This paper presents the comparison of the effects of three methods of production of silver spherical and near-spherical nanoparticles (AgNPs) on the titanium dioxide nanotubes (TNT) base: cyclic voltammetry, chronoamperometry, and sputter deposition. It also evaluates the influence of silver nanoparticles on the electrochemical properties of the developed electrodes. The novelty of this research was to fabricate regular AgNPs free of agglomerates uniformly distributed onto the TNT layer, which has not been accomplished with previous attempts. The applied methods do not require stabilizing and reducing reagents. The extensive electrochemical characteristic of AgNP/TNT was performed by open circuit potential and electrochemical impedance spectroscopy methods. For AgNPs/TNT obtained by each method, the impedance module of these electrodes was up to 50% lower when compared to TNT, which means that AgNPs enabled more efficient electron transfer due to the effective area increase. In addition, the presence of nanoparticles increases the corrosion resistance of the prepared electrodes. These substrates can be used as electrochemical sensors due to their high electrical conductivity, and also as implants due to the antibacterial properties of both the TNT and AgNPs.
The morphology of self-assembled TiO2 nanotubes layer plays a key role in electrical conductivity and biocompatibility properties in terms of cell proliferation, adhesion and mineralization. Many research studies have been reported in using a TiO2 nanotubes for different medical applications, there is a lack of unified correlation between TNT morphology and its electrochemical properties. The aim of this study was to examine the effects of diameter and annealing conditions on TiO2 nanotubes with identical height and their behaviour as biosensor platform. TiO2 nanotubes layer, 1000 nm thick with nanotubes of diameters in range: 25 ÷ 100 nm, was prepared by anodizing of the titanium foil in ethylene glycol solution. To change the crystal structure and improve the electrical conductivity of the semiconductive TiO2 nanotubes layer the thermal treatment by annealing in argon, nitrogen or air was used. Basing on the electrochemical tests, the XPS and scanning microscopy examinations, as well as the contact angle measurements and the amperometric detection of potassium ferricyanide, it was concluded that the 1000 nm thick TiO2 nanotubes layer with nanotubes of 50 nm diameter, annealed in argon, showed the best physicochemical properties, which helps investigate the adsorption immobilization mechanism. The possibility of using TNT as a biosensor platform was confirmed in hydrogen detection.
This paper presents the fabrication methodology of an electrochemical biosensor for the detection of heat shock protein 70 (HSP70) as a potential tumor marker with high diagnostic sensitivity. The sensor substrate was a composite based on titanium dioxide nanotubes (TNTs) and silver nanoparticles (AgNPs) produced directly on TNTs by electrodeposition, to which anti-HSP70 antibodies were attached by covalent functionalization. This manuscript contains a detailed description of the production, modification, and the complete characteristics of the material used as a biosensor platform. As-formed TNTs, annealed TNTs, and the final sensor platform—AgNPs/TNTs, were tested using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction analysis (XRD). In addition, open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) of these substrates were used to assess the influence of TNTs modification on their electrochemical characteristics. The EIS technique was used to monitor the functionalization steps of the AgNPs/TNTs electrode and the interaction between anti-HSP70 and HSP70. The produced composite was characterized by high purity, and electrical conductivity improved more than twice compared to unmodified TNTs. The linear detection range of HSP70 of the developed biosensor was in the concentration range from 0.1 to 100 ng/mL.
Nano-engineered implants are a promising orthopedic implant modification enhancing bioactivity and integration. Despite the lack of destruction of an oxide layer confirmed in ex vivo and in vivo implantation, the testing of a microrupture of an anodic layer initiating immune-inflammatory reaction is still underexplored. The aim of this work was to form the compact and nanotubular oxide layer on the Ti6Al4V ELI transpedicular screws and electrochemical detection of layer microrupture after implantation ex vivo by the Magerl technique using scanning electron microscopy and highly sensitive electrochemical methods. For the first time, the obtained results showed the ability to form the homogenous nanotubular layer on an Ti6Al4V ELI screw, both in α and β-phases, with favorable morphology, i.e., 35 ÷ 50 ± 5 nm diameter, 1500 ± 100 nm height. In contrast to previous studies, microrupture and degradation of both form layers were observed using ultrasensitive electrochemical methods. Mechanical stability and corrosion protection of nanotubular layer were significantly better when compared to compact oxide layer and bare Ti6Al4V ELI.
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