RESUMEN

Covalent cross-linked hydrogels based on chitosan and poly(maleic acid-alt-vinyl acetate) were prepared as spherical beads. The structural modifications of the beads during the preparation steps (dropping in liquid nitrogen and lyophilization, thermal treatment, washing with water, and treatment with NaOH) were monitored by FT-IR spectroscopy. The hydrogel beads have a porous inner structure, as shown by SEM microscopy; moreover, they are stable in acidic and basic pH due to the covalent crosslinking. The swelling degree is strongly influenced by the pH since the beads possess ionizable amine and carboxylic groups. The binding capacity for Cu2+ ions was examined in batch mode as a function of sorbent composition, pH, contact time, and the initial concentration of Cu2+. The kinetic data were well-fitted with the pseudo-second-order kinetic, while the sorption equilibrium data were better fitted with Langmuir and Sips isotherms. The maximum equilibrium sorption capacity was higher for the beads obtained with a 3:1 molar ratio between the maleic copolymer and chitosan (142.4 mg Cu2+ g-1), compared with the beads obtained using a 1:1 molar ratio (103.7 mg Cu2+ g-1). The beads show a high degree of reusability since no notable decrease in the sorption capacity was observed after five consecutive sorption/desorption cycles.

RESUMEN

The paper reports new hydrogels based on quaternary ammonium salts of chitosan designed as biocidal products. The chitosan derivative was crosslinked with salicylaldehyde via reversible imine bonds and supramolecular self-assemble to give dynamic hydrogels which respond to environmental stimuli. The crosslinking mechanism was demonstrated by 1H NMR and FTIR spectroscopy, and X-ray diffraction and polarized light microscopy. The hydrogel nature, self-healing and thixotropy were proved by rheological investigation and visual observation, and their morphology was assessed by scanning electron microscopy. The relevant properties for application as biocidal products, such as swelling, dissolution, bioadhesiveness, antimicrobial activity and ex-vivo hemocompatibility and in vivo local toxicity and biocompatibility on experimental mice were measured and analyzed in relationship with the imination degree and the influence of each component. It was found that the hydrogels are superabsorbent, have good adhesivity to skin and various surfaces and antimicrobial activity against relevant gram-positive and gram-negative bacteria, while being hemocompatible and biocompatible. Besides, the hydrogels are easily biodegraded in soil. All these properties recommend the studied hydrogels as ecofriendly biocidal agents for living tissues and surfaces, but also open the perspectives of their use as platform for in vivo applications in tissue engineering, wound healing, or drug delivery systems.

Asunto(s)

Materiales Biocompatibles , Quitosano , Hidrogeles , Compuestos de Amonio Cuaternario , Quitosano/química , Quitosano/farmacología , Hidrogeles/química , Hidrogeles/farmacología , Compuestos de Amonio Cuaternario/química , Compuestos de Amonio Cuaternario/farmacología , Animales , Materiales Biocompatibles/farmacología , Materiales Biocompatibles/química , Ratones , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Pruebas de Sensibilidad Microbiana , Desinfectantes/farmacología , Desinfectantes/química , Antiinfecciosos/farmacología , Antiinfecciosos/química , Bacterias Gramnegativas/efectos de los fármacos , Bacterias Grampositivas/efectos de los fármacos , Aldehídos

RESUMEN

Emulsion hydrogels are promising materials for encapsulating and stabilizing high amounts of hydrophobic essential oils in hydrophilic matrices. In this work, clove oil-loaded hydrogels (CS/OP-C) are synthesized by combining covalent and physical cross-linking approaches. First, clove oil (CO) was emulsified and stabilized in a chitosan (CS) solution, which was further hardened by Schiff base covalent cross-linking with oxidized pullulan (OP). Second, the hydrogels were subjected to freeze-thaw cycles and, as a result, the clove oil was stabilized in physically cross-linked polymeric walls. Moreover, due to cryogelation, the obtained hydrogels exhibited sponge-like porous interconnected morphology (160-250 µm). By varying the clove oil content in the starting emulsion and the degree of cross-linking, the hydrogels displayed a high water retention capacity (swelling ratios between 1300 and 2000%), excellent elastic properties with fast shape recovery (20 s) after 70% compression, and controlled in vitro clove oil release in simulated skin conditions for 360 h. Furthermore, the prepared clove oil-loaded hydrogels had a strong scavenging activity of 83% and antibacterial and antifungal properties, showing a bacteriostatic effect after 48 and 72 h against S. aureus and E. coli. Our results recommend the new clove oil-embedded emulsion hydrogels as promising future materials for application as wound dressings.

RESUMEN

Composite hydrogels containing apatite-like particles can act as scaffolds for osteoblast proliferation, with applications in bone tissue engineering. In this respect, porous biocompatible hydrogels were obtained from chitosan, oxidized pullulan, and PVA in different ratios. The stability of the hydrogels was ensured both by covalent bonds between aldehyde groups of oxidized pullulan and free amino groups of chitosan, and by physical bonds formed during freeze-thaw cycles and lyophilization. The deposition of calcium phosphates was performed by alternate soaking of the porous hydrogels into solutions with calcium and phosphate ions, assuring a basic pH required for hydroxyapatite formation. The mineralized hydrogels were characterized using FTIR spectroscopy, scanning electron microscopy, X-ray diffraction, and thermogravimetric analysis, showing that inorganic particles containing between 80 and 92% hydroxyapatite were deposited in a high amount on the pore walls of the polymeric matrix. The composition of the organic matrix influenced the crystallization of calcium phosphates and the mechanical properties of the composite hydrogels. In vitro biological tests showed that mineralized hydrogels support the proliferation of MG-63 osteoblast-like cells to a greater extent compared to pristine hydrogels.

RESUMEN

The therapeutic efficiency of plant extracts has been limited by their poor pharmaceutical availability. Hydrogels have promising potential to be applied as wound dressings due to their high capacity to absorb exudates and their enhanced performance in loading and releasing plant extracts. In this work, pullulan/poly (vinyl alcohol) (P/PVA) hydrogels were first prepared using an eco-friendly method based on both a covalent and physical cross-linking approach. Then, the hydrogels were loaded with the hydroalcoholic extract of Calendula officinalis by a simple post-loading immersion method. Different loading capacities were investigated in terms of the physico-chemical properties, chemical composition, mechanical properties, and water absorption. The hydrogels exhibited high loading efficiency due to the hydrogen bonding interactions between polymer and extract. The water retention capacity as well as the mechanical properties decreased with the increase in the extract amount in hydrogel. However, higher amounts of extract in the hydrogel improved the bioadhesiveness. The release of extract from hydrogels was controlled by the Fickian diffusion mechanism. Extract-loaded hydrogels expressed high antioxidant activity, reaching 70% DPPH radical scavenging after 15 min immersion in buffer solution at pH 5.5. Additionally, loaded hydrogels showed a high antibacterial activity against Gram-positive and Gram-negative bacteria and were non-cytotoxic against HDFa cells.

RESUMEN

In this study, a new strategy was adopted for obtaining polymer/protein hybrid hydrogels with shape stability and tunable mechanical or rheological characteristics by using non-toxic procedures. A chemical network was created using a poly(vinyl alcohol)(PVA)/bovine serum albumin (BSA) mixture in aqueous solution in the presence of genipin and reduced glutathione (GSH). Then, a second physical network was formed through PVA after applying freezing/thawing cycles. In addition, the protein macromolecules formed intermolecular disulfide bridges in the presence of GSH. In these conditions, multiple crosslinked networks were obtained, determining the strengthening and stiffening into relatively tough porous hydrogels with tunable viscoelasticity and a self-healing ability. A SEM analysis evidenced the formation of networks with interconnected pores of sizes between 20 µm and 50 µm. The mechanical or rheological investigations showed that the hydrogels' strength and response in different conditions of deformation were influenced by the composition and crosslinking procedure. Thus, the dynamics of the hybrid hydrogels can be adjusted to mimic the viscoelastic properties of the native tissues. The dynamic water vapor-sorption ability, swelling behavior in an aqueous environment, and bioadhesive properties were also investigated and are discussed in this paper. The hybrid hydrogels with tunable viscoelasticity can be designed on request, and they are promising candidates for tissue engineering, bioinks, and wound dressing applications.

RESUMEN

Local delivery of drugs or antimicrobial agents is a suitable approach in the management of periodontitis when the infection is localized deep in the pockets and does not adequately respond to mechanical debridement and/or systemic antibiotic treatment. In this context, the objective of this study was to prepare new biocomposite films with antimicrobial, anti-inflammatory, and good mechanical properties to be applied in periodontal pockets. The composite film is eco-friendly synthesized from poly(vinyl alcohol) (PVA) cross-linked with oxidized chitosan (OxCS). Silver nanoparticles (AgNps) were inserted during film synthesis by adding freshly chitosan-capped AgNps colloidal solution to the polymer mixture; the addition of AgNps up to 1.44 wt.% improves the physico-chemical properties of the film. The characterization of the films was performed by FT-IR, atomic mass spectrometry, X-ray spectroscopy, and SEM. The films displayed a high swelling ratio (162%), suitable strength (1.46 MPa), and excellent mucoadhesive properties (0.6 N). Then, ibuprofen (IBF) was incorporated within the best film formulation, and the IBF-loaded PVA/OxCS-Ag films could deliver the drug in a sustained manner up to 72 h. The biocomposite films have good antimicrobial properties against representative pathogens for oral cavities. Moreover, the films are biocompatible, as demonstrated by in vitro tests on HDFa cell lines.