Phosphorylated Curdlan Gel/Polyvinyl Alcohol Electrospun Nanofibres Loaded with Clove Oil with Antibacterial Activity.

Fibrous membranes based on natural polymers obtained by the electrospinning technique are a great choice for wound dressings. In order to promote an efficient wound repair, and to avoid antibiotics, antibacterial plant extracts can be incorporated. In the present work, the new electrospun nanofibre membranes based on monobasic phosphate curdlan (PCurd) and polyvinyl alcohol (PVA) were obtained for the first time. To establish the adequate mixing ratio for electrospinning, the behaviour of the PCurd and PVA mixture was studied by viscometry and rheology. In order to confer antimicrobial activity with the nanofibre membrane, clove essential oil (CEO) was incorporated into the electrospun solution. Well-defined and drop-free nanofibres with a diameter between 157 nm and 110 nm were obtained. The presence of CEO in the obtained nanofibres was confirmed by ATR-FTIR spectroscopy, by the phenolic and flavonoid contents, and by the antioxidant activity of the membranes. In physiological conditions, CEO was released from the membrane after 24 h. The in vivo antimicrobial tests showed a good inhibitory activity against E. coli and higher activity against S. aureus. Furthermore, the viability cell test showed the lack of cytotoxicity of the nanofibre membrane with and without CEO, confirming its potential use in wound treatment.

Eco-Friendly Synthesized PVA/Chitosan/Oxalic Acid Nanocomposite Hydrogels Embedding Silver Nanoparticles as Antibacterial Materials.

PVA/chitosan (PVA/CS) composite hydrogels incorporating silver nanoparticles (AgNPs) were prepared by double-cross-linked procedures: freeze−thawing and electrostatic interactions. Oxalic acid (OA) was used both for solubilization and ionic cross-linking of CS. AgNPs covered by CS (CS-AgNPs) with an average diameter of 9 nm and 18% silver were obtained in the presence of CS, acting as reducing agent and particle stabilizer. The increase of the number of freeze−thaw cycles, as well as of the PVA:CS and OA:CS ratios, resulted in an increase of the gel fraction and elastic modulus. Practically, the elastic modulus of the hydrogels increased from 3.5 kPa in the absence of OA to 11.6 kPa at a 1:1 OA:CS weight ratio, proving that OA was involved in physical cross-linking. The physicochemical properties were not altered by the addition of CS-AgNPs in low concentration; however, concentrations higher than 3% resulted in low gel fraction and elastic modulus. The amount of silver released from the composite hydrogels is very low (<0.4%), showing that AgNPs were well trapped within the polymeric matrix. The composite hydrogels displayed antimicrobial activity against S. aureus, K. pneumoniae or P. gingivalis. The low cytotoxicity and the antibacterial efficacy of hydrogels recommend them for wound and periodontitis treatment.

Dual Cross-Linked Chitosan/PVA Hydrogels Containing Silver Nanoparticles with Antimicrobial Properties.

Stable chitosan/PVA-based hydrogels were obtained by combining covalent and physical cross-linking methods. As covalent cross-linkers, epoxy agents with different chain lengths were used, while freeze-thaw cycles were applied for additional physical cross-linking. The chemical structure of the hydrogel was examined by FTIR spectroscopy whereas the morphology was analyzed by SEM, showing well-defined pores with dimensions of around 50 µm in diameter. It was proved that gel fraction and the network morphology were deeply influenced by the synthesis conditions. Chitosan/PVA hydrogel showed a relative high swelling rate, reaching equilibrium in the first hour. The values obtained for the elastic modulus were relatively low (3-30 kPa); as a result, these hydrogels are soft and very flexible, and are ideal candidates for medical applications as wound or oral dressings. In addition, the natural antimicrobial activity of chitosan was enhanced by in situ generation of silver nanoparticles (AgNPs) under UV irradiation. The total amount of Ag from hydrogel was determined by elemental analyses and its crystalline state was confirmed by XRD. The CS/PVA hydrogels entrapped with AgNPs exhibited high inhibitory activity against S. aureus and K. pneumonia. The vitality tests confirmed the lack of cytotoxicity of CS/PVA hydrogels without and with AgNPs.

Cationic curdlan: Synthesis, characterization and application of quaternary ammonium salts of curdlan.

Water-soluble curdlan derivatives containing quaternary ammonium groups with a degree of substitution up to 0.15 were synthesized using different cationic agents in alkaline medium. The chemical structure of curdlan derivatives was confirmed by FTIR, (13)C and (1)H NMR spectroscopy. The influence of some reaction conditions (temperature, time, and molar ratio) on the degree of substitution and the viscosimetic behaviour were studied. The degree of substitution increased with the amount of the cationization agent per anhydroglucose unit and was higher when the glycidyl reagents were used, compared with the case when the reagents contained chloro-hydroxypropyl groups. The viscosity behaviour of these new derivatives of curdlan in aqueous solutions and the values of intrinsic viscosities calculated using different semi-empirical equations denote a high hydrodynamic dimension of the macromolecular coils. The interaction of these cationic curdlan derivatives with an anionic curdlan (monobasic curdlan phosphate) was studied in situ by turbidimetric measurements and after 24h by optical density and dynamic light scattering. The formation of polyelectrolyte complexes was influenced by the degree of substitution, the nature of the quaternary substituent, and by the ionic strength of the aqueous solution. The morphology of the polyelectrolyte complexes particles in dry state was examined by atomic force microscopy.

Phosphorylated curdlan microgels. Preparation, characterization, and in vitro drug release studies.

Curdlan derivative with anionic phosphate groups was used for the first time to obtain hydrogel microspheres. The chemical cross-linking of the phosphorylated curdlan was performed with epichlorohydrin using the water-in-oil inverse emulsion technique. The optical and scanning electron microscopies were used to analyze the morphology of the microgels, whereas the FTIR spectroscopy was used to investigate their chemical structure. The main characteristics such as the swelling degree, the exchange capacity, and the thermal resistance were also studied. These new anionic microgels could be used as potential carriers for controlled release of opposite charged drugs retained through electrostatic forces. Diphenhydramine, a cationic model drug, was used to investigate the loading and the release processes in various pH media simulating physiological fluids. Several mathematical models were applied to evaluate the drug transport processes and to calculate the drug diffusion coefficients. The synthesized microspheres presented an excellent biocompatibility.