic generation imaging (SHG). Membrane fluidity was measured using the fluorescent dye LAURDAN and spectral phasor analysis. The results demonstrate that an increase in collagen stiffness alters the distribution of membrane fluidity, leading to an increasing amount of the LAURDAN fraction with a high degree of packing. These findings suggest that changes in the equilibrium of fluidity domains could represent a versatile and refined component of the signal transduction mechanism for cells to respond to the highly heterogeneous matrix structural composition. Overall, this study sheds light on the importance of the plasma membrane's role in adapting to the extracellular matrix's mechanical cues.

Impact of graphene oxide lateral dimensions on the properties of methacrylated gelatin nanocomposite hydrogels.

The size and shape of nanoparticles have a profound effect on the properties of nanocomposites. For instance, the lateral dimensions of graphene oxide (GO) platelets affect several properties, including their antibacterial and pharmacokinetic functions. However, the impact of lateral dimensions has been poorly studied in nanocomposites, and their effect on hydrogels is still unknown. The current study aims to determine the effect of GO lateral dimensions on the mechanical, rheological, thermal, and antibacterial properties of gelatin hydrogels. The hydrogels were fabricated via photopolymerization of methacrylated gelatin and GO derived from the oxidation of commercial graphene. The observations indicate that an increase in GO sheets improves the mechanical strength with an increase in compressive modulus and a low mechanical hysteresis (<10%). Furthermore, low mechanical energy is dissipated even after several deformation cycles. The nanocomposite hydrogels demonstrated bactericidal effects on two clinical strains with an extensively drug-resistant phenotype, primarily through contact. Additionally, an increment in lateral dimensions increased the bactericidal capacity of Gram-negative strains. Thus, the significant effect of the lateral dimensions of GO sheets on the properties of hydrogels is demonstrated.

Electrospun Poly(acrylic acid-co-4-styrene sulfonate) as Potential Drug-Eluting Scaffolds for Targeted Chemotherapeutic Delivery Systems on Gastric (AGS) and Breast (MDA-Mb-231) Cancer Cell Lines.

Potential drug-eluting scaffolds of electrospun poly(acrylic acid-co-styrene sulfonate) P(AA-co-SS) in clonogenic assays using tumorigenic gastric and ovarian cancer cells were tested in vitro. Electrospun polymer nanofiber (EPnF) meshes of PAA and PSSNa homo- and P(AA-co-SS) copolymer composed of 30:70, 50:50, 70:30 acrylic acid (AA) and sodium 4-styrene sulfonate (SSNa) units were performed by electrospinning (ES). The synthesis, structural and morphological characterization of all EPnF meshes were analyzed by optical and electron microscopy (SEM-EDS), infrared spectroscopy (FTIR), contact angle, and X-ray diffraction (XRD) measurements. This study shows that different ratio of AA and SSNa of monomers in P(AA-co-SS) EPnF play a crucial role in clonogenic in vitro assays. We found that 50:50 P(AA-co-SS) EPnF mesh loaded with antineoplastic drugs can be an excellent suppressor of growth-independent anchored capacities in vitro assays and a good subcutaneous drug delivery system for chemotherapeutic medication in vivo model for surgical resection procedures in cancer research.

Effect of low aspect ratio one-dimensional nanoparticles on properties of photocrosslinked alginate nanocomposite hydrogels.

One-dimensional nanoparticles such as fibers, wires, represent an exciting type of filler for obtaining nanocomposite hydrogels due to their high aspect ratio. Unlike continuous fibers, in composites with short fibers, stress transfer occurs not only at the cylindrical surface of the fiber but also at the fiber ends. This work aimed to study the influence of the length of low aspect ratio one-dimensional nanoparticles on the rheological, swelling and thermal properties of nanocomposite hydrogels. We synthesized nanocomposite hydrogels via photopolymerization of methacrylated alginate macromonomers and aluminum oxide nanoparticles, nanowires and nanofibers as fillers. The main difference between the nanoparticles lies in their length. Longer nanoparticles (nanofibers) provided a glassier structure and a more significant reinforcement to the hydrogel, for example, at the concentration of 0.5 wt% the complex modulus increased approximately 2-fold and 8-fold for nanowires and nanofibers, respectively. Similarly, the incorporation of nanofibers produced hydrogels with a lower swelling capacity (2.5-fold decrease), which was attributed to a more connected network structure due to the higher aspect ratio of the nanofibers. Finally, both nanoparticle types produced an increase in the activation energy of thermal degradation.

Antibiotics removal using a chitosan-based polyelectrolyte in conjunction with ultrafiltration membranes.

The emergence of antibiotics as pollutants in the environment is one of the worldwide concerns because the bacterial strains generate a threat to the aquatic ecosystem and human health. In this study, an alkylated chitosan polyelectrolyte (ChA-PE) was used in conjunction with ultrafiltration membranes to remove three commonly used antibiotics, including amoxicillin (AMX), tetracycline (TET), and ciprofloxacin (CIP), in aqueous systems. The removal study considered diverse experimental variables through two methods: washing (pH, ionic strength, polymer ratio, and antibiotic concentration) and enrichment (maximum retention capacity). The retention percentage reached 80% at a pH of 11.0 at different polymer/antibiotic molar ratios. The ChA-PE presented irreversibly bound antibiotic interaction values of 0.51, 0.74, and 0.92 for CIP, AMX, and TET, respectively, at a pH of 11, showing that the polymer presents stronger permanent interactions with AMX and TET. On the other hand, the ChA-PE presented maximum retention capacity values of 185.6, 420.2, and 632.8 mg g-1 for CIP, AMX, and TET, respectively, in accordance with the association efficiency percentage values of 73.54, 87.08, and 93.83% for CIP, AMX, and TET, respectively.

Tuning the softness of poly(2-hydroxyethyl methacrylate) nanocomposite hydrogels through the addition of PEG coated nanoparticles.

HYPOTHESIS: In nanocomposites, several factors govern the enhancement of properties when a nanofiller is added into a polymer matrix. Previously, our group have demonstrated that stabilizing nanoparticles improves the dispersion of nanoparticles in a hydrogel, but their effect on viscoelastic properties remain unclear. We hypothesized that coating the nanoparticles will block matrix-nanoparticle interactions, which would then affect the transfer of stress when the hydrogel is subjected to stress. EXPERIMENT: To this end, we investigated the effects that nanofillers coated with polyethylene glycol (PEG) of variable molar mass have on the properties of physical hydrogels made from poly(2-hydroxyethyl methacrylate). PEG with molar masses of 6, 20, and 35 kDa were used at different concentrations and the viscoelastic properties of the resulting hydrogels were studied and compared with control hydrogels with and without nanofillers. FINDINGS: The coated nanofiller resulted in enhanced dispersion stabilization as the molar mass and concentration of the PEG increased. However, there were noticeable changes in viscoelastic properties. In general, the nanocomposite hydrogels exhibited reduced shear modulus, greater creep, and more accentuated shear thinning behaviour. These effects were attributed to hindered matrix-nanoparticle interactions because of the PEG coating, an increased slippage of the PHEMA chains as well as a plasticizing effect.

Polyelectrolyte nanocomposite hydrogels filled with cationic and anionic clays.

Polyelectrolyte nanocomposite hydrogels (NHGs) were synthesized. NHGs were formed from a polymer matrix composed of a cationic, anionic, and alkylated chitosan polymer modified with vinyl groups (ChAV) to achieve greater crosslinking. Cationic and anionic clays montmorillonite and hydrotalcite, respectively, were used as nanofillers to introduce electrostatic interaction with the matrix. NHGs were obtained via in situ polymerization. The ChAV and NHGs were then characterized. Based on X-ray diffraction and transmission electron microscopy results, the morphology of the nanocomposite was generally intercalated with some nanocomposites showing exfoliation. Rheological studies revealed improvements in shear modulus of NHGs with respect to hydrogel without clay. Lower relaxation times were noted as the clay content increased and it was attributed to the interactions between the clay sheets and the polymer. In conclusion the rheological properties of the material are improved with the addition of clay and the interactions present with the polymer matrix.

Magnetic methacrylated gelatin-g-polyelectrolyte for methylene blue sorption.

The presence of organic dyes in wastewater is a problem of growing interest due to its effect on the environment and human health. The aim of this work was to obtain magnetic hydrogels of methacrylated gelatin-g-polyelectrolyte to be used for the removal of methylene blue (MB) used as a model contaminant dye. Grafted gelatins with two degrees of functionalization (48% and 76%) were obtained and subsequently crosslinked using 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS) and sodium 4-vinylbenzenesulfonate (SSNa) monomers. Magnetic nanoparticles were formed by an in situ precipitation method to easily remove the hydrogel from the adsorption medium. Our data show that the hydrogel with a low degree of methacrylation displayed a high degree of swelling and decreased stiffness due to its less connected polymer network. MB adsorption experiments showed that neither the low degree of methacrylation nor the presence of the aromatic group in the PSSNa polyelectrolyte generated an increase in the adsorption capacity of the hydrogel. However, a significant increase in the adsorption capacity was observed when dry hydrogels were combined compared to that of previously swollen hydrogel. The experimental data were non-linearly fitted to the pseudo-first and pseudo-second order models and in both cases, the highest q e values were obtained for the GelMA-HF/PAMPS and GelMA-LF/PAMPS hydrogels. The Freundlich isotherm model was the one with the best correlation with the data (r 2 > 0.9700). Higher k f values were obtained for the GelMA-HF/PAMPS and GelMA-LF/PAMPS hydrogels at 20 °C. The results obtained from this study demonstrated that magnetic polyelectrolyte-grafted gelatins are an efficient option for the removal of contaminant dyes from aqueous solutions.

Tetracycline removal by polyelectrolyte copolymers in conjunction with ultrafiltration membranes through liquid-phase polymer-based retention.

In this study, we used a liquid-phase polymer-based retention technique assisted by polyelectrolyte copolymers containing quaternary ammonium and sulfonate groups that are capable of removing the antibiotic tetracycline (TC) through electrostatic interactions. The polymers were synthesized using zwitterionic, anionic, and cationic monomers with the aim of obtaining copolymers with different charge balances at the ratios of 1:1, 2:1, and 1:2 (negative: positive). The parameters investigated for each copolymer included the pH, ionic strength, concentration of polymer, maximum retention capacity, and sorption-elution process at pH 11.0 and 3.0. The copolymers with a charge ratio of 1:2 achieved the highest retention (80.0%) at alkaline pH, while the copolymers with charge ratios of 2:1 and 1:1 exhibited the maximum retention (72.0%) at acidic pH. Based on these results, the pH and charge of the polyelectrolyte copolymers play important roles in the TC removal processes. Additionally, the maximum retention capacity (MRC) recorded was 731.2, 176.8, and 214.8 mg TC/g of copolymer in the first charge for the three copolymer polyelectrolytes, and the second charge of the MRC process did not improve compared with the first load.

Copolymer-hydrous zirconium oxide hybrid microspheres for arsenic sorption.

In this work, a hybrid organic-inorganic adsorbent based on polyelectrolyte copolymers of poly(4-vinylbenzyl trimethylammonium chloride-co-2-hydroxyethyl methacrylate) microspheres mixed with a hydrous zirconium oxide phase were applied to remove arsenic species from aqueous solutions. The hybrid adsorbent was synthesized in a two-step procedure: first, the polymeric microspheres were obtained through emulsion radical copolymerization, and then, the microspheres were impregnated with a zirconium oxide precursor followed by the subsequent sol-gel reaction. The purpose of this hybrid material was to combine properties of each component in the interaction with arsenic oxoanions and compare its performance with commercial adsorbents. The polymer hybrid microspheres were shown to remove arsenate, and the presence of the inorganic phase also allowed for the removal of arsenite. The hybrid adsorbent exhibited arsenic sorption independent of pH, is able to regenerate, displays fast kinetics and has the ability to reduce arsenic concentration in treated water below 10 µg L-1 even in real samples with an initial concentration as high as 380 µg L-1.

Physical nanocomposite hydrogels filled with low concentrations of TiO2 nanoparticles: Swelling, networks parameters and cell retention studies.

Physical nanocomposite hydrogels composed of poly(2-hydroxyethylmethacrylate) and titanium oxide nanoparticles at low concentrations (<1.0 wt%) were synthesized. The effect of the nanoparticle content on the water swelling and mechanical properties of the hydrogels was investigated. Additionally, to study the influence of the polymer-nanoparticle interactions, a second type of nanocomposite was synthesized using surface functionalized nanoparticles with 3-methacryloxypropyltrimethoxysilane as the filler. The pristine nanoparticles increased the swelling capacity, especially at short time scales, and greater solvent diffusion coefficients and initial swelling rates were achieved. In contrast, the nanocomposite filled with functionalized nanoparticles exhibited a diminished swelling capacity, a constant diffusion coefficient and a significant decrease in the initial swelling rate. The mechanical properties were studied by dynamic mechanical analyses using stress-relaxation tests. Two Maxwell models in parallel agreed well with the curves of the relaxation modulus as a function of time and indicated that at short relaxation times, the nanoparticles did not cause an effect, but that at longer times, the nanoparticles decreased the relaxation time. Finally, hydrogel network parameters determined by swelling measurements and mechanical experiments indicated that the hydrogel with well distributed nanoparticles decreases the molar mass between crosslink point and the mesh size, while poorly distributed nanoparticles lead to larger mesh size. Our functional studies show that the addition of titanium oxide nanoparticles improves the ability of nanocomposite hydrogels to retain aggregates of skeletal muscle cells, revealing their potential use as suitable scaffolds for tissue repair strategies.

Water-Soluble and Insoluble Polymers, Nanoparticles, Nanocomposites and Hybrids With Ability to Remove Hazardous Inorganic Pollutants in Water.

The polymeric materials have presented a great development in adsorption processes for the treatment of polluted waters. The aim of the current review is to present the recent developments in this field of study by examining research of systems like functional water-soluble polymers and water-soluble polymer-metal complexes coupled to ultrafiltration membranes for decontamination processes in liquid-liquid phase. Noticing that a water-soluble polymer can be turned into insoluble compounds by setting a crosslinking point, connecting the polymer chains leading to polymer resins suitable for solid-liquid extraction processes. Moreover, these crosslinked polymers can be used to develop more complex systems such as (nano)composite and hybrid adsorbents, combining the polymers with inorganic moieties such as metal oxides. This combination results in novel materials that overcome some drawbacks of each separated components and enhance the sorption performance. In addition, new trends in hybrid methods combining of water-soluble polymers, membranes, and electrocatalysis/photocatalysis to remove inorganic pollutants have been discussed in this review.

Learning from Synthetic Models of Extracellular Matrix; Differential Binding of Wild Type and Amyloidogenic Human Apolipoprotein A-I to Hydrogels Formed from Molecules Having Charges Similar to Those Found in Natural GAGs.

Among other components of the extracellular matrix (ECM), glycoproteins and glycosaminoglycans (GAGs) have been strongly associated to the retention or misfolding of different proteins inducing the formation of deposits in amyloid diseases. The composition of these molecules is highly diverse and a key issue seems to be the equilibrium between physiological and pathological events. In order to have a model in which the composition of the matrix could be finely controlled, we designed and synthesized crosslinked hydrophilic polymers, the so-called hydrogels varying the amounts of negative charges and hydroxyl groups that are prevalent in GAGs. We checked and compared by fluorescence techniques the binding of human apolipoprotein A-I and a natural mutant involved in amyloidosis to the hydrogel scaffolds. Our results indicate that both proteins are highly retained as long as the negative charge increases, and in addition it was shown that the mutant is more retained than the Wt, indicating that the retention of specific proteins in the ECM could be part of the pathogenicity. These results show the importance of the use of these polymers as a model to get deep insight into the studies of proteins within macromolecules.