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.

The goal of this research was to find the best conditions to prepare titanium dioxide nanotubes (TNTs) modified with gold nanoparticles (AuNPs). This paper, for the first time, reports on the influence of the parameters of cyclic voltammetry process (CV) -based AuNP deposition, i.e., the number of cycles and the concentration of gold salt solution, on corrosion resistance and the capacitance of TNTs. Another innovation was to fabricate AuNPs with well-formed spherical geometry and uniform distribution on TNTs. The AuNPs/TNTs were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and open-circuit potential measurement. From the obtained results, the correlation between the deposition process parameters, the AuNP diameters, and the electrical conductivity of the TNTs was found in a range from 14.3 ± 1.8 to 182.3 ± 51.7 nm. The size and amount of the AuNPs could be controlled by the number of deposition cycles and the concentration of the gold salt solution. The modification of TNTs using AuNPs facilitated electron transfer, increased the corrosion resistance, and caused better adsorption properties for bovine serum albumin.

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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The increasing interest of attachment of gold nanoparticles (AuNPs) on titanium dioxide nanotubes (TNTs) has been devoted to obtaining tremendous properties suitable for biosensor applications. Achieving precise control of the attachment and shape of AuNPs by methods described in the literature are far from satisfactory. This work shows the comparison of physical adsorption (PA), cyclic voltammetry (CV) and chronoamperometry (CA) methods and the parameters of these methods on TNTs properties. The structural, chemical, phase and electrochemical characterizations of TNTs, Au/TNTs, AuNPs/TNTs are carried out using scanning electron microscopy (SEM), electrochemical impedance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy. The use of PA methods does not allow the deposition of AuNPs on TNTs. CV allows easily obtaining spherical nanoparticles, for which the diameter increases from 20.3 ± 2.9 nm to 182.3 ± 51.7 nm as a concentration of tetrachloroauric acid solution increase from 0.1 mM to 10 mM. Increasing the AuNPs deposition time in the CA method increases the amount of gold, but the AuNPs diameter does not change (35.0 ± 5 nm). Importantly, the CA method also causes the dissolution of the nanotubes layer from 1000 ± 10.0 nm to 823 ± 15.3 nm. Modification of titanium dioxide nanotubes with gold nanoparticles improved the electron transfer and increased the corrosion resistance, as well as promoted the protein adsorption. Importantly, after the deposition of bovine serum albumin, an almost 5.5-fold (324%) increase in real impedance, compared to TNTs (59%) was observed. We found that the Au nanoparticles—especially those with smaller diameter—promoted the stability of bovine serum albumin binding to the TNTs platform. It confirms that the modification of TNTs with gold nanoparticles allows the development of the best platform for biosensing applications.

An inexpensive, easy to prepare, and label-free electrochemical impedance spectroscopy-based biosensor has been developed for the selective detection of human interleukin 6 (IL-6), interleukin 8 (CXCL8, IL-8), and tumor necrosis factor (TNFα)—potential inflammatory cancer biomarkers. We describe a, so far, newly developed and unexplored method to immobilize antibodies onto a titanium dioxide nanotube (TNT) array by physical adsorption. Immobilization of anti-IL-6, anti-IL-8, and anti-TNFα on TNT and the detection of human IL-6, IL-8, and TNFα were examined using electrochemical impedance spectroscopy (EIS). The impedimetric immunosensor demonstrates good selectivity and high sensitivity against human biomarker analytes and can detect IL-6, IL-8, and TNFα at concentrations as low as 5 pg/mL, equivalent to the standard concentration of these proteins in human blood. The calibration curves evidenced that elaborated biosensors are sensitive to three cytokines within 5 ÷ 2500 pg/mL in the 0.01 M phosphate-buffered saline solution (pH 7.4).

Current research on the antibacterial properties of implant surfaces has focused on using titanium nanotubes (TNTs) with diameters of 100 and 200 nm, which simultaneously show the best antibacterial properties, poor osseointegration, and ability to immobilize proteins. Therefore, the research aimed to develop an implantable material based on titanium dioxide nanotubes with a diameter of 50 nm doped with silver (AgNPs) and gold nanoparticles (AuNPs), indicating good absorption and antibacterial properties. Moreover, metallic nanoparticles deposited by varying methods should maintain sphericity and lack of agglomeration. For this purpose, the surface charge, wettability, stability of nanoparticles, and antibacterial properties against Gram-positive and Gram-negative bacteria, i. e., Staphylococcus epidermidis, Streptococcus mutans, and Pseudomonas aeruginosa , were performed. Obtained results indicate a greater resistance to leaching of silver nanoparticles compared to gold nanoparticles. These results are reflected in microbiological studies, both into the time and the effectiveness of the implantable material's antibacterial activity. A greater antibacterial effect of AgNPs than AuNPs has been confirmed. Also, AgNPs inhibit the multiplication of Gram-negative bacteria to a greater extent than Gram-positive bacteria. It has been proven that the TNT platforms deposited with metal nanoparticles via the voltammetric method are more effective in deactivating microorganisms. Besides, the results have proven that smaller TNTs effectively reduce live bacteria as nanotubes with a diameter of 100 and 200 nm.

Abstract. The aim of the study was to specify by an impedimetric method the changes observed on the inner wall of central venous catheters for hemodialysis leading to the formation of a biological film. To evaluate these changes a patient-dialyzer model was built in which experimental parameters were kept closely similar to the clinical conditions of hemodialysis. The impedance spectra and SEM/EDS analysis of the biological layer deposited on the inner surface of the distal part of the catheter gave an insight into the structure of film formation and its chemical composition. Since an early detection of biofilm formation inside the distal part of the catheter is crucial for the safety of medical treatment and it usually prompts the implementation of antibiotic therapy. Developed impedimetric method can minimize the risk of infection and ensure the continuity of treatment.