Theoretical-Experimental Approach of Chitosan/Quaternized Chitosan Nanofibers' Behavior in Wound Exudate Media.

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.

Evaluation of Poly(vinyl alcohol)-Xanthan Gum Hydrogels Loaded with Neomycin Sulfate as Systems for Drug Delivery.

In recent years, multidrug-resistant bacteria have developed the ability to resist multiple antibiotics, limiting the available options for effective treatment. Raising awareness and providing education on the appropriate use of antibiotics, as well as improving infection control measures in healthcare facilities, are crucial steps to address the healthcare crisis. Further, innovative approaches must be adopted to develop novel drug delivery systems using polymeric matrices as carriers and support to efficiently combat such multidrug-resistant bacteria and thus promote wound healing. In this context, the current work describes the use of two biocompatible and non-toxic polymers, poly(vinyl alcohol) (PVA) and xanthan gum (XG), to achieve hydrogel networks through cross-linking by oxalic acid following the freezing/thawing procedure. PVA/XG-80/20 hydrogels were loaded with different quantities of neomycin sulfate to create promising low-class topical antibacterial formulations with enhanced antimicrobial effects. The inclusion of neomycin sulfate in the hydrogels is intended to impart them with powerful antimicrobial properties, thereby facilitating the development of exceptionally efficient topical antibacterial formulations. Thus, incorporating higher quantities of neomycin sulfate in the PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations yielded promising cycling characteristics. These formulations exhibited outstanding removal efficiency, exceeding 80% even after five cycles, indicating remarkable and consistent adsorption performance with repeated use. Furthermore, both PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations outperformed the drug-free sample, PVA/XG-80/20, demonstrating a significant enhancement in maximum compressive stress.

Development of Hybrid Materials Based on Chitosan, Poly(Ethylene Glycol) and Laponite® RD: Effect of Clay Concentration.

In the context of increasing interest in biomaterials with applicability in cosmetics and medicine, this research aims to obtain and characterize some hybrid materials based on chitosan (CS) (antibacterial, biocompatible, and biodegradable), poly(ethylene glycol) (PEG) (non-toxic and prevents the adsorption of protein and cell) and Laponite® RD (Lap) (bioactive). The rheological properties of the starting dispersions were investigated and discussed related to the interactions developed between components. All samples exhibited gel-like properties, and the storage modulus of CS/PEG dispersion increased from 6.6 Pa to 657.7 Pa by adding 2.5% Lap. Structural and morphological characterization of the films, prepared by solution casting method, was performed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and polarized light microscopy (POM). These analyses proved the incorporation of Lap into CS/PEG films and revealed the morphological changes of the films by the addition of clay. Thereby, at the highest Lap concentration (43.8%), the "house of cards" structure formed by Lap platelets, which incorporate chitosan chains, as evidenced by SEM and POM. Two stages of degradation between 200 °C and 410 °C were evidenced for the films with Lap concentration higher than 38.5%, explained by the existence of a clay-rich phase (given by the clay network) and chitosan-rich one (due to the intercalation of chitosan in the clay network). CS/PEG film with 43.8% Lap showed the highest swelling degree of 240.7%. The analysis of the obtained results led to the conclusion that the addition of clay to the CS/PEG films increases their stability in water and gives them greater thermal stability.

Chitosan crosslinking with a vanillin isomer toward self-healing hydrogels with antifungal activity.

The purpose of the study was to develop new antimicrobial hydrogels from natural resources that may promote wound healing and prevent bacterial skin infection. The new hydrogels were synthesized by crosslinking chitosan with a vanillin isomer, 5-methoxysalicylaldehyde, by a friendly and easy method. To characterize these hydrogels, their structural and morphological properties were explored by FTIR, 1H NMR, SEM, POM, and TGA. In view of the targeted application, swelling behavior, biodegradability, antimicrobial activity and biocompatibility were investigated in vitro. Structural and morphological studies confirmed the formation of new hydrogels via the imination reaction concomitant with the supramolecular organization. The hydrogels were highly porous with the average pore diameter around 80 µm, and a swelling rate controlled by the crosslinking density and medium pH. The hydrogels showed a progressive weight loss in the presence of lysozyme up to 35%, during 21 days of testing. They proved non-cytotoxic effect on Normal Human Dermal Fibroblasts using MTS test and powerful antifungal activity against Candida Albicans, as determined by disk diffusion assay. All these properties indicate the new hydrogels as a promising option for the treatment of various skin lesions.

Modulation of the PLLA Morphology through Racemic Nucleation to Reach Functional Properties Required by 3D Printed Durable Applications.

This paper presents an alternative for enhancing the durability of poly (L-lactide) (PLLA) by racemic nucleation following stereo-complexation with a selected poly (D-lactide) (PLDA). The compounds are obtained by melt blending of a PLLA grade, previously designed for 3D printing but with a low heat deflection temperature and impact resistance, with grades of PLDA differing in their molecular weight (Mw), D-lactide content (DS) and concentration. Our method considered how to reveal the racemic nucleation caused by stereo-complexation and its influence on functional properties. The FTIR study we performed showed that, depending on Mw, DS and concentration of the stereo-complexer (PDLA) used, bigger or smaller spectral changes can occur. The stereo-complexation was confirmed by the DSC analysis and, for the selected compound, by the POM, SEM, AFM microscopies, functional property and shapeability as 3D printing filaments. All the obtained results sustain the idea that, if a PLLA with Mw of 4.5 × 104 g·mol-1 is modified with PDLA with a medium Mw of 11.6 × 104 g·mol-1, medium DS of 4% and 1% concentration, a racemic nucleation is possible. It produces a racemic polylactic acid (PDLLA) with improved durability and good shapeability as 3D printing filaments. These results are explicable if the dependence of the intermolecular interactions appears between the PLLA and stereo-complexer PDLA. To enlarge the durable applicability of racemic polylactic acid (PDLLA), future research should identify other parameters controling the PLA stereo-complexing as the intensifying the mobility of the macromolecules, the finding of the optimal recemic cristalization window.

Dynamic Mechanical Analysis Investigations of PLA-Based Renewable Materials: How Are They Useful?

Interest in renewable polymers increased exponentially in the last decade and in this context poly(lactic acid) (PLA) became the leader mainly for practical reasons. Nevertheless, it is outstanding also from a scientific point of view, because its thermal and morphological properties are offering challenging new insights. With regard to dynamic mechanical analysis (DMA), PLA does not have the classical behavior of a thermoplastic polymer. Often, overlapping events (enthalpic relaxation, glass transition and crystallization) that occur as the temperature increases make the DMA result of a PLA look inexplicable even for polymer scientists. This review offers a perspective of the main phenomena that can be revealed in a DMA experiment and systematizes the information that can be obtained for every region (glassy, glass transition, rubbery, cold-crystallization and melting). Also, some unusual patterns registered in some cases will be commented upon. The review intends to offer indices that one should pay attention to in the interpretation of a DMA experiment, even if the investigator has only basic skills with DMA investigations.

A theoretical mathematical model for assessing diclofenac release from chitosan-based formulations.

The paper reports a new mathematical model for understanding the mechanism delivery from drug release systems. To do this, two drug release systems based on chitosan and diclofenac sodium salt as a drug model, were prepared by in situ hydrogelation in the presence of salicylaldehyde. The morphology of the systems was analyzed by scanning electron microscopy and polarized light microscopy and the drug release was in vitro investigated into a medium mimicking the in vivo environment. The drug release mechanism was firstly assessed by fitting the in vitro release data on five traditional mathematical model. In the context of pharmacokinetics behavioral analysis, a new mathematical procedure for describing drug release dynamics in polymer-drug complex systems was proposed. Assuming that the dynamics of polymer-drug system's structural units take place on continuous and nondifferentiable curves (multifractal curves), it was showed that in a one-dimensional hydrodynamic formalism of multifractal variables the drug release mechanism is given through synchronous dynamics at a differentiable and non-differentiable scale resolutions.

A Theoretical Multifractal Model for Assessing Urea Release from Chitosan Based Formulations.

This paper reports the calibration of a theoretical multifractal model based on empirical data on the urea release from a series of soil conditioner systems. To do this, a series of formulations was prepared by in situ hydrogelation of chitosan with salicylaldehyde in the presence of different urea amounts. The formulations were morphologically characterized by scanning electron microscopy and polarized light microscopy. The in vitro urea release was investigated in an environmentally simulated medium. The release data were fitted on five different mathematical models, Korsmeyer-Peppas, Zero order, First order, Higuchi and Hixson-Crowell, which allowed the establishment of a mechanism of urea release. Furthermore, a multifractal model, used for the fertilizer release for the first time, was calibrated using these empirical data. The resulting fit was in good agreement with the experimental data, validating the multifractal theoretical model.

New formulations based on salicyl-imine-chitosan hydrogels for prolonged drug release.

The objective of this paper was to investigate the new formulations based on salicyl-imine-chitosan hydrogels as potential controlled drug release systems. They were prepared by in situ hydrogelation of chitosan with salicylaldehyde in the presence of diclofenac sodium salt (DCF) as model drug. FTIR, X-ray Spectroscopy, POM and SEM techniques were used to confirm the structural, supramolecular and morphological particularities of the formulations. Swelling test, in vitro enzymatic biodegradation and release profile were investigated in similar conditions mimicking the in vivo environment, and the release mechanism was assessed by fitting into five mathematical models. It was established that the formulations have the capacity to release DCF in a sustained manner for 10 days rate, the drug release rate being correlated to the crosslinking density and hydrogelation speed. The biodegradation occurred in three main stages, reaching a mass loss of 48% after 21 days. In order to be used in the biomedical field, the in vivo biocompatibility of the formulations was investigated on experimental rats. After 7 days of subcutaneous implantation, no influence on the hematologic profile, liver, kidney or immune defence capacity were observed, suggesting these formulations as valuable materials for biomedical devices.

Designing chitosan based eco-friendly multifunctional soil conditioner systems with urea controlled release and water retention.

The paper reports new soil conditioner systems obtained by in situ hydrogelation of chitosan with salicylaldehyde in the presence of urea fertilizer, designed to address both fertilization and water retention of the soil. The new systems were structural, supramolecular and morphological characterized by FTIR spectroscopy, XRD diffraction, POM and SEM microscopy. The rate of urea release has been investigated by NMR analysis and the release mechanism has been assessed by fitting five mathematical models. The formulations showed high water absorbency of 68 g/g, and they induced water holding capacity in soil up to 154% and an increment of the nitrogen content in soil to almost double, leading to a growth of plants with almost 70% higher compared to the reference soil. All these data revealed the new systems as new multifunctional soil conditioner ecoproducts capable to address both fertilizing and water retention issues, with high potential of application for sustainable agriculture.

Chiral betulin-imino-chitosan hydrogels by dynamic covalent sonochemistry.

A series of chiral hydrogels was prepared from a homogeneous mixture of chitosan and betulinic aldehyde in different molar ratios, under the effect of ultrasound. The hydrogelation mechanism has been investigated by FTIR and CD spectroscopy, wide angle X-ray diffraction and polarized light microscopy. The morphology of hydrogels was examined by SEM. The swelling ability has been tested in three media of different pH. It was concluded that hydrogelation occurred by different pathways, closely related to the peculiarities of the chitosan-betulin systems. Circular dichroism measurements revealed chiroptical properties of the hydrogels, correlated to their content and crosslinking pathway.

Salicyl-imine-chitosan hydrogels: Supramolecular architecturing as a crosslinking method toward multifunctional hydrogels.

Hydrogels based on chitosan and salicyladehyde were obtained by dynamic covalent chemistry. The unusual chitosan gelling in the presence of the monoaldehyde has been deciphered following and correlating data of NMR, FTIR, single crystal and wide angle XRD, POM and optical measurements. Of significant importance in understanding the crosslinking features was the synthesis of a model compound and the successfully growth as single crystal allowing the study of its supramolecular peculiarities. The hydrogels exhibited in SEM a porous or fibrous morphology, in good correlation with the crosslinking degree. They swelled very fast, similar to the superporous hydrogels of third generation and exhibited self-healing properties. Rheological investigation demonstrated good mechanical properties, thermosensitivity and thixotropy. The paper revealed a hydrogel with suitable properties for use in bio-medical applications, and moreover, revealed a new concept of obtaining chitosan hydrogels using monoaldehydes - which are widespread in nature, cheap and beneficial to the human body.