Impedimetric Detection of Femtomolar Levels of Interleukin6, Interleukin 8, and Tumor Necrosis Factor Alpha Based on Thermally Modified Nanotubular Titanium Dioxide Arrays.

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).

Comparison of Gold Nanoparticles Deposition Methods and Their Influence on Electrochemical and Adsorption Properties of Titanium Dioxide Nanotubes.

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.

Influence of geometry and annealing temperature in argon atmosphere of TiO2 nanotubes on their electrochemical properties.

PURPOSE: In this paper, electrochemical properties of the as-formed and thermally treated titanium dioxide (TiO2) nanotubes with diameter in the range of 20-100 nm and height in the range of 100-1000 nm were presented. In addition, the effects of annealing temperature (450-550 °C) on the electrochemical characteristics of these structures, as well as the influence of diameter and height of TiO2 nanotubes on these properties were examined. The results were referred to a compact TiO2 layer (100 nm thick). METHODS: The electrochemical test included open circuit potential, impedance spectroscopy and cyclic voltammetry measurements. The scanning electron microscope with energy dispersive spectroscopy analyser, x-ray photoelectron spectroscopy, and x-ray diffraction analysers were used for surface morphology characterisation as well as elemental, phase and chemical composition of TiO2 layers. RESULTS: It was found that nanotubes with the diameter of 50 and 75 nm (height of 1000 nm) annealed at 550 °C exhibit the lowest impedance and phase angle values. However, the voltammetric detection of potassium ferricyanide indicated that the closest to 1 Ipc /Ipa ratio were shown by nanotubes with a diameter of 50 and 75 nm annealed at 450 °C. CONCLUSIONS: On the basis of performed analysis, it can be stated that the TiO2 layer with nanotubes of 50 nm in diameter and of 1000 nm in height, annealed in 450 °C may be indicated as the ones having the most favourable sensing and biosensing properties.

Evaluation of the Antibacterial Activity of Ag- and Au-Nanoparticles Loaded TiO2 Nanotubes.

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.

The Influence of the Parameters of a Gold Nanoparticle Deposition Method on Titanium Dioxide Nanotubes, Their Electrochemical Response, and Protein Adsorption.

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.

Surface analysis of long-term hemodialysis catheters made of carbothane (poly(carbonate)urethane) before and after implantation in the patients' bodies.

PURPOSE: The vascular cannulation is associated with a number of complications. The aim of this work was to study the composition and distribution of the film covering the surfaces of Mahurkar Maxid and Palindrome catheters, which were removed from the body of long-term hemodialysis patients. Moreover, the roughness and contact angle of the catheters were evaluated. METHODS: Two brand new (as a reference) and thirty used catheters were the subject of the study. Their implantation period lasted from 4 months to a year and the reason for removal was the production of another vascular access or obstruction. Surfaces were analyzed by scanning electron microscope, atomic force microscope and goniometer. RESULTS: The inner surfaces of the used catheters were covered with a film of various complexity which includes a plurality of protein, blood cell counts and the crystals. The closer to the distal part the film becomes more complex and multi-layered. Even the surfaces of brand new catheter were not completely smooth. The only significant difference between analyzed models was the presence of thrombus in the distal part of Mahurkar Maxid catheters, not in the Palindrome. CONCLUSIONS: The distal part of the catheters is the place most exposed to obstruction and infection, which may be due to not reaching the anticoagulant agent into this part. Not only the occurrence of side holes affects the formation of thrombus, but also their quantity, geometry and distribution which effect on fluid mechanics. The surface of the catheters needs to improvement to minimize the occurrence of defects and cracks.

Influence of Thermal Modification and Morphology of TiO2 Nanotubes on Their Electrochemical Properties for Biosensors Applications.

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.