Search Results (11)

Due to the bio-inert nature of titanium (Ti) and subsequent accompanying chronic inflammatory response, an implant’s stability and function can be significantly affected, which is why various surface modifications have been employed, including the deposition of titanium oxide (TiO₂) nanotubes (TNTs) onto the native surface through the anodic oxidation method. While the influence of nanotube diameter on cell behaviour and osteogenesis is very well documented, information regarding the effects of nanotube lateral spacing on the in vivo new bone formation process is insufficient and hard to find. Considering this, the present study’s aim was to evaluate the mechanical properties and the osteogenic ability of two types of TNTs-based pins with different lateral spacing, e.g., 25 nm (TNTs) and 92 nm (spTNTs). The mechanical properties of the TNT-coated implants were characterised from a morphological point of view (tube diameter, spacing, and tube length) using scanning electron microscopy (SEM). In addition, the chemical composition of the implants was evaluated using X-ray photoelectron spectroscopy, while surface roughness and topography were characterised using atomic force microscopy (AFM). Finally, the implants’ hardness and elastic modulus were investigated using nanoindentation measurements. The in vivo new bone formation was histologically evaluated (haematoxylin and eosin—HE staining) at 6 and 30 days post-implantation in a rat model. Mechanical characterisation revealed that the two morphologies presented a similar chemical composition and mechanical strength, but, in terms of surface roughness, the spTNTs exhibited a higher average roughness. The microscopic examination at 1 month post-implantation revealed that spTNTs pins (57.21 ± 34.93) were capable of promoting early new bone tissue formation to a greater extent than the TNTs-coated implants (24.37 ± 6.5), with a difference in the average thickness of the newly formed bone tissue of ~32.84 µm, thus highlighting the importance of this parameter when designing future dental/orthopaedic implants. Full article

Anodic TiO₂ nanotube arrays decorated with Ni, Cu, and NiCu alloy thin films were investigated for the first time for the photocatalytic degradation of paracetamol in water solution under UV irradiation. Metallic co-catalysts were deposited on TiO₂ nanotubes using magnetron sputtering. The influence of the metal layer composition and thickness on the photocatalytic activity was systematically studied. Photocatalytic experiments showed that only Cu-rich co-catalysts provide enhanced paracetamol degradation rates, whereas Ni-modified photocatalysts exhibit no improvement compared with unmodified TiO₂. The best-performing material was obtained by sputtering a 20 nm thick film of 1:1 atomic ratio NiCu alloy: this material exhibits a reaction rate more than doubled compared with pristine TiO₂, enabling the complete degradation of 10 mg L⁻¹ of paracetamol in 8 h. The superior performance of NiCu-modified systems over pure Cu-based ones is ascribed to a Ni and Cu synergistic effect. Kinetic tests using selective holes and radical scavengers unveiled, unlike prior findings in the literature, that paracetamol undergoes direct oxidation at the photocatalyst surface via valence band holes. Finally, Chemical Oxygen Demand (COD) tests and High-Resolution Mass Spectrometry (HR-MS) analysis were conducted to assess the degree of mineralization and identify intermediates. In contrast with the existing literature, we demonstrated that the mechanistic pathway involves direct oxidation by valence band holes. Full article

In the last few years, the progress made in the field of nanotechnology has allowed researchers to develop and synthesize nanosized materials with unique physicochemical characteristics, suitable for various biomedical applications. Amongst these nanomaterials, metal oxide nanoparticles (MONPs) have gained increasing interest due to their excellent properties, which to a great extent differ from their bulk counterpart. However, despite such positive advantages, a substantial body of literature reports on their cytotoxic effects, which are directly correlated to the nanoparticles’ physicochemical properties, therefore, better control over the synthetic parameters will not only lead to favorable surface characteristics but may also increase biocompatibility and consequently lower cytotoxicity. Taking into consideration the enormous biomedical potential of MONPs, the present review will discuss the most recent developments in this field referring mainly to synthesis methods, physical and chemical characterization and biological effects, including the pro-regenerative and antitumor potentials as well as antibacterial activity. Moreover, the last section of the review will tackle the pressing issue of the toxic effects of MONPs on various tissues/organs and cell lines. Full article

With a distinct electronic structure and unsaturated coordination centers, supported single-atoms (SAs) have shown great potential in heterogeneous catalysis due to their superior activity, stability, and selectivity. Over the last few years, the fascination of SA-use spread also over photocatalysis, i.e., a particular case of heterogeneous catalysis in which chemical reactions are activated by charge transfer from an illuminated semiconductor. Titanium dioxide (TiO₂) is one of the most studied photocatalytic materials. It is widely used as a light absorbing semiconductor decorated with metallic (nanoparticles and single-atom) co-catalysts. In the current review, we emphasize the role of SAs as a co-catalyst in photocatalysis, and clearly set it apart from the use of single atoms in classic heterogeneous catalysis. The review first briefly describes the principal features of SAs, and gives an overview of most important examples of single-atom co-catalysts. Then, we discuss photocatalysis and key examples of single-atom co-catalysts used on TiO₂ photocatalysts and their applications. At last, we provide an outlook for further exploring TiO₂-based single-atom photocatalytic systems. Full article

With the introduction of a new interdisciplinary field, osteoimmunology, today, it is well acknowledged that biomaterial-induced inflammation is modulated by immune cells, primarily macrophages, and can be controlled by nanotopographical cues. Recent studies have investigated the effect of surface properties in modulating the immune reaction, and literature data indicate that various surface cues can dictate both the immune response and bone tissue repair. In this context, the purpose of the present study was to investigate the effects of titanium dioxide nanotube (TNT) interspacing on the response of the macrophage-like cell line RAW 264.7. The cells were maintained in contact with the surfaces of flat titanium (Ti) and anodic TNTs with an intertube spacing of 20 nm (TNT20) and 80 nm (TNT80), under standard or pro-inflammatory conditions. The results revealed that nanotube interspacing can influence macrophage response in terms of cell survival and proliferation, cellular morphology and polarization, cytokine/chemokine expression, and foreign body reaction. While the nanostructured topography did not tune the macrophages’ differentiation into osteoclasts, this behavior was significantly reduced as compared to flat Ti surface. Overall, this study provides a new insight into how nanotubes’ morphological features, particularly intertube spacing, could affect macrophage behavior. Full article

Porous BiVO₄ electrodes were conformally decorated with CdS via a chemical bath deposition process. The highest photocurrent at 1.1 V vs. RHE was achieved for a BiVO₄/CdS composite (4.54 mA cm⁻²), compared with CdS (1.19 mA cm⁻²) and bare BiVO₄ (2.1 mA cm⁻²), under AM 1.5G illumination. This improvement in the photoefficiency can be ascribed to both the enhanced optical absorption properties and the charge separation due to the heterojunction formation between BiVO₄ and CdS. Furthermore, the BiVO₄/CdS photoanode was protected with a CoO_x layer to substantially increase the photostability of the material. The new BiVO₄/CdS/CoO_x nanostructure exhibited a highly stable photocurrent density of ~5 mA cm⁻². The capability to produce O₂ was locally investigated by scanning photoelectrochemical microscope, which showed a good agreement between photocurrent and O₂ reduction current maps. This work develops an efficient route to improve the photo-electrochemical performance of BiVO₄ and its long-term stability. Full article

Highly ordered multi-leg TiO₂ nanotubes (MLTNTs) functionalized with platinized cyanographene are proposed as a hybrid photoelectrode for enhanced photoelectrochemical water splitting. The platinized cyanographene and cyanographene/MLTNTs composite yielded photocurrent densities 1.66 and 1.25 times higher than those of the pristine MLTNTs nanotubes, respectively. Open circuit V_OC decay (V_OCD), electrochemical impedance spectroscopy (EIS), and intensity-modulated photocurrent spectroscopy (IMPS) analyses were performed to study the recombination rate, charge transfer characteristics, and transfer time of photogenerated electrons, respectively. According to the V_OCD and IMPS results, the addition of (platinized) cynographene decreased the recombination rate and the transfer time of photogenerated electrons by one order of magnitude. Furthermore, EIS results showed that the (platinized) cyanographene MLTNTs composite has the lowest charge transfer resistance and therefore the highest photoelectrochemical performance. Full article

Titanium dioxide (TiO₂) nanotube coated substrates have revolutionized the concept of implant in a number of ways, being endowed with superior osseointegration properties and local drug delivery capacity. While accumulating reports describe the influence of nanotube diameter on cell behavior, little is known about the effects of nanotube lateral spacing on cells involved in bone regeneration. In this context, in the present study the MC3T3-E1 murine pre-osteoblast cells behavior has been investigated by using TiO₂ nanotubes of ~78 nm diameter and lateral spacing of 18 nm and 80 nm, respectively. Both nanostructured surfaces supported cell viability and proliferation in approximately equal extent. However, obvious differences in the cell spreading areas, morphologies, the organization of the actin cytoskeleton and the pattern of the focal adhesions were noticed. Furthermore, investigation of the pre-osteoblast differentiation potential indicated a higher capacity of larger spacing nanostructure to enhance the expression of the alkaline phosphatase, osteopontin and osteocalcin osteoblast specific markers inducing osteogenic differentiation. These findings provide the proof that lateral spacing of the TiO₂ nanotube coated titanium (Ti) surfaces has to be considered in designing bone implants with improved biological performance. Full article

Anatase and rutile mixed-phase TiO₂ with an ideal ratio has been proven to significantly enhance photoelectrochemical (PEC) activity in water-splitting applications due to suppressing the electron–hole recombination. However, the mechanism of this improvement has not been satisfactory described yet. The PEC water oxidation (oxygen evolution) at the interface of TiO₂ photoanode and electrolyte solution is determined by the fraction of the photogenerated holes that reach the solution and it is defined as the hole transfer efficiency. The surface and bulk recombination processes in semiconductor photoanodes majorly influence the hole transfer efficiency. In this work, we study the hole transfer process involved in mixed-phase TiO₂ nanotube arrays/solution junction using intensity-modulated photocurrent and photovoltage spectroscopy (IMPS and IMVS); then, we correlate the obtained hole transfer rate constants to (photo)electrochemical impedance spectroscopy (PEIS) measurements. The results suggest that the enhanced performance of the TiO₂ mixed-phase is due to the improved hole transfer rate across the TiO₂/liquid interface as well as to the decrease in the surface trap recombination of the holes. Full article

Hematite is a low band gap, earth abundant semiconductor and it is considered to be a promising choice for photoelectrochemical water splitting. However, as a bulk material its efficiency is low because of excessive bulk, surface, and interface recombination. In the present work, we propose a strategy to prepare a hematite (α-Fe₂O₃) photoanode consisting of hematite nanorods grown onto an iron oxide blocking layer. This blocking layer is formed from a sputter deposited thin metallic iron film on fluorine doped tin oxide (FTO) by using cyclic voltammetry to fully convert the film into an anodic oxide. In a second step, hematite nanorods (NR) are grown onto the layer using a hydrothermal approach. In this geometry, the hematite sub-layer works as a barrier for electron back diffusion (a blocking layer). This suppresses recombination, and the maximum of the incident photon to current efficiency is increased from 12% to 17%. Under AM 1.5 conditions, the photocurrent density reaches approximately 1.2 mA/cm² at 1.5 V vs. RHE and the onset potential changes to 0.8 V vs. RHE (using a Zn-Co co-catalyst). Full article

Transfer of semiconductor thin films on transparent and or flexible substrates is a highly desirable process to enable photonic, catalytic, and sensing technologies. A promising approach to fabricate nanostructured TiO₂ films on transparent substrates is self-ordering by anodizing of thin metal films on fluorine-doped tin oxide (FTO). Here, we report pulsed direct current (DC) magnetron sputtering for the deposition of titanium thin films on conductive glass substrates at temperatures ranging from room temperature to 450 °C. We describe in detail the influence that deposition temperature has on mechanical, adhesion and microstructural properties of titanium film, as well as on the corresponding TiO₂ nanotube array obtained after anodization and annealing. Finally, we measure the photoelectrochemical water splitting activity of different TiO₂ nanotube samples showing that the film deposited at 150 °C has much higher activity correlating well with the lower crystallite size and the higher degree of self-organization observed in comparison with the nanotubes obtained at different temperatures. Importantly, the film showing higher water splitting activity does not have the best adhesion on glass substrate, highlighting an important trade-off for future optimization. Full article