RESUMO
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.
Assuntos
Antifúngicos/farmacologia , Quitosana/química , Liberação Controlada de Fármacos , Modelos Teóricos , Aldeídos/química , Fractais , Hidrogéis/química , Iminas/químicaRESUMO
This paper focuses on the preparation of chitosan-based nanofibers embedding copper oxide nanoparticles to create multifunctional materials that meet the demands of contemporary applications. To this end, a mixture of chitosan, quaternized chitosan and poly (ethylene glycol) was used as polymeric matrix, considering their own contribution to the final material's properties and their ability to stabilize the copper oxide nanoparticles. An exhaustive investigation of the nanofibers was done in order to assess their composition and morphology (FTIR, 1H NMR, WXRD, TGA, SEM, TEM, POM, UV-vis) and to study their mechanical, antimicrobial and antioxidant properties, air and water permeability and ability for air filtration. It was shown that the copper oxide nanoparticles were anchored into the polymeric matrix via strong hydrogen bonding and electrostatic interactions, which induced the improvement of the mechanical properties and antioxidant activity. The copper oxide nanoparticles favored the thinning of the fibers during electrospinning process and improved the antibacterial activity and dust filtration capacity. Besides, the fibers displayed air permeability and vapor water transmission rate similar to synthetic nanofibers, while being biodegradable. All these performances recommend the new materials for developing antibacterial eco-materials with good breathability to be used as hygienic textiles, masks, or air filters.
Assuntos
Quitosana , Nanofibras , Nanopartículas , Quitosana/química , Antioxidantes/farmacologia , Nanofibras/química , Cobre , Antibacterianos/farmacologia , Antibacterianos/química , Nanopartículas/química , Água , ÓxidosRESUMO
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.
Assuntos
Quitosana , Nanofibras , Humanos , Ratos , Animais , Engenharia Tecidual , Medicina Regenerativa , Óxido de Etileno , Antibacterianos/farmacologiaRESUMO
The paper reports new chitosan-based nanofibers, designed to address the healing of burn wounds. To this aim, mesoporous chitosan fiber mats were prepared by electrospinning using poly(ethylene oxide) as sacrificial additive, followed by loading with norfloxacin and coating with an antifungal agent via dynamic imine bonds. Dynamic vapor sorption experiment proved intra-fiber mesopores around 2.7 nm, and UV-vis, FTIR, and NMR spectroscopy confirmed the norfloxacin embedding and the imination reaction. SEM, AFM and POM techniques displayed semicrystalline nanofibers with average diameter around 170 nm entangled into a non-woven mat. Their mesoporous nature favored a rapid adsorption of fluids up to 17 g/g, and a biodegradation rate fitting the wound healing rate, i.e. up to 30 % mass loss in media of pH characteristic to wound exudate and total degradation in that characteristic to normal dermis. The composite fibers released the NFX and 2FPBA in a controlled manner, and showed antimicrobial activity against gram positive, gram negative and fungal strains. They had no cytotoxic effect on normal human dermal fibroblasts, and showed biocompatibility on experimental rats. The investigation of wound healing ability on second/third-degree burn model in rats revealed wound closure and total restoration of the fully functional dermis and epidermis.
Assuntos
Quitosana , Nanofibras , Humanos , Animais , Ratos , Implantes Absorvíveis , Norfloxacino , Cicatrização , BandagensRESUMO
The paper aimed to prepare quaternary chitosan-based nanofibers as bioabsorbable wound dressings. To this aim, fully biodegradable chitosan/N,N,N-trimethyl chitosan (TMC) nanofibers were designed and prepared via electrospinning, using poly(ethylene glycol) as sacrificial additive. The new biomaterials were structurally and morphologically characterized by FTIR and NMR spectroscopy, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy, and their properties required for wound dressings application were investigated and discussed in detail. Thus, the nanofiber behavior was investigated by swelling, dynamic vapor sorption, and in vitro biodegradation in media mimicking the wound exudate. The mechanical properties were analysed from the stress-strain curves, the bioadhesivity from the texture analysis and the mucoadhesivity from the Zeta potential and transmittance measurements. The antimicrobial activity was assessed against S. aureus and E. coli strains, and the biocompatibility was tested in vitro on normal human dermal fibroblasts, and in vivo on rats. The application of the fiber mats with the best balance of properties as dressings on deep burn wound models in rats showed wound closure and active healing, with fully restoration of epithelia. It was concluded that the combination of chitosan with TMC into nanofibers provides new potential bioabsorbable wound dressing, opening new perspectives in regenerative medicine.
Assuntos
Quitosana , Nanofibras , Ratos , Humanos , Animais , Quitosana/química , Antibacterianos/farmacologia , Antibacterianos/química , Nanofibras/química , Staphylococcus aureus , Escherichia coli , Implantes Absorvíveis , BandagensRESUMO
The industrial production of chitosan, initiated over 50 years ago, has transformed its application across diverse industries, agriculture, and medicine. To enhance its properties, numerous chitosan derivatives have been synthesized. The quaternization of chitosan has proven beneficial, as it not only enhances its properties but also imparts water solubility, expanding its potential for a wider range of applications. Specifically, the utilization of quaternized chitosan-based nanofibers has leveraged the synergistic benefits of quaternized chitosan (including hydrophilicity, bioadhesiveness, antimicrobial, antioxidant, hemostatic, and antiviral activities, as well as ionic conductivity) in combination with the distinctive characteristics of nanofibers (such as a high aspect ratio and 3D architecture). This combination has permitted numerous possibilities, spanning from wound dressings, air and water filters, drug delivery scaffolds, antimicrobial textiles, to energy storage systems and alkaline fuel cells. In this comprehensive review, we examine the preparation methods, properties, and applications of various composite fibers containing quaternized chitosan. The advantages and disadvantages of each method and composition are meticulously summarized, while relevant diagrams and figures illustrate the key findings.
Assuntos
Anti-Infecciosos , Quitosana , Hemostáticos , Nanofibras , Quitosana/farmacologia , Anti-Infecciosos/farmacologia , Água , AntibacterianosRESUMO
This study aimed to investigate the behavior of chitosan/quaternized chitosan fibers in media mimicking wound exudates to understand their capacities as wound dressing. Fiber analysis of the fibers using dynamic vapor sorption proved their ability to adsorb moisture up to 60% and then to desorb it as a function of humidity, indicating their outstanding breathability. Dissolution analyses showed that quaternized chitosan leached from the fibers in water and PBS, whereas only small portions of chitosan were solubilized in water. In media containing lysozyme, the fibers degraded with a rate determined by their composition and pH, reaching a mass loss of up to 47% in media of physiologic pH. Notably, in media mimicking the wound exudate during healing, they adsorbed moisture even when their mass loss due to biodegradation was high, whereas they were completely degraded in the media of normal tissues, indicating bioabsorbable dressing capacities. A mathematical model was constructed, which characterized the degradation rate and morphology changes of chitosan/quaternized chitosan fibers through analyses of dynamics in scale space, using the Theory of Scale Relativity. The model was validated using experimental data, making it possible to generalize it to the degradation of other biopolymeric systems that address wound healing.
RESUMO
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.
RESUMO
The development of intelligent materials for protective equipment applications is still growing, with enormous potential to improve the safety of personnel functioning in specialized professions, such as firefighters. The design and production of such materials by the chemical modification of biodegradable semisynthetic polymers, accompanied by modern manufacturing techniques such as electrospinning, which may increase specific properties of the targeted material, continue to attract the interest of researchers. Phosphorus-modified poly(vinyl alcohol)s have been, thus, synthesized and utilized to prepare environmentally friendly electrospun mats. Poly(vinyl alcohol)s of three different molecular weights and degrees of hydrolysis were phosphorylated by polycondensation reaction in solution in the presence of phenyl dichlorophosphate in order to enhance their flame resistance and thermal stability. The thermal behavior and the flame resistance of the resulting phosphorus-modified poly(vinyl alcohol) products were investigated by thermogravimetric analysis and by cone calorimetry at a micro scale. Based on the as-synthesized phosphorus-modified poly(vinyl alcohol)s, electrospun mats were successfully fabricated by the electrospinning process. Rheology studies were performed to establish the optimal conditions of the electrospinning process, and scanning electron microscopy investigations were undertaken to observe the morphology of the phosphorus-modified poly(vinyl alcohol) electrospun mats.