This work presents results on the influence of thickness on the structure and biological response of Cu-O coatings deposited on commercially pure titanium (cpTi) substrates using direct current (DC) magnetron sputtering. The deposition times were 5, 10, and 15 min to obtain coatings with different thicknesses. The results show that the films deposited for 5, 10, and 15 min correspond to thicknesses of 41, 74, and 125 nm, respectively. The phase composition of the coatings is in the form of a double-phase structure of CuO and Cu2O in all considered cases. The roughness is on the nanometric scale and no obvious trend as a function of the thickness can be observed for the deposited films. Also, it was found that, with an increase in the thickness of the films, the distribution of the heights becomes closer to symmetrical. The antimicrobial efficacy of different Cu-O-coated cpTi substrates was examined using a direct contact experiment. A possible bactericidal effect was investigated by inoculating a 200 μL bacterial suspension on CuO-coated cpTi and cpTi (control) for 24 h at 37 °C. The results showed that Cu-O-coated cpTi substrates have a 50%–60% higher antimicrobial activity than the substrate. At the same time, human osteosarcoma (MG-63) cells growing on Cu-O-coated cpTi substrates showed 80% viability following 24 h incubation. Depending on magnetron sputtering process parameters, a different coating thickness, various crystallite phase compositions, and diverse biocompatibility were obtained.
One of the primary risk factors for implant failure is thought to be implant-related infections during the early healing phase. Developing coatings with cell stimulatory behaviour and bacterial adhesion control is still difficult for bone implants. This study proposes an approach for one-step deposition of biocompatible and antimicrobial Cu-doped TiO2 coatings via glow-discharge sputtering of a mosaic target. During the deposition, the bias of the Ti6Al4V substrates was changed. Structure examination, phase analysis, and surface morphology were carried out using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The hardness values and hydrophilic and corrosion performance were also evaluated together with cytocompatible and antibacterial examinations against E. coli and S. aureus. The results show great chemical and phase control of the bias identifying rutile, anatase, CuO, or ternary oxide phases. It was found that by increasing the substrate bias from 0 to −50 V the Cu content increased from 15.3 up to 20.7 at% while at a high bias of −100 V, the copper content reduced to 3 at%. Simultaneously, apart from the Cu2+ state, Cu1+ is also found in the biased samples. Compared with the bare alloy, the hardness, the water contact angle and corrosion resistance of the biased coatings increased. According to an assessment of in vitro cytocompatibility, all coatings were found to be nontoxic to MG-63 osteoblast cells over the time studied. Copper release and cell-surface interactions generated an antibacterial effect against E. coli and S. aureus strains. The −50 V biased coating combined the most successful results in inhibiting bacterial growth and eliciting the proper responses from osteoblastic cells because of its phase composition, electrochemical stability, hydrophilicity, improved substrate adhesion, and surface roughness. Using this novel surface modification approach, we achieved multifunctionality through controlled copper content and oxide phase composition in the sputtered films.
Titanium alloys are widely used for biomedical implants, but their performance is limited by wear, corrosion, and susceptibility to bacterial colonisation. To overcome these drawbacks, multilayer Ti–Cu oxide coatings were deposited on Ti6Al4V substrates using direct current magnetron sputtering. Two multilayer architectures (6 × 2 and 12 × 2 TiO2/CuO bilayers) were fabricated and evaluated for their structural, mechanical, electrochemical, and biological properties. SEM/EDS and XRD confirmed well-adhered crystalline coatings consisting of rutile/anatase TiO2 and monoclinic CuO with uniform elemental distribution. The coatings increased surface roughness, improved adhesion, and enhanced hardness by up to ~180% compared to uncoated Ti6Al4V alloy. Compared to the bare substrate, electrochemical testing in simulated body fluid showed higher corrosion resistance of both coated samples, but particularly for the 12 × 2 multilayers. Both architectures provided sustained Cu2+ release over seven days without a burst effect. In vitro biological testing showed that both multilayer coatings achieved over 96% inhibition of Gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis, while exhibiting moderate antibacterial effects against Gram-negative strains (Escherichia coli, Pseudomonas aeruginosa). Despite the presence of copper, MG-63 osteoblast-like cells demonstrated sustained viability and successful extracellular matrix mineralisation, indicating excellent cytocompatibility of the coatings with bone-forming cells. These results demonstrate that multilayer Ti–Cu oxide coatings can effectively balance antibacterial performance, corrosion resistance, mechanical strength, and support bone cell integration, making them a promising strategy for the surface modification of titanium-based biomedical implants.
Nanostructured TiO2/Cu coatings were deposited on Ti6Al4V alloy by a two-step glow-discharge sputtering process and evaluated for their structural, electrochemical, and biological properties. Dual-acid etching produced microroughened substrates before TiO2 layer deposition, followed by surface Cu sputtering with varied deposition times. Characterisation by AFM, OM, SEM/EDS, and XRD confirmed the formation of TiO2 with Cu/Cu2O-containing hybrid coatings with good adhesion to the substrate. Increasing Cu deposition enhanced surface hydrophobicity and copper ion release. EIS measurements proved that the coatings retained stable protective behaviour in simulated body fluid (SBF). Antibacterial tests against Escherichia coli showed up to 98% improved efficacy compared to bare Ti6Al4V, confirming the strong antimicrobial role of copper. However, MG63 osteoblast-like cells exhibited reduced viability even after pre-immersion in PBS, suggesting that cytotoxicity was associated not only with excess Cu ion release but also with direct interaction between cells and surface Cu nanostructures. Overall, the results indicate that TiO2/Cu coatings provide excellent antimicrobial activity, good protection and strong adhesion, but their limited biocompatibility highlights the need for fine-tuned copper incorporation in future biomedical implant applications.
Early biofilm formation could be inhibited by applying a thin biocompatible copper coating to reduce periprosthetic infections. In this study, we deposited crystalline Cu-doped TiO2 films using one-step DC magnetron sputtering in an oxygen atmosphere on a biased Ti6Al4V alloy without external heating. The bias voltage varied from −25 V to −100 V, and the resultant substrate temperature was measured. The deposited coatings were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), microhardness, scratch and hydrophilicity tests, potentiodynamic polarization measurements, and antibacterial assays against S. aureus and E. coli. The findings demonstrated that when a higher negative bias is applied, the substrate temperature drops, and the anatase to rutile transformation is initiated without indicating obvious Cu-containing phases. The SEM images of the films showed spherical agglomerates with homogeneously distributed Cu with decreasing Cu content as the bias value increased. Higher bias results in the grain refinement of the thinning coatings with more lattice microstrain and more defects, together with an increase in water contact angles and hardness values. Samples biased at −75 V exhibited the highest adhesive strength between coatings and substrate, whereas the specimen biased at −50 V demonstrated higher corrosion resistance. Cu-containing TiO2 coatings with pure anatase phase composition and Cu concentrations of 2.62 wt.% demonstrated excellent bactericidal activity against both S. aureus and E. coli. The layers containing 2.34 wt.% Cu exhibited very good antibacterial properties against S. aureus, only. According to these findings, the produced copper-doped TiO2 coatings have high bactericidal qualities in vitro and may be used to prepare orthopaedic and dental implants in the future.
31 January 2023 in Journal of Chemical Technology and Metallurgy
The non-enzymatic glycosylation (glycation) is a natural process occurring in living organisms, which is associated with aging and diabetic complications. This non-enzymatic reaction affects not only long-lived proteins, such as eye crystalline, but also DNA, RNA and aminolipids. The long-standing search for substances that can inhibit this process is still ongoing. In this study we examined the effect of two natural compounds, resveratrol and glucosamine, on the formation of early and fluorescent advanced glycation end products (AGEs). We found that resveratrol inhibited formation of fluorescent AGEs in bovine serum albumin (BSA) glycated with D-ribose, with inhibition percentage of 80 %, while glucosamine inhibited the formation of the same products in the same test system only by 4 % compared to a control sample of glycated BSA. Both test compounds, resveratrol and glucosamine, did not inhibit the formation of early glycation products in the glycated BSA. Our results showed that resveratrol has strong antiglycation activity in contrast to glucosamine demonstrating very low antiglycation potential.