Anca Mazare

One-dimensional titanium dioxide nanomaterials: nanotubes.

In the present review we try to give a comprehensive and most up to date view to the field, with an emphasis on the currently most investigated anodic TiO2 nanotube arrays. We will first give an overview of different synthesis approaches to produce TiO2 nanotubes and TiO2 nanotube arrays, and then deal with physical and chemical properties of TiO2 nanotubes and techniques to modify them. Finally, we will provide an overview of the most explored and prospective applications of nanotubular TiO2.

Titanium nanostructures for biomedical applications

Titanium and titanium alloys exhibit a unique combination of strength and biocompatibility, which enables their use in medical applications and accounts for their extensive use as implant materials in the last 50 years. Currently, a large amount of research is being carried out in order to determine the optimal surface topography for use in bioapplications, and thus the emphasis is on nanotechnology for biomedical applications. It was recently shown that titanium implants with rough surface topography and free energy increase osteoblast adhesion, maturation and subsequent bone formation. Furthermore, the adhesion of different cell lines to the surface of titanium implants is influenced by the surface characteristics of titanium; namely topography, charge distribution and chemistry. The present review article focuses on the specific nanotopography of titanium, i.e. titanium dioxide (TiO2) nanotubes, using a simple electrochemical anodisation method of the metallic substrate and other processes such as the hydrothermal or sol-gel template. One key advantage of using TiO2 nanotubes in cell interactions is based on the fact that TiO2 nanotube morphology is correlated with cell adhesion, spreading, growth and differentiation of mesenchymal stem cells, which were shown to be maximally induced on smaller diameter nanotubes (15 nm), but hindered on larger diameter (100 nm) tubes, leading to cell death and apoptosis. Research has supported the significance of nanotopography (TiO2 nanotube diameter) in cell adhesion and cell growth, and suggests that the mechanics of focal adhesion formation are similar among different cell types. As such, the present review will focus on perhaps the most spectacular and surprising one-dimensional structures and their unique biomedical applications for increased osseointegration, protein interaction and antibacterial properties.

Reduced inflammatory activity of RAW 264.7 macrophages on titania nanotube modified Ti surface.

Macrophages play a pivotal role in the hosts response to biomaterials being considered as an essential cell type during both optimal tissue-implant integration and pathologic process of implant failure. Hence, understanding of their cellular activity on biomaterials is important for improving evaluation and design of biomaterials for biomedical applications. In the present study, we have comparatively investigated the interactions of titania nanotubes (78 nm diameter) and commercial pure Ti with RAW 264.7 macrophages in both standard and pro-inflammatory (stimulation with lipopolysaccharide, LPS) culture conditions. In vitro tests showed that TiO2 nanotubes exhibited significantly decreased inflammatory activity of macrophages with respect to cytokine and chemokine gene expression/protein secretion, induction of foreign body giant cells (FBGCs) and nitric oxide (NO) release thereby mitigating the inflammatory response induced by LPS as compared to flat Ti surface. Therefore, our results suggest a novel role of TiO2 nanotubes in modulating macrophage response in biomaterial-associated bacterial infections. Overall, the current study provides new insight into how TiO2 nanotubes can be involved in macrophage activation and supports the great promise of such surface modifications for biomedical applications.

Enhancing the Water Splitting Efficiency of Sn‐Doped Hematite Nanoflakes by Flame Annealing

The effect of flame annealing on the water-splitting properties of Sn decorated hematite (α-Fe2O3) nanoflakes has been investigated. It is shown that flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm(-2)) conditions compared to classic furnace annealing treatments. Optimizing the annealing time (10 s at 1000 °C) leads to a photocurrent of 1.1 mA cm(-2) at 1.23 V (vs. RHE) with a maximum value 1.6 mA cm(-2) at 1.6 V (vs. RHE) in 1 M KOH. The improvement in photocurrent can be attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects.

Binding of plasma proteins to titanium dioxide nanotubes with different diameters

Titanium and titanium alloys are considered to be one of the most applicable materials in medical devices because of their suitable properties, most importantly high corrosion resistance and the specific combination of strength with biocompatibility. In order to improve the biocompatibility of titanium surfaces, the current report initially focuses on specifying the topography of titanium dioxide (TiO2) nanotubes (NTs) by electrochemical anodization. The zeta potential (ζ-potential) of NTs showed a negative value and confirmed the agreement between the measured and theoretically predicted dependence of ζ-potential on salt concentration, whereby the absolute value of ζ-potential diminished with increasing salt concentrations. We investigated binding of various plasma proteins with different sizes and charges using the bicinchoninic acid assay and immunofluorescence microscopy. Results showed effective and comparatively higher protein binding to NTs with 100 nm diameters (compared to 50 or 15 nm). We also showed a dose-dependent effect of serum amyloid A protein binding to NTs. These results and theoretical calculations of total available surface area for binding of proteins indicate that the largest surface area (also considering the NT lengths) is available for 100 nm NTs, with decreasing surface area for 50 and 15 nm NTs. These current investigations will have an impact on increasing the binding ability of biomedical devices in the body leading to increased durability of biomedical devices.

Adherence of oral streptococci to nanostructured titanium surfaces.

OBJECTIVES Peri-implantitis and peri-mucositis pose a severe threat to the success of dental implants. Current research focuses on the development of surfaces that inhibit biofilm formation while not inferring with tissue integration. This study compared the adherence of two oral bacterial species, Streptococcus sanguinis and Streptococcus mutans to nanostructured titanium surfaces. METHODS The samples included TiO2 nanotubes formed by anodization of titanium foil of 100, 50 and 15nm diameter (NT15, NT50, NT100), a nanoporous (15nm pore diameter) surface and compact TiO2 control. Adherent surviving bacteria were enumerated after 1h in an artificial saliva medium containing bovine mucin. RESULTS Lowest numbers of adherent bacteria of both species were recovered from the original titanium foil and nanoporous surface and highest numbers from the Ti100 nanotubes. Numbers of attached S. sanguinis increased in the order (NT15<NT50<NT100), correlated with increasing percentage of surface fluoride. The lowest adhesion of S. sanguinis and S. mutans on TiO2 nanostructured surfaces was observed for small diameter nanoporous surfaces which coincides with the highest osteoblast adhesion on small diameter nanotubular/nanoporous surfaces shown in previous work. SIGNIFICANCE This study indicates that the adherence of oral streptococci can be modified by titanium anodization and nanotube diameter.

Highly Conducting Spaced TiO2 Nanotubes Enable Defined Conformal Coating with Nanocrystalline Nb2O5 and High Performance Supercapacitor Applications

Establishing self-organized spacing between TiO2 nanotubes allows for highly conformal Nb2 O5 deposition that can be adjusted to optimized supercapacitive behavior.

The two step nanotube formation on TiZr as scaffolds for cell growth

Various TiO2 nanotubes on Ti50Zr alloy have been fabricated via a two step anodization method in glycol with 15vol.% H2O and 0.2M NH4F under anodization controlled voltages of 15, 30 and 45V. A new sonication treatment in deionized water with three steps and total sonication time as 1min was performed after the first anodization step in order to remove the oxide layer grown during 2h. The second step of anodization was for 1h and took place at the same conditions. The role of removed layer as a nano-prepatterned surface was evidenced in the formation of highly ordered nanotubular structures and morphological features were analyzed by SEM, AFM and surface wettability. The voltage-controlled anodization leads to various nanoarhitectures, with diameters in between 20 and 80nm. As biological assay, cell culture tests with MG63 cell line originally derived from a human osteosarcoma were performed. A correlation between nanostructure morphological properties as a result of voltage-controlled anodization and cell response was established.

Influence of various sterilization procedures on TiO2 nanotubes used for biomedical devices

Sterilization is the final surface treatment procedure of all implantable devices and is one of the key factors which have to be considered before implementation. Since different sterilization procedures for all implantable devices influence mechanical properties as well as biological response, the influence of different sterilization techniques on titanium nanotubes was studied. Commonly used sterilization techniques such as autoclaving, ultra-violet light sterilization, hydrogen peroxide plasma sterilization as well as the not so frequently used gaseous oxygen plasma sterilization were used. Three different nanotube diameters; 15 nm, 50 nm and 100 nm were employed to study the effects of various sterilization techniques. It was observed that autoclave sterilization resulted in destruction of nanotubular features on all three studied nanotube diameters, while UV-light and both kinds of plasma sterilization did not cause any significant morphological changes on the surfaces. Differences between the sterilization techniques employed influenced cytocompatibility, especially in the case of nanotubes with 100 nm diameter.

Attenuation of the macrophage inflammatory activity by TiO2 nanotubes via inhibition of MAPK and NF-κB pathways

Biomaterial implantation in a living tissue triggers the activation of macrophages in inflammatory events, promoting the transcription of pro-inflammatory mediator genes. The initiation of macrophage inflammatory processes is mainly regulated by signaling proteins of mitogen-activated protein kinase (MAPK) and by nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) pathways. We have previously shown that titania nanotubes modified Ti surfaces (Ti/TiO2) mitigate the immune response, compared with flat Ti surfaces; however, little is known regarding the underlying mechanism. Therefore, the aim of this study is to investigate the mechanism(s) by which this nanotopography attenuates the inflammatory activity of macrophages. Thus, we analyzed the effects of TiO2 nanotubes on the activation of MAPK and NF-κB signaling pathways in standard and lipopolysaccharide-evoked conditions. Results showed that the Ti/TiO2 significantly reduce the expression levels of the phosphorylated forms of p38, ERK1/2, c-Jun NH2-terminal kinase (JNK), IKKβ, and IkB-α. Furthermore, a significant reduction in the p65 nuclear accumulation on the nanotubular surface was remarked. Following, by using specific MAPK inhibitors, we observed that lipopolysaccharide-induced production of monocyte chemotactic protein-1 and nitric oxide was significantly inhibited on the Ti/TiO2 surface via p38 and ERK1/2, but not via JNK. However, the selective inhibitor for JNK signaling pathway (SP600125) was effective in reducing tumor necrosis factor alpha release as well as monocyte chemotactic protein-1 and nitric oxide production. Altogether, these data suggest that titania nanotubes can attenuate the macrophage inflammatory response via suppression of MAPK and NF-κB pathways providing a potential mechanism for their anti-inflammatory activity.