Polycaprolactone Nanofibers Functionalized by Fibronectin/Gentamicin and Implanted Silver for Enhanced Antibacterial Properties, Cell Adhesion, and Proliferation.

Novel nanomaterials used for wound healing should have many beneficial properties, including high biological and antibacterial activity. Immobilization of proteins can stimulate cell migration and viability, and implanted Ag ions provide an antimicrobial effect. However, the ion implantation method, often used to introduce a bactericidal element into the surface, can lead to the degradation of vital proteins. To analyze the surface structure of nanofibers coated with a layer of plasma COOH polymer, fibronectin/gentamicin, and implanted with Ag ions, a new X-ray photoelectron spectroscopy (XPS) fitting method is used for the first time, allowing for a quantitative assessment of surface biomolecules. The results demonstrated noticeable changes in the composition of fibronectin- and gentamicin-modified nanofibers upon the introduction of Ag ions. Approximately 60% of the surface chemistry has changed, mainly due to an increase in hydrocarbon content and the introduction of up to 0.3 at.% Ag. Despite the significant degradation of fibronectin molecules, the biological activity of Ag-implanted nanofibers remained high, which is explained by the positive effect of Ag ions inducing the generation of reactive oxygen species. The PCL nanofibers with immobilized gentamicin and implanted silver ions exhibited very significant antipathogen activity to a wide range of Gram-positive and Gram-negative strains. Thus, the results of this work not only make a significant contribution to the development of new hybrid fiber materials for wound dressings but also demonstrate the capabilities of a new XPS fitting methodology for quantitative analysis of surface-related proteins and antibiotics.

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.

Amorphous/Nanocrystalline High-Entropy CoCrFeNiTix Thin Films with Low Thermal Coefficient of Resistivity Obtained via Magnetron Deposition.

High-entropy alloys are promising materials for novel thin-film resistors since they have high resistivity and a low-temperature coefficient of resistivity (TCR). In this work, a new high-entropy thin-film CoCrFeNiTix was deposited on a Si/SiO2 substrate by means of magnetron sputtering of the multi-component target produced by hot pressing of the powder mixture. The samples possessed a thickness of 130-230 nm and an amorphous atomic structure with nanocrystallite traces. This structure persisted after being annealed up to 400 °C, which was confirmed using X-ray and electron diffraction. The film had a single-phase structure with a smooth surface and a uniform distribution of all elements. The obtained film served for microresistor elaboration, which was produced using the lithography technique and tested in a temperature range from -60 °C up to 200 °C. Resistivity at room temperature was estimated as 2.37 µOhm·m. The results have demonstrated that TCR depends on temperature according to the simple linear law in a range from -60 °C up to 130 °C, changing its value from -78 ppm/°C at low temperatures to -6.6 ppm/°C at 130 °C. Such characteristics show the possibility of using these high-entropy alloy films for resistive elements in contemporary and future micro-electronic devices.

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.

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.

Biodegradable Nanohybrid Materials as Candidates for Self-Sanitizing Filters Aimed at Protection from SARS-CoV-2 in Public Areas.

The COVID-19 pandemic has raised the problem of efficient, low-cost materials enabling the effective protection of people from viruses transmitted through the air or via surfaces. Nanofibers can be a great candidate for efficient air filtration due to their structure, although they cannot protect from viruses. In this work, we prepared a wide range of nanofibrous biodegradable samples containing Ag (up to 0.6 at.%) and Cu (up to 20.4 at.%) exhibiting various wettability. By adjusting the magnetron current (0.3 A) and implanter voltage (5 kV), the deposition of TiO2 and Ag+ implantation into PCL/PEO nanofibers was optimized in order to achieve implantation of Ag+ without damaging the nanofibrous structure of the PCL/PEO. The optimal conditions to implant silver were achieved for the PCL-Ti0.3-Ag-5kV sample. The coating of PCL nanofibers by a Cu layer was successfully realized by magnetron sputtering. The antiviral activity evaluated by widely used methodology involving the cultivation of VeroE6 cells was the highest for PCL-Cu and PCL-COOH, where the VeroE6 viability was 73.1 and 68.1%, respectively, which is significantly higher compared to SARS-CoV-2 samples without self-sanitizing (42.8%). Interestingly, the samples with implanted silver and TiO2 exhibited no antiviral effect. This difference between Cu and Ag containing nanofibers might be related to the different concentrations of ions released from the samples: 80 µg/L/day for Cu2+ versus 15 µg/L/day for Ag+. The high antiviral activity of PCL-Cu opens up an exciting opportunity to prepare low-cost self-sanitizing surfaces for anti-SARS-CoV-2 protection and can be essential for air filtration application and facemasks. The rough cost estimation for the production of a biodegradable nanohybrid PCL-Cu facemask revealed ~$0.28/piece, and the business case for the production of these facemasks would be highly positive, with an Internal Rate of Return of 34%.

Structure and Properties of Zr-Mo-Si-B-(N) Hard Coatings Obtained by d.c. Magnetron Sputtering of ZrB2-MoSi2 Target.

Coatings in a Zr-Mo-Si-B-N system were deposited by the magnetron sputtering of ZrB2-MoSi2 targets in argon and nitrogen. The structure of the coatings was investigated using scanning electron microscopy, X-ray diffraction, energy-dispersive spectroscopy, and glow-discharge optical emission spectroscopy. Mechanical and tribological properties were measured using nanoindentation and pin-on-disc testing. Oxidation resistance and oxidation kinetics were estimated via annealing in air at 1000-1500 °C and precision weight measurements. We found that the coatings deposited in Ar demonstrate a superior combination of properties, including hardness of 36 GPa, elastic recovery of 84%, a friction coefficient of 0.6, and oxidation resistance at temperatures up to 1200 °C. High oxidation resistance is realized due to the formation of the protective (SiO2 + ZrO2)/SiO2 oxide layer, which inhibits the diffusion of oxygen into the coating.

FeZrN Films: Magnetic and Mechanical Properties Relative to the Phase-Structural State.

The paper presents results of investigation of Fe65.3-100Zr34.7-0N7.5-0 films prepared by dc magnetron deposition on glass substrates and subsequent 1-hour annealing at temperatures of 300-600 °C. The influence of the chemical and phase compositions and structure of the films, which were studied by TEM, SEM, XRD, and GDOES, on their mechanical properties determined by nanoindentation and static magnetic properties measured by VSM method is analyzed. The studied films exhibit the hardness within a range of 14-21 GPa, low elastic modulus (the value can reach 156 Gpa), and an elastic recovery of 55-83%. It was shown that the films are strong ferromagnets with the high saturation induction Bs (up to 2.1 T) and low coercive field Hc (as low as 40 A/m). The correlations between the magnetic and mechanical properties, on one hand, and the chemical composition of the films, their phase, and structural states as well, on the other hand, are discussed.

Manufacturing of Conductive, Wear-Resistant Nanoreinforced Cu-Ti Alloys Using Partially Oxidized Electrolytic Copper Powder.

Reactive powder composites Cu-(0-15%)TiH2 containing up to 5% native Cu2O were manufactured by high energy ball milling and then hot-pressed to produce bulk nanostructured copper-matrix alloys reinforced by Cu3Ti3O inclusions. Two high-energy ball-milling (HEBM) protocols were employed for the fabrication of Cu-Ti alloys: single-stage and two-stage ball milling, resulting in an order of magnitude refinement of TiH2 particles in the reactive mixtures. Single-stage HEBM processing led to the partial retention of Ti in the microstructure of hot-pressed specimens as the α-Ti phase and formation of fine-grained (100-200 nm) copper matrix interspersed with 5-20 nm Cu3Ti3O precipitates, whereas the two-stage HEBM led to the complete conversion of TiH2 into the Cu3Ti3O phase during the hot pressing but produced a coarser copper matrix (1-2 µm) with 0.1-0.2 µm wide polycrystalline Cu3Ti3O layers on the boundaries of Cu grains. The alloy produced using single-stage HEBM was characterized by the highest strength (up to 950 MPa) and electrical conductivity (2.6 × 107 Sm/m) as well as the lowest specific wear rate (1.1 × 10-5 mm3/N/m). The tribological performance of the alloy was enhanced by the formation of Cu3Ti3O microfibers in the wear debris, which reduced the friction coefficient against the Al2O3 counter-body. The potential applications of the developed alloys are briefly discussed.

Two-Layer Nanocomposite TiC-Based Coatings Produced by a Combination of Pulsed Cathodic Arc Evaporation and Vacuum Electro-Spark Alloying.

A novel two-stage technology combining vacuum electro-spark alloying (VESA) and pulsed cathodic arc evaporation (PCAE) was approbated for the deposition of TiC-based coatings in inert (Ar) and reactive (C2H4) atmospheres. The deposition was carried out using a TiC-NiCr-Eu2O3 electrode and 5140 steel substrates. Structural, elemental, and phase compositions of the deposited coatings were investigated by scanning electron microscopy, energy-dispersive spectrometry, and X-ray diffraction. The mechanical properties of the coatings were measured by nanoindentation using a 4 mN load. The tribological properties of the coatings were measured using the pin-on-disc setup in air and in distilled water at a 5 N load. The experimental data suggest that VESA coatings are characterized by surface defects, a hardness of 12.2 GPa, and a friction coefficient of 0.4. To ensure good adhesion between the VESA coating and the upper layer containing diamond-like carbon (DLC), an intermediate layer was deposited by PCAE in the Ar atmosphere. The intermediate layer had a hardness of up to 31 GPa. The upper layer of the coating ensured a low and stable friction coefficient of 0.2 and high wear resistance due to the formation of an sp2-sp3 bound carbon phase. Multilayer TiC-based coating with the upper DLC layer, in addition to high tribological properties, was characterized by the lowest corrosion current density (12 µÐ/cm2).

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.

Plasma Surface Polymerized and Biomarker Conjugated Boron Nitride Nanoparticles for Cancer-Specific Therapy: Experimental and Theoretical Study.

A new low-pressure plasma-based approach to activate the surface of BN nanoparticles (BNNPs) in order to facilitate the attachment of folate acid (FA) molecules for cancer-specific therapy is described. Plasma treatment of BNNPs (BNNPsPT) was performed in a radiofrequency plasma reactor using ethylene and carbon dioxide monomers. The carboxyl groups deposited on the surface of BNNPsPT were activated by N,N'-dicyclohexylcarbodiimide (DCC) and participated in the condensation reaction with ethylene diamine (EDA) to form a thin amino-containing layer (EDA-BNNPPT). Then, the DCC-activated FA was covalently bonded with BNNPsPT by a chemical reaction between amino groups of EDA-BNNPsPT and carboxyl groups of FA. Density functional theory calculations showed that the pre-activation of FA by DCC is required for grafting of the FA to the EDA-BNNPsPT. It was also demonstrated that after FA immobilization, the electronic characteristics of the pteridine ring remain unchanged, indicating that the targeting properties of the FA/EDA-BNNPsPT nanohybrids are preserved.