Detection of Four Distinct Volatile Indicators of Colorectal Cancer using Functionalized Titania Nanotubular Arrays.

Screening of colorectal cancer is crucial for early stage diagnosis and treatment. Detection of volatile organic compounds (VOCs) of the metabolome present in exhaled breath is a promising approach to screen colorectal cancer (CRC). Various forms of volatile organic compounds (VOCs) that show the definitive signature for the different diseases including cancers are present in exhale breathe. Among all the reported CRC VOCs, cyclohexane, methylcyclohexane, 1,3-dimethyl- benzene and decanal are identified as the prominent ones that can be used as the signature for CRC screening. In the present investigation, detection of the four prominent VOCs related to CRC is explored using functionalized titania nanotubular arrays (TNAs)-based sensor. These signature biomarkers are shown to be detected using nickel-functionalized TNA as an electrochemical sensor. The sensing mechanism is based on the electrochemical interaction of nickel-functionalized nanotubes with signature biomarkers. A detailed mechanism of the sensor response is also presented.

Electrochemical capacitance of iron oxide nanotube (Fe-NT): effect of annealing atmospheres.

The effect of annealing atmosphere on the supercapacitance behavior of iron oxide nanotube (Fe-NT) electrodes has been explored and reported here. Iron oxide nanotubes were synthesized on a pure iron substrate through an electrochemical anodization process in an ethylene glycol solution containing 3% H2O and 0.5 wt.% NH4F. Subsequently, the annealing of the nanotubes was carried out at 500 °C for 2 h in various gas atmospheres such as air, oxygen (O2), nitrogen (N2), and argon (Ar). The morphology and crystal phases evolved after the annealing processes were examined via field emission scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical capacitance properties of the annealed Fe-NT electrodes were evaluated by conducting cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy tests in the Li2SO4 electrolyte. Based on these experiments, it was found that the capacitance of the Fe-NT electrodes annealed in air and O2 atmospheres shows mixed behavior comprising both the electric double layer and pseudocapacitance. However, annealing in N2 and Ar environments resulted in well-defined redox peaks in the CV profiles of the Fe-NT electrodes, which are therefore attributed to the relatively higher pseudonature of the capacitance in these electrodes. Based on the galvanostatic charge-discharge studies, the specific capacitance achieved in the Fe-NT electrode after annealing in Ar was about 300 mF cm(-2), which was about twice the value obtained for N2-annealed Fe-NTs and three times higher than those annealed in air and O2. The experiments also demonstrated excellent cycle stability for the Fe-NT electrodes with 83%-85% capacitance retention, even after many charge-discharge cycles, irrespective of the gas atmospheres used during annealing. The increase in the specific capacitance was discussed in terms of increased oxygen vacancies as a result of the enhanced transformation of the hematite (α-Fe2O3) phase to the magnetite (Fe3O4) phase for the electrodes annealed in the N2 and Ar atmospheres.

Site-specific and patterned growth of TiO2 nanotube arrays from e-beam evaporated thin titanium film on Si wafer.

Growth of TiO(2) nanotubes on thin Ti film deposited on Si wafers with site-specific and patterned growth using a photolithography technique is demonstrated for the first time. Ti films were deposited via e-beam evaporation to a thickness of 350-1000 nm. The use of a fluorinated organic electrolyte at room temperature produced the growth of nanotubes with varying applied voltages of 10-60 V (DC) which remained stable after annealing at 500 °C. It was found that variation of the thickness of the deposited Ti film could be used to control the length of the nanotubes regardless of longer anodization time/voltage. Growth of the nanotubes on a SiO(2) barrier layer over a Si wafer, along with site-specific and patterned growth, enables potential application of TiO(2) nanotubes in NEMS/MEMS-type devices.

On the Structure and Lithium Adsorption Mechanism of Layered H2TiO3.

Layered H2TiO3 has been studied as an ionic sieve material for the selective concentration of lithium from solutions. The accepted mechanism of lithium adsorption on H2TiO3 ion sieves is that it occurs via Li+-H+ ion exchange with no chemical bond breakage. However, in this work, we demonstrate that lithium adsorption on H2TiO3 occurs via O-H bond breakage and the formation of O-Li bonds, contrary to previously proposed mechanisms. Thermogravimetric analysis results show that the weight loss due to dehydroxylation decreases from 2.96 wt % to 0.8 wt % after lithium adsorption, indicating that surface hydroxyl groups break during lithium adsorption. Raman and Fourier transform infrared spectroscopy studies indicate that H2TiO3 contains isolated OH groups and hydrogen-bonded OH groups. Among these two hydroxyl groups, isolated OH groups present in the HTi2 layers are more actively involved in lithium adsorption than hydrogen-bonded OH groups. As a result, the actual adsorption capacity is limited by the number of isolated OH groups, whereas hydrogen-bonded OH groups involved are for stabilizing the layered structure. We also show that H2TiO3 contains a high concentration of stacking faults and structural disorders which play a crucial role in controlling lithium adsorption properties.

Self-Ordered Titanium Dioxide Nanotube Arrays: Anodic Synthesis and Their Photo/Electro-Catalytic Applications.

Metal oxide nanotubes have become a widely investigated material, more specifically, self-organized titania nanotube arrays synthesized by electrochemical anodization. As a highly investigated material with a wide gamut of applications, the majority of published literature focuses on the solar-based applications of this material. The scope of this review summarizes some of the recent advances made using metal oxide nanotube arrays formed via anodization in solar-based applications. A general methodology for theoretical modeling of titania surfaces in solar applications is also presented.

Redox-induced enhancement in interfacial capacitance of the titania nanotube/bismuth oxide composite electrode.

Bismuth oxide (Bi2O3) decorated titania nanotube array (T-NT) composite materials were synthesized by a simple, yet versatile electrodeposition method. The effects of deposition current density and time on morphology evolution of the bismuth oxide phase were analyzed. It was found that an optimum deposition condition in terms of current density and time could be reached to achieve uniform and equiaxed crystal morphology of the deposited oxide phase. The morphology, shape, size distribution, and crystal structure of the bismuth oxide phase were evaluated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopic techniques. The electrochemical capacitance of the T-NT/Bi2O3 composites was studied by conducting cyclic voltammetry and galvanostatic charge-discharge experiments. These studies indicated that the capacitance behavior of the composite material was dependent on the morphology and distribution of the bismuth oxide phase. The capacitance was greatly enhanced for the composite having equiaxed and uniformly distributed bismuth oxide particles. The maximum interfacial capacitance achieved in this study was approximately 430 mF cm(-2). Galvanostatic charge-discharge experiments conducted on the composite materials suggested stable capacitance behavior together with excellent capacitance retention even after 500 cycles of continuous charge-discharge operation.

Light-assisted anodized TiO2 nanotube arrays.

Self-assembled arrays of titania nanotubes are synthesized via electrochemical anodization of Ti foils under the presence of UV-vis irradiation. Compared to control samples (anodized without light), the light-assisted anodized samples exhibit larger diameters as well as thicker nanotube walls, whereas the length of the nanotubes remains the same under otherwise similar synthesis conditions. Enhanced photoelectrochemical performance with light-assisted anodized samples under simulated AM 1.5 irradiation is observed by an increase in photocurrent density of 45-73% at 1.23 V (RHE). The enhanced photoelectrochemical performance is correlated to improved charge separation analyzed by Mott-Schottky. A mechanism on the photoeffect during anodization is presented. The morphology and improved properties obtained from the synthesis methodology may also find application in other fields such as sensing and catalysis.

Growth and characterization of TiO2 nanotubes from sputtered Ti film on Si substrate.

In this paper, we present the synthesis of self-organized TiO2 nanotube arrays formed by anodization of thin Ti film deposited on Si wafers by direct current (D.C.) sputtering. Organic electrolyte was used to demonstrate the growth of stable nanotubes at room temperature with voltages varying from 10 to 60 V (D.C.). The tubes were about 1.4 times longer than the thickness of the sputtered Ti film, showing little undesired dissolution of the metal in the electrolyte during anodization. By varying the thickness of the deposited Ti film, the length of the nanotubes could be controlled precisely irrespective of longer anodization time and/or anodization voltage. Scanning electron microscopy, atomic force microscopy, diffuse-reflectance UV-vis spectroscopy, and X-ray diffraction were used to characterize the thin film nanotubes. The tubes exhibited good adhesion to the wafer and did not peel off after annealing in air at 350 °C to form anatase TiO2. With TiO2 nanotubes on planar/stable Si substrates, one can envision their integration with the current micro-fabrication technique large-scale fabrication of TiO2 nanotube-based devices.

Improved photocatalytic degradation of textile dye using titanium dioxide nanotubes formed over titanium wires.

Titanium dioxide (TiO2) nanotubes formed by anodization over titanium wires show a significant improvement in photocatalytic activity compared to the nanotubes formed over foils. This is evident when the fractional conversion of a textile dye, methyl orange, increased from 19% over a foil to 40% over wires in the presence of nanotubes of identical dimensions illuminated over the same geometrical area. Higher degradation rates with Pt-TiO2 nanotubes over foils are matched by the Pt-free TiO2 nanotubes over the wires. The higher photocatalytic activity over the anodized wires can be attributed to the efficient capture of reflected and refracted light by the radially outward oriented TiO2 nanotubes formed over the circumference of the titanium wire. The formation of TiO2 nanotubes over wires can be considered as an effective alternate to improve photodegradation rates by avoiding expensive additives.