Surface modification of the laser powder bed-fused Ti-Zr-Nb scaffolds by dynamic chemical etching and Ag nanoparticles decoration.

Metallic lattice scaffolds are designed to mimic the architecture and mechanical properties of bone tissue and their surface compatibility is of primary importance. This study presents a novel surface modification protocol for metallic lattice scaffolds printed from a superelastic Ti-Zr-Nb alloy. This protocol consists of dynamic chemical etching (DCE) followed by silver nanoparticles (AgNP) decoration. DCE, using an 1HF + 3HNO3 + 12H2O23% based solution, was used to remove partially-fused particles from the surfaces of different as-built lattice structures (rhombic dodecahedron, sheet gyroid, and Voronoi polyhedra). Subsequently, an antibacterial coating was synthesized on the surface of the scaffolds by a controlled (20 min at a fixed volume flowrate of 500 mL/min) pumping of the functionalization solutions (NaBH4 (2 mg/mL) and AgNO3 (1 mg/mL)) through the porous structures. Following these treatments, the scaffolds' surfaces were found to be densely populated with Ag nanoparticles and their agglomerates, and manifested an excellent antibacterial effect (Ag ion release rate of 4-8 ppm) suppressing the growth of both E. coli and B. subtilis bacteria up to 99 %. The scaffold extracts showed no cytotoxicity and did not affect cell proliferation, indicating their safety for subsequent use as implants. A cytocompatibility assessment using MG-63 spheroids demonstrated good attachment, spreading, and active migration of cells on the scaffold surface (over 96 % of living cells), confirming their biotolerance. These findings suggest the promise of this surface modification approach for developing superelastic Ti-Zr-Nb scaffolds with superior antibacterial properties and biocompatibility, making them highly suitable for bone implant applications.

Structure and antibacterial properties of Ag-doped micropattern surfaces produced by photolithography method.

Photolithography methods offer ample opportunities for creating biological surface patterns over large areas. Herein, samples with patterned surface having the same Ag total coverage area and content, but different surface topography made of periodically spaced Ag/Si pillars with a diameter of 10 and 50 µm and a height of 3, 1, and 0.2 µm were produced by photolithography technique and studied to uncover the dependences of bactericide ion release on surface topography and antibacterial effect on Ag+ ion concentration. Reactive ion etching of Si wafers in areas unprotected by Ag capping layer was accompanied by a number of competing processes: (i) formation of Ag particles on the tops of pillars due to temperature-activated diffusion and coalescence, (ii) sputtering of Ag from the pillar to surface and redeposition into the etching cavities, resulting in the formation of small Ag nanoparticles located in areas between pillars, (iii) precipitation of AgSix phase as a result of chemical interaction of sputtered Si ions with Ag ions and atoms in surrounding plasma. Samples with the largest pillar heights which had also Ag particles formed between pillars demonstrated the fastest Ag+ ion release and, correspondingly, a noticeable antibacterial effect toward antibiotic-resistant hospital Escherichia coli K-261 strains already after 3 h. All samples showed 100% antibacterial effect after 24 h. Thus our results open up new possibilities for the production of scalable micropattern surfaces with controlled bactericide ion release and pronounced antibacterial characteristics for future applications in the orthopedic field.

Antibacterial Performance of TiCaPCON Films Incorporated with Ag, Pt, and Zn: Bactericidal Ions Versus Surface Microgalvanic Interactions.

It is very important to prevent bacterial colonization at the early postoperative stages. There are four major strategies and their corresponding types of antibacterial surfaces specifically designed to fight infection: bactericide release, anti-adhesion, pH-sensitive, and contact-killing. Herein, we aimed at determining the antibacterial efficiency of different types of bactericidal ions and revealing the possible contribution of surface microgalvanic effects arising from a potential difference on heterogeneous surfaces. We considered five types of TiCaPCON films, with Ag, Zn, Pt, Ag + Zn, and Pt + Zn nanoparticles (NPs) on their surface. The Ag-modified film demonstrated a pronounced antibacterial effect at a very low Ag ion concentration of 0.11 ppb in physiological solution that was achieved already after 3 h of immersion in Escherichia coli ( E. coli) bacterial culture. The Zn-containing sample also showed a noticeable antibacterial effect against E. coli and Staphylococcus aureus ( S. aureus) strains, wherein the concentration of Zn ions was 2 orders of magnitude higher (15 ppb) compared with the Ag ions. The presence of Ag NPs accelerated the leaching of Zn ion out of the TiCaPCON-Ag-Zn film, but no synergistic effect of the simultaneous presence of the two bactericidal components was observed. After the incubation of the samples with Ag, Zn, and Ag + Zn NPs in E. coli and S. aureus suspensions for 24 and 8 h, respectively, all bacterial cells were completely inactivated. The Pt-containing film showed a very low Pt ion release, and therefore the contribution of this type of ions to the total bactericidal effect could be neglected. The results of the electrochemical studies and Kelvin probe force microscopy indicated that microgalvanic couples were formed between the Pt NPs and the TiCaPCON film, but no noticeable antibacterial effect against either E. coli or S. aureus strains was observed. All ion-modified samples provided good osteoblastic cell attachment, spreading, and proliferation and therefore were concluded to be nontoxic for cells. In addition, the TiCaPCON films with Ag, Pt, and Zn NPs on their surface demonstrated good osteoconductive characteristics.