Impedimetric Detection of Femtomolar Levels of Interleukin 6, 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)

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

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

Electrochemical Evaluation of the Compact and Nanotubular Oxide Layer Destruction under Ex Vivo Ti6Al4V ELI Transpedicular Screw Implantation

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

Fabrication of Electrochemical Biosensor Based on Titanium Dioxide Nanotubes and Silver Nanoparticles for Heat Shock Protein 70 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

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

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

Numerical Analyses of Fracture Mechanism of the Pelvic Ring during Side-Impact Load

The aim of this study is the analysis of the multiple pelvis fracture mechanism in side-impact dynamic load cases. The elaborated numerical model of a pelvis complex includes pelvic and sacral bones as well as soft tissues such as ligaments and cartilages. The bone has been modelled as a viscoelasticity material based on the Johnson–Cook model. The model parameters have been chosen based on the experimental data. The uniqueness of a presented approach refers to the selection of crack criteria for the bone. Thus, it was allowed to analyse the process of multiple fractures inside the pelvic bones. The analysis was evaluated for the model in which the deformation rate influences the bone material properties. As a result, the stress distributions inside particular bones were changed. It has been estimated that the results can vary by 50% or even more depending on the type of boundary conditions adopted. The second step of work was a numerical analysis of military vehicle subjected to an IED. An analysis of the impactor’s impact on the pelvis of the Hybrid ES-2RE mannequin was conducted. It was shown that the force in the pelvis exceeds the critical value by a factor of 10. The results of the numerical analysis were then used to validate the model of a military vehicle with a soldier. It was shown that for the adopted loading conditions, the critical value of the force in the pelvis was not exceeded

Spectrum of Bacterial Pathogens from Urinary Infections Associated with Struvite and Metabolic Stones

Objective: The purposes of this multi-center study were to evaluate the rate of infection stones and to evaluate the urine cultures of patients with infection stones. Materials: Charts of adulpatients with urinary stones were reviewed and data on stone analyses and urine cultures were collected. Results: In total, 1204 renal stone formers (RSFs) from 10 countries were included (776 males, 428 females). Fifty-six patients (4.6%) had struvite stones. The highest frequency of struvite stones was observed in India (23%) and Pakistan (18%). Lower rates were reported in Canada (2%), China (3%), Argentina (3%), Iraq (3%), Italy (3.5%) and Poland (3%), and intermediate rates in Egypt (5.5%) and Bulgaria (5.4%). Urine cultures were retrieved from 508 patients. Patients with struvite stones had a positive culture in 64.3% of the samples and patients with other stones, in 26.7%. In struvite stones, the most common isolates were Escherichia coli (27.7%) and Proteus spp. (27.7%), followed by Klebsiella spp. (16.7%); in other types of stone, it was Escherichia coli (47.6%), followed by Gram-positive bacteria (14.0%) Conclusions: The struvite stone composition was associated with a urinary infection, although an infection was not demonstrable with a conventional midstream urine culture in about 30%