Search

Background Quaternary chitosan based fibers have emerged as promising biomaterials for tissue engineering, wound healing and hygiene related textiles, but their in vivo application is restricted by the lack of biodegradability of the synthetic polymers used as co-spinning agents. Herein, we report fully biodegradable chitosan/N,N,N-trimethyl chitosan (TMC) nanofibers prepared via electrospinning, when using poly(ethylene glycol) as sacrificial additive, as potential bioabsorbable wound dressings.Methods The composition and morphology of the fiber mats was confirmed by Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, thermogravimetric analysis, wide angle X-ray diffraction, polarized optical microscopy and scanning electron microscopy. Their properties required for in vivo application, such as behavior in moisture media (dynamic vapor sorption, swelling and enzymatic degradation tests), muco- and bio-adhesive character, mechanical properties and antimicrobial activity were measured. The in vitro biocompatibility on normal human dermal fibroblasts was investigated in line with standards for biomedical devices and in vivo acute toxicity and biocompatibility was assessed by monitoring hematological, biochemical and immunological profile on Wistar rats. Wound closure and healing was studied on burn wound healing models in rats.Results The combination of chitosan with its TMC derivative into nanofibers enabled high swelling ability and fluid exchange, biodegradability rate controlled by the TMC content and pH of media, muco- and bio-adhesive character, mechanical properties similar to skin tissue, strong antimicrobial activity against relevant pathogens and in vitro and in vivo biocompatibility. Moreover, their subcutaneous implantation in rats revealed in vivo biodegradation and lack of toxicity. As a proof of concept, the fiber mats application on burn wound healing models in rats showed wound closure and active healing, with fully restoration of epithelia.Conclusions The use of poly(ethylene glycol) with double role, electrospinning and sacrificial additive, is a straight pathway to the obtaining of chitosan/TMC nanofibers. The combination of chitosan with its N,N,N-trimethyl chitosan derivative into nanofiber mats provide a bioabsorbable bandage which favors rapid wound closure and fully restoration of the skin tissue.

The paper aimed to prepare imino-chitosan fibers by the imination reaction in a heterogenous system, targeting the improvement of anti-pathogenic activity. To this end, porous neat chitosan fibers were prepared by electrospinning of the polyethylene glycol/chitosan blend, followed by polyethylene glycol removal. Imination of the neat chitosan fibers was carried out in three liquid phase systems using solvents of different polarity and, consequently, different ability to swell the solid phase chitosan fibers. The successful imination was qualitatively and quantitatively assessed by FTIR and 1H-NMR spectroscopy, and the impact of the liquid phase on the fibers’ morphology was evaluated by SEM, POM and AFM microscopy. Further, the antimicrobial activity of the imino-chitosan fibers was investigated on relevant bacterial and fungal strains. It was concluded that the prior swelling in water of the fibers improved the imination degree, while the use of a less polar solvent, such as toluene, favored the preservation of the fibrous morphology. The imination with an antimicrobial aldehyde endowed the chitosan fibers with the ability to create a physical barrier against pathogens.

Chitosan based nanofibers are emerging biomaterials with a plethora of applications, especially in medicine and healthcare. Herein, binary quaternized chitosan/chitosan fibers are reported for the first time. Their preparation strategy consisted in the electrospinning of ternary chitosan/quaternized chitosan/poly(ethylene oxide) solutions followed by the selective removal of poly(ethylene oxide). Their morphology and performances were systematically investigated and discussed in detail. It was found that the fibers had reversible water vapor adsorption/desorption and showed swelling degrees similar to commercial wound dressings. They presented good mechanical properties and the content of quaternized chitosan modulated their bioadhesion, mucoadhesion and biodegradation rate and conferred them strong antimicrobial activity. Tests on normal human fibroblasts confirmed their safely use in contact with tissues and the biocompatibility investigation on rats showed no harmful effect when subcutaneous implanted. All these proved the binary quaternized chitosan/chitosan fibers as bioactive materials suitable for tissue regeneration, wound healing and drug delivery systems.

Microporous chitosan nanofibers functionalized with different amounts of an antimicrobial agent via imine linkage were prepared by a three-step procedure including the electrospinning of a chitosan/PEO blend, PEO removal and acid condensation reaction in a heterogeneous system with 2-formylphenylboronic acid. The fibers’ characterization was undertaken keeping in mind their application to wound healing. Thus, by FTIR and 1H-NMR spectroscopy, it was confirmed the successful imination of the fibers and the conversion degree of the amine groups of chitosan into imine units. The fiber morphology in terms of fiber diameter, crystallinity, inter- and intra-fiber porosity and strength of intermolecular forces was investigated using scanning electron microscopy, polarized light microscopy, water vapor sorption and thermogravimetric analysis. The swelling ability was estimated in water and phosphate buffer by calculating the mass equilibrium swelling. The fiber biodegradation was explored in five media of different pH, corresponding to different stages of wound healing and the antimicrobial activity against the opportunistic pathogens inflicting wound infection was investigated according to standard tests. The biocompatibility and bioadhesivity were studied on normal human dermal fibroblast cells by direct contact procedure. The dynamic character of the imine linkage of the functionalized fibers was monitored by UV-vis spectroscopy. The results showed that the functionalization of the chitosan microporous nanofibers with antimicrobial agents via imine linkage is a great route towards bio-absorbable wound dressings with “on demand” antimicrobial properties and biodegradation rate matching the healing stages.

Microporous chitosan nanofibers functionalized with different amounts of an antimicrobial agent via imine linkage were prepared by a three-step procedure including the electrospinning of a chitosan/PEO blend, PEO removal and acid condensation reaction in a heterogeneous system with 2-formylphenylboronic acid. The fibers’ characterization was undertaken keeping in mind their application to wound healing. Thus, by FTIR and 1H-NMR spectroscopy, it was confirmed the successful imination of the fibers and the conversion degree of the amine groups of chitosan into imine units. The fiber morphology in terms of fiber diameter, crystallinity, inter- and intra-fiber porosity and strength of intermolecular forces was investigated using scanning electron microscopy, polarized light microscopy, water vapor sorption and thermogravimetric analysis. The swelling ability was estimated in water and phosphate buffer by calculating the mass equilibrium swelling. The fiber biodegradation was explored in five media of different pH, corresponding to different stages of wound healing and the antimicrobial activity against the opportunistic pathogens inflicting wound infection was investigated according to standard tests. The biocompatibility and bioadhesivity were studied on normal human dermal fibroblast cells by direct contact procedure. The dynamic character of the imine linkage of the functionalized fibers was monitored by UV-vis spectroscopy. The results showed that the functionalization of the chitosan microporous nanofibers with antimicrobial agents via imine linkage is a great route towards bio-absorbable wound dressings with “on demand” antimicrobial properties and biodegradation rate matching the healing stages.

The aim of the study was to create a mathematical model useful for monitoring the release of bioactive aldehydes covalently bonded to the chitosan by reversible imine linkage, considered as a polymer–drug system. For this purpose, two hydrogels were prepared by the acid condensation reaction of chitosan with the antifungal 2-formyl-phenyl-boronic acid and their particularities, influencing the release of the antifungal aldehyde by shifting the imination equilibrium to the reagents was considered, i.e., the supramolecular nature of the hydrogels was highlighted by polarized light microscopy, while scanning electron microscopy showed their microporous morphology. Furthermore, the in vitro fungicidal activity was investigated on two fungal strains and the in vitro release curves of the antifungal aldehyde triggered by the pH stimulus were drawn. The theoretical model was developed starting from the hypothesis that the imine-chitosan system, both structurally and functionally, can be assimilated, from a mathematical point of view, with a multifractal object, and its dynamics were analyzed in the framework of the Scale Relativity Theory. Thus, through Riccati-type gauges, two synchronous dynamics, one in the scale space, associated with the fungicidal activity, and the other in the usual space, associated with the antifungal aldehyde release, become operational. Their synchronicity, reducible to the isomorphism of two SL(2R)-type groups, implies, by means of its joint invariant functions, bioactive aldehyde compound release dynamics in the form of “kink–antikink pairs” dynamics of a multifractal type. Finally, the theoretical model was validated through the experimental data.

The paper reports the preparation and characterization of a series of functionalized chitosan nanofibers designed for tissue engineering. Their functionalization was done by imination with two aldehydes with complementary bioactivity, one possessing antimicrobial activity and the other one having potential to enhance it by improving the cell permeability. The degree of imination of the fibers and the dynamic character of the imine units were investigated by FTIR, 1H NMR and UV–vis spectroscopy, while their morphology was assessed by scanning electron microscopy and polarized light microscopy. The swelling ability and biodegradation were determined in conditions mimicking the physiological environment, i.e. saline buffer and lysozyme medium at 37 °C. Preliminary biocompatibility and antimicrobial properties were evaluated by MTS assay on normal human dermal fibroblasts, and by disk diffusion method against relevant bacterial and fungal reference strains. The fibers showed fast swelling, biodegradation in the presence of lysozyme, biocompatibility and antimicrobial activity. It was concluded that the imination of chitosan nanofibers with two different aldehydes is a promising route towards biomaterials with improved properties for tissue engineering.

Chitosan is a biopolymer originating from renewable resources, with great properties which make it an attractive candidate for plenty of applications of contemporary interest. By manufacturing chitosan into nanofibers using the electrospinning method, its potential is amplified due to the enhancement of the active surface and the low preparation cost. Many attempts were made with the aim of preparing chitosan-based nanofibers with controlled morphology targeting their use for tissue engineering, wound healing, food packaging, drug delivery, air and water purification filters. This was a challenging task, which resulted in a high amount of data, sometimes with apparent contradictory results. In this light, the goal of the paper is to present the main routes reported in the literature for chitosan electrospinning, stressing the advantages and disadvantages of each of them. Special emphasis is placed on the influence of various electrospinning parameters on the morphological characteristics of the fibers and their suitability for distinct applications.