Preparation and Characterization of Polymeric Microparticles Based on Poly(ethylene brassylate-co-squaric Acid) Loaded with Norfloxacin.

In recent years, increasing interest has been accorded to polyester-based polymer microstructures, driven by their promising potential as advanced drug delivery systems. This study presents the preparation and characterization of new polymeric microparticles based on poly(ethylene brassylate-co-squaric acid) loaded with norfloxacin, a broad-spectrum antibiotic. Polymacrolactone was synthesised in mild conditions through the emulsion polymerization of bio-based and renewable monomers, ethylene brassylate, and squaric acid. The microparticles were obtained using the precipitation technique and subsequently subjected to comprehensive characterization. The impact of the copolymer/drug ratio on various properties of the new system was systematically evaluated, confirming the structure of the copolymer and the encapsulation of norfloxacin. The microspheres are approximately spherical and predominantly homogeneously distributed. The average hydrodynamic diameter of the microparticles falls between 400 and 2000 nm, a decrease that is observed with the increase in norfloxacin content. All samples showed good encapsulation efficiency and drug loading capacity, with the highest values obtained for microparticles synthesised using an equal ratio of copolymer and drug. In vitro drug release results disclose that norfloxacin molecules are released in a sustained biphasic manner for up to 24 h. Antimicrobial activity was also studied, with samples showing very good activity against E. coli and moderate activity against S. aureus and E. faecalis. In addition, HDFA human fibroblast cell cultures demonstrated the cytocompatibility of the microparticles.

Photothermal Hydrogel Composites Featuring G4-Carbon Nanomaterial Networks for Staphylococcus aureus Inhibition.

Microbial infections represent a significant health risk, often leading to severe complications and, in some cases, even fatalities. As a result, there is an urgent need to explore innovative drug delivery systems and alternative therapeutic techniques. The photothermal therapy has emerged as a promising antibacterial approach and is the focus of this study. Herein, we report the successful synthesis of two distinct supramolecular composite hydrogels by incorporating graphene oxide (GO) and single-walled carbon nanotubes (SWNTs) into guanosine quadruplex (G4) based hydrogels containing covalently bound ß-cyclodextrin (ß-CD). The G4 matrix was synthesized through a two-step process, establishing a robust network between G4 and ß-CDs, followed by the encapsulation of either GO or SWNTs. Comprehensive characterization of these composite hydrogels were conducted using analytical techniques, including circular dichroism, Raman spectroscopy, rheological investigations, X-ray diffraction, and scanning electron microscopy. A notable discovery from the conducted research is the differential photothermal responses exhibited by the hydrogels when exposed to near-infrared laser irradiation. Specifically, SWNT-based hydrogels demonstrated superior photothermal performance, achieving a remarkable temperature increase of up to 52 °C, in contrast to GO-based hydrogels, which reached a maximum of 34 °C. These composite hydrogels showed good cytotoxicity evaluation results and displayed synergistic antibacterial activity against Staphylococcus aureus, positioning them as promising candidates for antibacterial photothermic platforms, particularly in the context of wound treatment. This study offers a valuable contribution to the development of advanced and combined therapeutic strategies for combating microbial infections and highlights the potential of carbon nanomaterial-enhanced supramolecular hydrogels in photothermal therapy applications.

Chitosan nanofibers encapsulating copper oxide nanoparticles: A new approach towards multifunctional ecological membranes with high antimicrobial and antioxidant efficiency.

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.

Zein/Polysaccharide Nanoscale Electrostatic Complexes: Preparation, Drug Encapsulation and Antibacterial Properties.

Characterization of zein aqueous solutions, as a function of the ethanol content and pH, was performed, giving information on the zein aggregation state for the construction of complexes. The aggregation state and surface charge of zein was found to depend on the mixed solvent composition and pH. Nonstoichiometric complex nanoparticles (NPECs) were prepared by electrostatically self-assembling zein, as the polycation, and sodium alginate or chondroitin sulfate, as the polyanions, at a pH of 4. A wide range of parameters were investigated: the alcohol-water content in the zein solutions, the charge molar ratios, the solution addition order and the addition rate. The resulting nanoparticles were characterized by dynamic and electrophoretic light scattering, circular dichroism and scanning electron microscopy. The smallest size for the NPECs (100 nm) was obtained when the polysaccharides acted as the titrate with an addition rate of 0.03 mL·min-1. The NPECs with the best characteristics were selected for loading with ciprofloxacin and then deposited on a cellulosic material in order to evaluate their antibacterial activity. Substantial drug encapsulation with desired drug release profiles were found together with notable antibacterial efficiency, showing the tunability of the properties for both the zein and its complexes with polysaccharides, together with their application potential in the biomedical field.

Dextran coated iron oxide nanoparticles loaded with protocatechuic acid as multifunctional therapeutic agents.

Nowadays, there is a growing interest in multifunctional therapeutic agents as valuable tools to improve and expand the applicability field of traditional bioactive compounds. In this context, the synthesis and main characteristics of dextran-coated iron oxide nanoparticles (IONP-Dex) loaded with both an antioxidant, protocatechuic acid (PCA), and an antibiotic, ceftazidime (CAZ) or levofloxacin (LEV) are herein reported for the first time, with emphasis on the potentiation effect of PCA on drugs activity. All nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, vibrating sample magnetometry, differential scanning calorimetry and dynamic light scattering. As evidenced by DPPH method, IONP-Dex loaded with PCA and LEV had similar antioxidant activity like those with PCA only, but higher than PCA and CAZ loaded ones. A synergy of action between PCA and each antibiotic co-loaded on IONP-Dex has been highlighted by an enhanced activity against reference bacterial strains, such as S. aureus and E. coli after 40 min of incubation. It was concluded that PCA, which is the main cause of the antioxidative properties of loaded nanoparticles, further improves the antimicrobial activity of IONP-Dex nanoparticles when was co-loaded with CAZ or LEV antibiotics. All constructs also showed a good biocompatibility with normal human dermal fibroblasts.

Thermosensitive Polyurethane-Based Hydrogels as Potential Vehicles for Meloxicam Delivery.

Meloxicam (MX) is a nonsteroidal anti-inflammatory drug (NSAID) used mainly to reduce pain, inflammation, and fever. In the present study, thermosensitive polyurethane (PU)-based hydrogels with various excipients (PEG, PVP, HPC, and essential oil) were prepared and loaded with MX. Rheological investigations were carried out on the PU-based formulations in various shear regimes, and their viscoelastic characteristics were determined. The average size of the PU micelles was 35.8 nm at 37 °C and slightly increased at 37 nm in the presence of MX. The zeta potential values of the hydrogels were between -10 mV and -11.5 mV. At pH = 6 and temperature of 37 °C, the formulated PU-based hydrogels loaded with MX could deliver significant amounts of the active substance, between 60% and 80% over 24-48 h and more than 90% within 2 weeks. It was found that anomalous transport phenomena dominated MX's release mechanism from the PU-based networks. The results are encouraging for further studies aiming to design alternative carriers to commercial dosage forms of nonsteroidal anti-inflammatory drugs.

Mesoporous chitosan nanofibers loaded with norfloxacin and coated with phenylboronic acid perform as bioabsorbable active dressings to accelerate the healing of burn wounds.

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.

Drug delivery based on a supramolecular chemistry approach by using chitosan hydrogels.

Microbial infections are a serious healthcare related problem, causing several complications and even death. That is why, the development of new drug delivery systems with prolonged effect represents an interesting research topic. This study presents the synthesis and characterization of new hydrogels based on chitosan and three halogenated monoaldehydes. Further, the hydrogels were used as excipients for the development of drug delivery systems (DDS) by the incorporation of fluconazole, an antifungal drug. The systems were structurally characterized by Fourier Transformed Infrared Spectroscopy and Nuclear Magnetic Resonance, both methods revealing the formation of the imine linkages between chitosan and the aldehydes. The samples presented a high degree of ordering at supramolecular level, as demonstrated by WXRD and POM and a good water-uptake, reaching a maximum of 1.6 g/g. The obtained systems were biodegradable, loosing between 38 and 49 % from their initial mass in the presence of lysozyme in 21 days. The ability to release the antifungal drug in a sustained manner for seven days, along with the high values of the inhibition zone diameter, reaching a maximum of 64 mm against Candida parapsilosis for the chlorine containing sample, recommend these systems as promising materials for bioapplications.

Biodegradable trimethyl chitosan nanofiber mats by electrospinning as bioabsorbable dressings for wound closure and healing.

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.

New Hydrogels Nanocomposites Based on Chitosan, 2-Formylphenylboronic Acid, and ZnO Nanoparticles as Promising Disinfectants for Duodenoscopes Reprocessing.

New hydrogels nanocomposites, based on iminoboronate hydrogels and ZnO nanoparticles (ZnO-NPs), were obtained and characterised in order to develop a new class of disinfectants able to fight the nosocomial infections produced by duodenoscopes investigation procedures. The formation of the imine linkages between chitosan and the aldehyde was demonstrated using NMR and FTIR spectroscopy, while the supramolecular architecture of the developed systems was evaluated via wide-angle X-ray diffraction and polarised optical microscopy. The morphological characterisation of the systems via scanning electron microscopy revealed the highly porous structure of the materials, in which no ZnO agglomeration could be observed, indicating the very fine and homogenous encapsulation of the nanoparticles into the hydrogels. The newly synthetised hydrogels nanocomposites was proven to have synergistic antimicrobial properties, being very efficient as disinfectants against reference strains as: Enterococcus faecalis, Klebsiella pneumoniae, and Candida albicans.

New Smart Bioactive and Biomimetic Chitosan-Based Hydrogels for Wounds Care Management.

Wound management represents a continuous challenge for health systems worldwide, considering the growing incidence of wound-related comorbidities, such as diabetes, high blood pressure, obesity, and autoimmune diseases. In this context, hydrogels are considered viable options since they mimic the skin structure and promote autolysis and growth factor synthesis. Unfortunately, hydrogels are associated with several drawbacks, such as low mechanical strength and the potential toxicity of byproducts released after crosslinking reactions. To overcome these aspects, in this study new smart chitosan (CS)-based hydrogels were developed, using oxidized chitosan (oxCS) and hyaluronic acid (oxHA) as nontoxic crosslinkers. Three active product ingredients (APIs) (fusidic acid, allantoin, and coenzyme Q10), with proven biological effects, were considered for inclusion in the 3D polymer matrix. Therefore, six API-CS-oxCS/oxHA hydrogels were obtained. The presence of dynamic imino bonds in the hydrogels' structure, which supports their self-healing and self-adapting properties, was confirmed by spectral methods. The hydrogels were characterized by SEM, swelling degree, pH, and the internal organization of the 3D matrix was studied by rheological behavior. Moreover, the cytotoxicity degree and the antimicrobial effects were also investigated. In conclusion, the developed API-CS-oxCS/oxHA hydrogels have real potential as smart materials in wound management, based on their self-healing and self-adapting properties, as well as on the benefits of APIs.

Cryogel System Based on Poly(vinyl alcohol)/Poly(ethylene brassylate-co-squaric acid) Platform with Dual Bioactive Activity.

The inability to meet and ensure as many requirements as possible is fully justified by the continuous interest in obtaining new multifunctional materials. A new cryogel system based on poly(vinyl alcohol) (PVA) and poly(ethylene brassylate-co-squaric acid) (PEBSA) obtained by repeated freeze-thaw processes was previously reported and used for the incorporation of an antibacterial essential oil-namely, thymol (Thy). Furthermore, the present study aims to confer antioxidant properties to the PVA/PEBSA_Thy system by encapsulating α-tocopherol (α-Tcp), targeting a double therapeutic effect due to the presence of both bioactive compounds. The amphiphilic nature of the PEBSA copolymer allowed for the encapsulation of both Thy and α-Tcp, via an in situ entrapment method. The new PVA/PEBSA_Thy_α-Tcp systems were characterized in terms of their influence on the composition, network morphology and release profiles, as well as their antimicrobial and antioxidant properties. The study underlined the cumulative antioxidant efficiency of Thy and α-Tcp, which in combination with the PEBSA copolymer have a synergistic effect (97.1%). We believe that the convenient and simple strategy offered in this study increases applicability for these new PVA/PEBSA_Thy_α-Tcp cryogel systems.

New Hydrogels and Formulations Based on Piperonyl-Imino-Chitosan Derivatives.

Candida infections have been always a serious healcare related problem. The present study reports the preparation of hydrogels and formulations based on piperonyl-imino-chitosan derivatives and Amphotericin B drug for the treatment of Candida infections. The hydrogels were obtained by the imination reaction of chitosan with piperonal monoaldehyde, followed by the self-assembling of the resulted imines, while the formulations were obtained by an in situ hydrogelation method of chitosan with piperonal in the presence of Amphotericin B antifungal drug. The structural characterization of both hydrogels and formulations by Fourier transform infrared spectroscopy and Nuclear magnetic resonance spectroscopy revealed the formation of imine units between the reagents, while their supramolecular characterization using polarized optical microscopy and wide angle X-ray diffraction demonstrated that hydrophilic/hydrophobic segregation is the process which governed the formation of gel like systems. The systems were further investigated from the point of view of their further applications revealing that they were biodegradable, presented high swelling ability and were able to release the antifungal drug in a sustained manner, presenting promising antifungal activity against five Candida strains.

Temperature Induced Gelation and Antimicrobial Properties of Pluronic F127 Based Systems.

Different formulations containing Pluronic F127 and polysaccharides (chitosan, sodium alginate, gellan gum, and κ-carrageenan) were investigated as potential injectable gels that behave as free-flowing liquid with reduced viscosity at low temperatures and displayed solid-like properties at 37 °C. In addition, ZnO nanoparticles, lysozyme, or curcumin were added for testing the antimicrobial properties of the thermal-sensitive gels. Rheological investigations evidenced small changes in transition temperature and kinetics of gelation at 37 °C in presence of polysaccharides. However, the gel formation is very delayed in the presence of curcumin. The antimicrobial properties of Pluronic F127 gels are very modest even by adding chitosan, lysozyme, or ZnO nanoparticles. A remarkable enhancement of antimicrobial activity was observed in the presence of curcumin. Chitosan addition to Pluronic/curcumin systems improves their viscoelasticity, antimicrobial activity, and stability in time. The balance between viscoelastic and antimicrobial characteristics needs to be considered in the formulation of Pluronic F127 gels suitable for biomedical and pharmaceutical applications.

Quaternized chitosan/chitosan nanofibrous mats: An approach toward bioactive materials for tissue engineering and regenerative medicine.

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.

Surface Degradation of DGEBA Epoxy Resins Cured with Structurally Different Amine Hardeners: Effects of UV Radiation.

In this study, the effects of three diamine curing agents (aromatic, cycloaliphatic, aliphatic) on the photochemical behavior of bisphenol A diglycidyl ether networks were comparatively examined. In order to monitor structural changes and study the curing agents' action mode, the cured epoxy resins were characterized before and after photoirradiation by means of Fourier-transform infrared spectroscopy, contact angle, differential scanning calorimetry, scanning electron microscopy, and energy-dispersive X-ray analysis, mass loss, and color modification measurements. Water absorption tests were also conducted. The cured epoxy resins are to be used in different multicomponent polymer materials for outdoor protection. The presence of the cycloaliphatic hardener led to reduced water absorption, and after UV irradiation, an increase in the glass transition temperature and lowest mass loss of the corresponding cured epoxy resin compared to the ones cured with aromatic and aliphatic hardener.

One-Step Preparation of Carboxymethyl Cellulose-Phytic Acid Hydrogels with Potential for Biomedical Applications.

Hydrogels based on natural, biodegradable materials have gained considerable interest in the medical field due to their improved drug delivery profiles and tissue-mimicking architecture. In this regard, this study was devoted to the preparation and characterization of new physically crosslinked hydrogels based on carboxymethyl cellulose and an unconventional crosslinking agent, phytic acid. Phytic acid, in addition to its antioxidant and antibacterial effects, can improve the biological properties and stability of gels, without adding toxicity. Fourier transform infrared (FTIR) spectroscopy, rheological studies and thermal analysis confirmed the hydrogel formation. The influence of the ratio between the cellulose derivative and the crosslinker upon the morphological structure and water uptake was evidenced by scanning electron microscopy (SEM) and swelling measurements in simulated body fluids. Furthermore, procaine was entrapped within the hydrogels and used as a model drug for in vitro studies, which highlighted the dependence of the drug release on the phytic acid content of the matrix. The materials demonstrated antibacterial effects against Escherichia coli and Staphylococcus aureus bacteria. The biocompatibility was assessed on fibroblast cells, and according to our results, hydrogels can improve cell viability highlighting the potential of these systems as therapeutic scaffolds for skin tissue engineering.

Development of a new polymer network system carrier of essential oils.

The study presents the development of a new copolymacrolactone structure based on ethylene brassylate (EB) and squaric acid (SA) with different ratios between comonomers. The new system was tested as a network for essential oils encapsulation. The structure of the copolymers was confirmed by spectroscopic investigations and correlated in interdependence with the comonomers content. The interfacial characteristics of the poly(ethylene brassylate-co-squaric acid) copolymers were determined, and the transition from a moderate hydrophilic surface towards a hydrophobic region by increasing the molar content of SA comonomer was highlighted. The affinity for hydrophobic substances of the synthesised macromolecular compounds was used in a process of encapsulation of thymol (Thy) and carvacrol (CC). The newly prepared bioactive compounds were characterised by in vivo biocompatibility tests, and antimicrobial activity, Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC).

Effect of Hardener Type on the Photochemical and Antifungal Performance of Epoxy and Oligophosphonate S-IPNs.

Due to their highly reactive character and multiple crosslinking capacity, epoxy resins are one of the worldwide market-dominating classes of thermosetting polymers and are present in a wide range of technical applications, including structural adhesives, coatings and polymer matrices for composite materials. Despite their excellent features, epoxy resins are known to be highly flammable and possess low thermal stability and a brittle character and crack easily under impact forces. An efficient approach towards eliminating such drawbacks resides in obtaining epoxy-based semi-interpenetrating polymer networks, which possess excellent control over the morphology. The article describes the comparative effect of three hardeners (aromatic, cycloaliphatic and aliphatic) in the presence of an oligophosphonate (-R-O-PO(C6H5)-O-) (2 wt.% phosphorus) on the photochemical, fire and antifungal performance of bisphenol A diglycidyl ether semi-interpenetrating polymer networks. The networks are designed as future potential outdoor protective coatings for different substrates. The fire resistance capacity of the networks was undertaken with microscale combustion calorimetry before and after photochemical aging. Structural changes during photoirradiation were monitored via color modification studies, Fourier-transform infrared spectroscopy, differential scanning calorimetry, morphological assessment through scanning electron microscopy and mass loss measurements in order to propose the action mode of the hardeners and the oligophosphonate on the material properties. Microbiological testing was also undertaken with the aid of three specific wood decaying fungi as a first substrate.

Does Protocatechuic Acid Affect the Activity of Commonly Used Antibiotics and Antifungals?

The aim of this study is to evaluate the efficiency of protocatechuic acid (PCA) in enhancing the commonly used drugs used to fight against nosocomial infection. These drugs are represented by routinely used antibiotics, synthetic chemotherapeutic agents with an antimicrobial spectrum, and antifungals. Three concentrations of PCA were added to 12 types of commercial disks used for antibiotic and antifungal susceptibility and tested against bacterial and yeast strains represented by Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans. The results proved that PCA increased up to 50% of the antibacterial activity, especially that of levofloxacin against Staphylococcus aureus and Escherichia coli. These formulations will lead to new drug design ideas containing a smaller amount of antibiotics with the same effectiveness.