Self-Sanitizing Polycaprolactone Electrospun Nanofiber Membrane with Ag Nanoparticles.

The objective of this research was to develop an environment-friendly and scalable method for the production of self-sanitizing electrospun nanofibers. This was achieved by immobilizing silver nanoparticles (Ag NPs) onto plasma-treated surfaces of biodegradable polycaprolactone (PCL) nanofibers. The plasma deposited polymer layer containing carboxyl groups played a critical role in providing a uniform distribution of Ag NPs on the nanofiber surface. Ag ions were absorbed by electrostatic interaction and then reduced under the action of UV-light. The concentration and release of Ag ions were analyzed using the EDXS/XPS and ICP AES methods, respectively. Although high levels of Ag ions were detected after 3 h of immersion in water, the material retained a sufficient amount of silver nanoparticles on the surface (~2.3 vs. 3.5 at.% as determined by XPS), and the release rate subsequently decreased over the next 69 h. The antipathogenic properties of PCL-Ag were tested against gram-negative and gram-positive bacteria, fungi, and biofilm formation. The results showed that the PCL-Ag nanofibers exhibit significant antimicrobial activity against a wide range of microorganisms, including those that cause human infections. The incorporation of Ag NPs into PCL nanofibers resulted in a self-sanitizing material that can be used in variety of applications, including wound dressings, water treatment, and air filtration. The development of a simple, scalable, and environmentally friendly method for the fabrication of these nanofibers is essential to ensure their widespread use in various industries. The ability to control the concentration and release rate of Ag ions in the PCL nanofibers will be critical to optimize their efficacy while minimizing their potential toxicity to human cells and the environment.

Immobilization and Release of Platelet-Rich Plasma from Modified Nanofibers Studied by Advanced X-ray Photoelectron Spectroscopy Analyses.

Platelet-rich Plasma (PRP) is an ensemble of growth factors, extracellular matrix components, and proteoglycans that are naturally balanced in the human body. In this study, the immobilization and release of PRP component nanofiber surfaces modified by plasma treatment in a gas discharge have been investigated for the first time. The plasma-treated polycaprolactone (PCL) nanofibers were utilized as substrates for the immobilization of PRP, and the amount of PRP immobilized was assessed by fitting a specific X-ray Photoelectron Spectroscopy (XPS) curve to the elemental composition changes. The release of PRP was then revealed by measuring the XPS after soaking nanofibers containing immobilized PRP in buffers of varying pHs (4.8; 7.4; 8.1). Our investigations have proven that the immobilized PRP would continue to cover approximately fifty percent of the surface after eight days.

Synergistic Catalytic Effect of Ag and MgO Nanoparticles Supported on Defective BN Surface in CO Oxidation Reaction.

Micron-sized supports of catalytically active nanoparticles (NPs) can become a good alternative to nanocarriers if their structure is properly tuned. Here, we show that a combination of simple and easily scalable methods, such as defect engineering and polyol synthesis, makes it possible to obtain Ag and MgO nanoparticles supported on defective hexagonal BN (h-BN) support with high catalytic activity in the CO oxidation reaction. High-temperature annealing in air of Mg-containing (<0.2 at.%) h-BN micropellets led to surface oxidation, the formation of hexagonal-shaped surface defects, and defect-related MgO NPs. The enhanced catalytic activity of Ag/MgO/h-BN materials is attributed to the synergistic effect of h-BN surface defects, ultrafine Ag and MgO NPs anchored at the defect edges, and MgO/Ag heterostructures. In addition, theoretical simulations show a shift in the electron density from metallic Ag towards MgO and the associated decrease in the negative charge of oxygen adsorbed on the Ag surface, which positively affects the catalytic activity of the Ag/MgO/h-BN material.

Electrospun Polycaprolactone/ZnO Nanocomposite Membranes with High Antipathogen Activity.

The spread of bacterial, fungal, and viral diseases by airborne aerosol flows poses a serious threat to human health, so the development of highly effective antibacterial, antifungal and antiviral filters to protect the respiratory system is in great demand. In this study, we developed ZnO-modified polycaprolactone nanofibers (PCL-ZnO) by treating the nanofiber surface with plasma in a gaseous mixture of Ar/CO2/C2H4 followed by the deposition of ZnO nanoparticles (NPs). The structure and chemical composition of the composite fibers were characterized by SEM, TEM, EDX, FTIR, and XPS methods. We demonstrated high material stability. The mats were tested against Gram-positive and Gram-negative pathogenic bacteria and pathogenic fungi and demonstrated high antibacterial and antifungal activity.

Effect of h-BN Support on Photoluminescence of ZnO Nanoparticles: Experimental and Theoretical Insight.

Herein we report a simple and easily scalable method for fabricating ZnO/h-BN composites with tunable photoluminescence (PL) characteristics. The h-BN support significantly enhances the ultraviolet (UV) emission of ZnO nanoparticles (NPs), which is explained by the ZnO/h-BN interaction and the change in the electronic structure of the ZnO surface. When h-BN NPs are replaced with h-BN microparticles, the PL in the UV region increases, which is accompanied by a decrease in visible light emission. The dependence of the PL properties of ZnO NPs on the thickness of h-BN carriers, observed for the first time, is explained by a change in the dielectric constant of the support. A quantum chemical analysis of the influence of the h-BN thickness on the electron density redistribution at the wZnO/h-BN interface and on the optical properties of the wZnO/h-BN composites was carried out. Density functional theory (DFT) calculations show the appearance of hybridization at the h-BN/wZnO interface and an increase in the intensity of absorption peaks with an increase in the number of h-BN layers. The obtained results open new possibilities for controlling the properties of ZnO/h-BN heterostructures for various optical applications.

Antibacterial, UV-Protective, Hydrophobic, Washable, and Heat-Resistant BN-Based Nanoparticle-Coated Textile Fabrics: Experimental and Theoretical Insight.

The use of nanoparticles (NPs) to modify the surface of cotton fabric is a promising approach to endowing the material with a set of desirable characteristics that can significantly expand the functionality, wear comfort, and service life of textile products. Herein, two approaches to modifying the surface of hexagonal boron nitride (h-BN) NPs with a hollow core and a smooth surface by treatment with maleic anhydride (MA) and diethylene triamine (DETA) were studied. The DETA and MA absorption on the surface of h-BN and the interaction of surface-modified h-NPs with cellulose as the main component of cotton were modeled using density functional theory with the extended Perdew-Burke-Ernzerhof functional. Theoretical modeling showed that the use of DETA as a binder agent can increase the adhesion strength of BN NPs to textile fabric due to the simultaneous hydrogen bonds with cellulose and BN. Due to the difference in zeta potentials (-38.4 vs -25.8 eV), MA-modified h-BN NPs form a stable suspension, while DETA-modified BN NPs tend to agglomerate. Cotton fabric coated with surface-modified NPs exhibits an excellent wash resistance and high hydrophobicity with a water contact angle of 135° (BN-MA) and 146° (BN-DETA). Compared to the original textile material, treatment with MA- and DETA-modified h-BN NPs increases heat resistance by 10% (BN-MA fabric) and 15% (BN-DETA fabric). Cotton fabrics coated with DETA- and MA-modified BN NPs show enhanced antibacterial activity against Escherichia coli U20 and Staphylococcus aureus strains and completely prevent the formation of an E. coli biofilm. The obtained results are important for the further development of fabrics for sports and medical clothing as well as wound dressings.

A New Insight into the Mechanisms Underlying the Discoloration, Sorption, and Photodegradation of Methylene Blue Solutions with and without BNOx Nanocatalysts.

Methylene blue (MB) is widely used as a test material in photodynamic therapy and photocatalysis. These applications require an accurate determination of the MB concentration as well as the factors affecting the temporal evolution of the MB concentration. Optical absorbance is the most common method used to estimate MB concentration. This paper presents a detailed study of the dependence of the optical absorbance of aqueous methylene blue (MB) solutions in a concentration range of 0.5 to 10 mg·L-1. The nonlinear behavior of optical absorbance as a function of MB concentration is described for the first time. A sharp change in optical absorption is observed in the range of MB concentrations from 3.33 to 4.00 mg·L-1. Based on the analysis of the absorption spectra, it is concluded that this is due to the formation of MB dimers and trimers in the specific concentration range. For the first time, a strong, thermally induced discoloration effect of the MB solution under the influence of visible and sunlight was revealed: the simultaneous illumination and heating of MB solutions from 20 to 80 °C leads to a twofold decrease in the MB concentration in the solution. Exposure to sunlight for 120 min at a temperature of 80 °C led to the discoloration of the MB solution by more than 80%. The thermally induced discoloration of MB solutions should be considered in photocatalytic experiments when tested solutions are not thermally stabilized and heated due to irradiation. We discuss whether MB is a suitable test material for photocatalytic experiments and consider this using the example of a new photocatalytic material-boron oxynitride (BNOx) nanoparticles-with 4.2 and 6.5 at.% of oxygen. It is shown that discoloration is a complex process and includes the following mechanisms: thermally induced MB photodegradation, MB absorption on BNOx NPs, self-sensitizing MB photooxidation, and photocatalytic MB degradation. Careful consideration of all these processes makes it possible to determine the photocatalytic contribution to the discoloration process when using MB as a test material. The photocatalytic activity of BNOx NPs containing 4.2 and 6.5 at.% of oxygen, estimated at ~440 µmol·g-1·h-1. The obtained results are discussed based on the results of DFT calculations considering the effect of MB sorption on its self-sensitizing photooxidation activity. A DFT analysis of the MB sorption capacity with BNOx NPs shows that surface oxygen defects prevent the sorption of MB molecules due to their planar orientation over the BNOx surface. To enhance the sorption capacity, surface oxygen defects should be eliminated.

Recent Progress in Fabrication and Application of BN Nanostructures and BN-Based Nanohybrids.

Due to its unique physical, chemical, and mechanical properties, such as a low specific density, large specific surface area, excellent thermal stability, oxidation resistance, low friction, good dispersion stability, enhanced adsorbing capacity, large interlayer shear force, and wide bandgap, hexagonal boron nitride (h-BN) nanostructures are of great interest in many fields. These include, but are not limited to, (i) heterogeneous catalysts, (ii) promising nanocarriers for targeted drug delivery to tumor cells and nanoparticles containing therapeutic agents to fight bacterial and fungal infections, (iii) reinforcing phases in metal, ceramics, and polymer matrix composites, (iv) additives to liquid lubricants, (v) substrates for surface enhanced Raman spectroscopy, (vi) agents for boron neutron capture therapy, (vii) water purifiers, (viii) gas and biological sensors, and (ix) quantum dots, single photon emitters, and heterostructures for electronic, plasmonic, optical, optoelectronic, semiconductor, and magnetic devices. All of these areas are developing rapidly. Thus, the goal of this review is to analyze the critical mass of knowledge and the current state-of-the-art in the field of BN-based nanomaterial fabrication and application based on their amazing properties.

Ag-Contained Superabsorbent Curdlan-Chitosan Foams for Healing Wounds in a Type-2 Diabetic Mice Model.

This study focused on the synthesis and characterization of pure curdlan-chitosan foams (CUR/CS), as well as foams containing Ag nanoparticles (CUR/CS/Ag), and their effect on the skin repair of diabetic mice (II type). The layer of antibacterial superabsorbent foam provides good oxygenation, prevents bacterial infection, and absorbs exudate, forming a soft gel (moist environment). These foams were prepared from a mixture of hydrolyzed curdlan and chitosan by lyophilization. To enhance the antibacterial properties, an AgNO3 solution was added to the curdlan/chitosan mixture during the polymerization and was then reduced by UV irradiation. The membranes were further investigated for their structure and composition using optical microscopy, scanning electron microscopy, energy-dispersive spectroscopy, FT-IR spectroscopy, and XPS analysis and modeling. In vivo tests demonstrated that CUR/CS/Ag significantly boosted the regeneration process compared with pure CUR/CS and the untreated control.

Surface modification and antibacterial properties of superelastic Ti-Zr-based alloys for medical application.

To date, significant progress has been achieved in the development of biomedical superelastic Ti-based alloys with high mechanical properties. In view of the high probability of implant-associated infection, an urgent task is to impart bactericidal properties to the material. Herein, advanced superelastic Ti-18Zr-15Nb alloys were surface-etched in a piranha solution, and then Ag nanoparticles were deposited on their surface using a polyol process. This led to the formation of a porous surface layer with a thickness of approximately 100 nm and pore size of less than 20 nm, filled with metallic Ag nanoparticles with an average size of 14 nm. The surface-modified samples showed superior antibacterial activity against E.coli cells. The enhanced bactericidal efficiency is explained by the combination of a higher rate of Ag+ ions release and direct contact of E.coli cells with Ag nanoparticles.

Amorphous MoSxOy/h-BNxOy Nanohybrids: Synthesis and Dye Photodegradation.

Molybdenum sulfide is a very promising catalyst for the photodegradation of organic pollutants in water. Its photocatalytic activity arises from unsaturated sulfur bonds, and it increases with the introduction of structural defects and/or oxygen substitutions. Amorphous molybdenum sulfide (a-MoSxOy) with oxygen substitutions has many active sites, which create favorable conditions for enhanced catalytic activity. Here we present a new approach to the synthesis of a-MoSxOy and demonstrate its high activity in the photodegradation of the dye methylene blue (MB). The MoSxOy was deposited on hexagonal boron oxynitride (h-BNO) nanoflakes by reacting h-BNO, MoCl5, and H2S in dimethylformamide (DMF) at 250 °C. Both X-ray diffraction analysis and high-resolution TEM show the absence of crystalline order in a-MoSxOy. Based on the results of Raman and X-ray photoelectron spectroscopy, as well as analysis by the density functional theory (DFT) method, a chain structure of a-MoSxOy was proposed, consisting of MoS3 clusters with partial substitution of sulfur by oxygen. When a third of the sulfur atoms are replaced with oxygen, the band gap of a-MoSxOy is approximately 1.36 eV, and the valence and conduction bands are 0.74 eV and -0.62 eV, respectively (relative to a standard hydrogen electrode), which satisfies the conditions of photoinduced splitting of water. When illuminated with a mercury lamp, a-MoSxOy/h-BNxOy nanohybrids have a specific mass activity in MB photodegradation of approximately 5.51 mmol g-1 h-1, which is at least four times higher than so far reported values for nonmetal catalysts. The photocatalyst has been shown to be very stable and can be reused.

Ag-Doped and Antibiotic-Loaded Hexagonal Boron Nitride Nanoparticles as Promising Carriers to Fight Different Pathogens.

Utilization of antibacterial components-conjugated nanoparticles (NPs) is emerging as an attractive strategy for combating various pathogens. Herein, we demonstrate that Ag/BN NPs and antibiotic-loaded BN and Ag/BN nanoconjugates are promising carriers to fight bacterial and fungal infections. Extensive biological tests included two types of Gram-positive methicillin-resistant Staphylococcus aureus strains (B8469 and MW2), two types of Gram-negative Pseudomonas aeruginosa strains (ATCC27853 and B1307/17), and 47 types of Escherichia coli strains (including 41 multidrug-resistant ones), as well as five types of fungal cultures: Candida albicans (candidiasis-thrush) ATCC90028 and ATCC24433, Candida parapsilosis ATCC90018, Candida auris CBS109113, and Neurospora crassa wt. We have demonstrated that, even within a single genus Escherichia, there are many hospital E. coli strains with multi-drug resistance to different antibiotics. Gentamicin-loaded BN NPs have high bactericidal activity against S. aureus, P. aeruginosa, and 38 types of the E. coli strains. For the rest of the tested E. coli strains, the Ag nanoparticle-containing nanohybrids have shown superior bactericidal efficiency. The Ag/BN nanohybrids and amphotericin B-loaded BN and Ag/BN NPs also reveal high fungicidal activity against C. albicans, C. auris, C. parapsilosis, and N. crassa cells. In addition, based on the density functional theory calculations, the nature of antibiotic-nanoparticle interaction, the sorption capacity of the BN and Ag/BN nanohybrids for gentamicin and amphotericin B, and the most energetically favorable positions of the drug molecules relative to the carrier surface, which lead to lowest binding energies, have been determined. The obtained results clearly show high therapeutic potential of the antibiotic-loaded Ag/BN nanocarriers providing a broad bactericidal and fungicidal protection against all of the studied pathogens.

Comparison of Different Approaches to Surface Functionalization of Biodegradable Polycaprolactone Scaffolds.

Due to their good mechanical stability compared to gelatin, collagen or polyethylene glycol nanofibers and slow degradation rate, biodegradable poly-ε-caprolactone (PCL) nanofibers are promising material as scaffolds for bone and soft-tissue engineering. Here, PCL nanofibers were prepared by the electrospinning method and then subjected to surface functionalization aimed at improving their biocompatibility and bioactivity. For surface modification, two approaches were used: (i) COOH-containing polymer was deposited on the PCL surface using atmospheric pressure plasma copolymerization of CO2 and C2H4, and (ii) PCL nanofibers were coated with multifunctional bioactive nanostructured TiCaPCON film by magnetron sputtering of TiC-CaO-Ti3POx target. To evaluate bone regeneration ability in vitro, the surface-modified PCL nanofibers were immersed in simulated body fluid (SBF, 1×) for 21 days. The results obtained indicate different osteoblastic and epithelial cell response depending on the modification method. The TiCaPCON-coated PCL nanofibers exhibited enhanced adhesion and proliferation of MC3T3-E1 cells, promoted the formation of Ca-based mineralized layer in SBF and, therefore, can be considered as promising material for bone tissue regeneration. The PCL-COOH nanofibers demonstrated improved adhesion and proliferation of IAR-2 cells, which shows their high potential for skin reparation and wound dressing.