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.

X-ray and UV Irradiation-Induced Reactive Oxygen Species Mediated Antibacterial Activity in Fe and Pt Nanoparticle-Decorated Si-Doped TiCaCON Films.

Bone implants with biocompatibility and the ability to biomineralize and suppress infection are in high demand. The occurrence of early infections after implant placement often leads to repeated surgical treatment due to the ineffectiveness of antibiotic therapy. Therefore, an extremely attractive solution to this problem would be the ability to initiate bacterial protection of the implant by an external influence. Here, we present a proof-of-concept study based on the generation of reactive oxygen species (ROS) by the implant surface in response to X-ray irradiation, including through a layer of 3 mm adipose tissue, providing bactericidal protection. The effect of UV and X-ray irradiation of the implant surface on the ROS formation and the associated bactericidal activity was compared. The focus of our study was light-sensitive Si-doped TiCaCON films decorated with Fe and Pt nanoparticles (NPs) with photoinduced antibacterial activity mediated by ROS. In the visible and infrared range of 300-1600 nm, the films absorb more than 60% of the incident light. The high light absorption capacity of TiO2/TiC and TiO2/TiN heterostructures was demonstrated by density functional theory calculations. After short-term (5-10 s) low-dose X-ray irradiation, the films generated significantly more ROS than after UV illumination for 1 h. The Fe/TiCaCON-Si films showed enhanced biomineralization capacity, superior cytocompatibility, and excellent antibacterial activity against multidrug-resistant hospital Escherichia coli U20 and K261 strains and methicillin-resistant Staphylococcus aureus MW2 strain. Our study clearly demonstrates that oxidized Fe NPs are a promising alternative to the widely used Ag NPs in antibacterial coatings, and X-rays can potentially be used in ROS-regulating therapy to suppress inflammation in case of postimplant complications.

Osteoconductive, Osteogenic, and Antipathogenic Plasma Electrolytic Oxidation Coatings on Titanium Implants with BMP-2.

We report a one-pot plasma electrolytic oxidation (PEO) strategy for forming a multi-element oxide layer on the titanium surface using complex electrolytes containing Na2HPO4, Ca(OH)2, (NH2)2CO, Na2SiO3, CuSO4, and KOH compounds. For even better bone implant ingrowth, PEO coatings were additionally loaded with bone morphogenetic protein-2 (BMP-2). The samples were tested in vivo in a mouse craniotomy model. Tests for bactericidal and fungicidal activity were carried out using clinically isolated multi-drug-resistant Escherichia coli (E. coli) K261, E. coli U20, methicillin-resistant Staphylococcus aureus (S. aureus) CSA154 bacterial strains, and Neurospora crassa (N. crassa) and Candida albicans (C. albicans) D2528/20 fungi. The PEO-Cu coating effectively inactivated both Gram-positive and Gram-negative bacteria at low concentrations of Cu2+ ions: minimal bactericidal concentration for E. coli and N. crassa (99.9999%) and minimal inhibitory concentration (99.0%) for S. aureus were 5 ppm. For all studied bacterial and fungal strains, PEO-Cu coating completely prevented the formation of bacterial and fungal biofilms. PEO and PEO-Cu coatings demonstrated bone remodeling and moderate osteoconductivity in vivo, while BMP-2 significantly enhanced osteoconduction and osteogenesis. The obtained results are encouraging and indicate that Ti-based materials with PEO coatings loaded with BMP-2 can be widely used in customized medicine as implants for orthopedics and cranio-maxillofacial surgery.

Structure Formation and Tribological Properties of Mo-Si-B-Hf Electrospark Coatings Based on Mo2Ni3Si Laves Phase.

Coatings were produced on the EP741NP nickel alloy substrates by electrospark deposition (ESD) in argon using an MoSi2-MoB-HfB2 electrode. In situ high-resolution transmission electron microscopy and X-ray diffraction analysis studies have identified the temperature above which the strengthening Mo2Ni3Si Laves phase is formed in the coatings. At 25 °C, the coatings with a predominant content of the Laves phase are characterized by enhanced wear resistance, as well as a lower coefficient of friction compared to the non-annealed coatings containing binary silicides. At 700 °C, the EP741NP substrate was characterized by the lowest friction coefficient (Ktr = 0.35), and its wear was approximately at the same level as the wear of both coatings.

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%.

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).