Structural and surface property characterization of titanium dioxide nanotubes for orthopedic implants

This research focused on the to modification of the surface structure of titanium implants with nanostructured morphology of TiO2 nanotubes and studied the interaction of nanotubes with osteoblast cells to understand the parameters that affect the cell growth. The electrical, mechanical, and structural properties of TiO2 nanotubes were characterized to establish a better understanding on the properties of such nanoscale morphological structures. To achieve the objectives of this research work I transformed the titanium and its alloys, either in bulk sheet form, bulk machined form, or thin film deposited on another substrate into a surface of titania nanotubes using a low cost and environmentally friendly process. The process requires only a simple electrolyte, low cost electrode, and a DC power supply. With this simple approach of scalable nanofabrication, a typical result is nanotubes that are each approximately 100nm in diameter and have a wall thickness of about 20nm. By changing the fabrication parameters, independent nanotubes can be fabricated with open volume between them. Titanium in this form is termed onedimensional since electron transport is narrowly confined along the length of the nanotube. My Ph.D. accomplishments have successfully shown that osteoblast cells, the cells that are the precursors to bone, have a strong tendency to attach to the inside and outside of the titanium nanotubes onto which they are grown using their filopodia – cell’s foot used for locomotion – anchored to titanium nanotubes. In fact it was shown that the cell prefers to find many anchoring sites. These sites are critical for cell locomotion during the first several weeks of maturity and upon calcification as a strongly anchored bone cell. In addition I have shown that such a surface has a greater cell density than a smooth titanium surface. My work also developed a process that uses a focused and controllably rastered ion beam as a nano-scalpel to cut away sections of the osteoblast cells to probe the attachment beneath the main cell body. Ultimately the more rapid growth of osteoblasts, coupled with a stronger cell-surface interface, could provide cost reduction, shorter rehabilitation, and fewer follow-on surgeries due to implant loosening

Compositions, methods and devices for generating nanotubes on a surface

A method for modifying a surface by generating nanotubes at one or more selected sites on the surface, the surface including a first metal. The method includes the steps of positioning at least one cathode and at least one anode relative to the surface in an electrolyte solution including a fluoride salt of a second metal, and applying a voltage between the at least one anode and the at least one cathode sufficient to generate nanotubes at one or more selected sites on the surface and to inhibit nanotube formation at one or more of the other selected sites, wherein the nanotubes include the first metal and the second metal.https://digitalcommons.mtu.edu/patents/1130/thumbnail.jp

Cerium oxide nanoparticle aggregates affect stress response and function in Caenorhabditis elegans

Objective: The continual increase in production and disposal of nanomaterials raises concerns regarding the safety of nanoparticles on the environmental and human health. Recent studies suggest that cerium oxide (CeO2) nanoparticles may possess both harmful and beneficial effects on biological processes. The primary objective of this study is to evaluate how exposure to different concentrations (0.17–17.21 µg/mL) of aggregated CeO2 nanoparticles affects indices of whole animal stress and survivability in Caenorhabditis elegans. Methods: Caenorhabditis elegans were exposed to different concentrations of CeO2 nanoparticles and evaluated. Results: Our findings demonstrate that chronic exposure of CeO2 nanoparticle aggregates is associated with increased levels of reactive oxygen species and heat shock stress response (HSP-4) in Caenorhabditis elegans, but not mortality. Conversely, CeO2 aggregates promoted strain-dependent decreases in animal fertility, a decline in stress resistance as measured by thermotolerance, and shortened worm length. Conclusion: The data obtained from this study reveal the sublethal toxic effects of CeO2 nanoparticle aggregates in Caenorhabditis elegans and contribute to our understanding of how exposure to CeO2 may affect the environment

The role of electron irradiation history in liquid cell transmission electron microscopy.

In situ liquid cell transmission electron microscopy (LC-TEM) allows dynamic nanoscale characterization of systems in a hydrated state. Although powerful, this technique remains impaired by issues of repeatability that limit experimental fidelity and hinder the identification and control of some variables underlying observed dynamics. We detail new LC-TEM devices that improve experimental reproducibility by expanding available imaging area and providing a platform for investigating electron flux history on the sample. Irradiation history is an important factor influencing LC-TEM results that has, to this point, been largely qualitatively and not quantitatively described. We use these devices to highlight the role of cumulative electron flux history on samples from both nanoparticle growth and biological imaging experiments and demonstrate capture of time zero, low-dose images on beam-sensitive samples. In particular, the ability to capture pristine images of biological samples, where the acquired image is the first time that the cell experiences significant electron flux, allowed us to determine that nanoparticle movement compared to the cell membrane was a function of cell damage and therefore an artifact rather than visualizing cell dynamics in action. These results highlight just a subset of the new science that is accessible with LC-TEM through the new multiwindow devices with patterned focusing aides

Cerium oxide nanoparticles attenuate acute kidney injury induced by intra-abdominal infection in Sprague-Dawley rats

Background Intra-abdominal infection or peritonitis is a cause for great concern due to high mortality rates. The prognosis of severe intra-abdominal infection is significantly diminished in the presence of acute kidney injury (AKI) which is often characterized by renal tubular cell death that can lead to renal failure. The purpose of the current study is to examine the therapeutic efficacy of cerium oxide (CeO2) nanoparticles for the treatment of peritonitis-induced AKI by polymicrobial insult. Results A one-time administration of CeO2 nanoparticles (0.5 mg/kg) in the absence of antibiotics or other supportive care, attenuated peritonitis-induced tubular dilatation and the loss of brush border in male Sprague–Dawley rats. These improvements in renal structure were accompanied by decreases in serum cystatin-C levels, reduced renal oxidative stress, diminished Stat-3 phosphorylation and an attenuation of caspase-3 cleavage suggesting that the nanoparticle treatment improved renal glomerular filtration rate, diminished renal inflammation and reduced renal apoptosis. Consistent with these data, further analysis demonstrated that the CeO2 nanoparticle treatment diminished peritonitis-induced increases in serum kidney injury molecule-1 (KIM-1), osteopontin, β-2 microglobulin and vascular endothelial growth factor-A (VEGF-A) levels. In addition, the nanoparticle attenuated peritonitis-induced hyperglycemia along with increases in blood urea nitrogen (BUN), serum potassium and sodium. Conclusion CeO2 nanoparticles scavenge reactive oxygen species and attenuate polymicrobial insult induced increase in inflammatory mediators and subsequent AKI. Taken together, the data indicate that CeO2 nanoparticles may be useful as an alternative therapeutic agent or in conjunction with standard medical care for the treatment of peritonitis induced acute kidney injury

Improved tribocorrosion performance of bio-functionalized TiO₂ nanotubes under two-cycle sliding actions in artificial saliva

After insertion into bone, dental implants may be subjected to tribocorrosive conditions resulting in the release of metallic ions and solid wear debris, which can induce to peri-implant inflammatory reactions accompanied by bone loss, and ultimately implant loosening. Despite the promising ability of TiO2 nanotubes (NTs) to improve osseointegration and avoid infection-related failures, the understanding of their degradation under the simultaneous action of wear and corrosion (tribocorrosion) is still very limited. This study aims, for the first time, to study the tribocorrosion behavior of bio-functionalized TiO2 NTs submitted to two-cycle sliding actions, and compare it with conventional TiO2 NTs. TiO2 NTs grown by anodization were doped with bioactive elements, namely calcium (Ca), phosphorous (P), and zinc (Zn), through reverse polarization anodization treatments. Characterization techniques such as scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and scanning transmission electron microscopy (STEM), were used to characterize the films. Tribocorrosion tests were carried out in artificial saliva (AS) by applying two cycles of reciprocating sliding actions. The open circuit potential (OCP) was monitored before,during, andafterboth cyclesofsliding, duringwhichthe coefficientoffriction (COF)was calculated. The resulting wear scars were analyzed by SEM and EDS, and wear volume measurements were performed by 2D profilometry. Finally, the mechanical features of TiO2 NTs were accessed by nanoindentation. The results show that bio-functionalized TiO2 NTs display an enhanced tribocorrosion performance, ascribed to the growth of a nano-thick oxide film at Ti/TiO2 NTs interface, which significantly increased their adhesion strength to the substrate and consequently their hardness. Furthermore, it was discovered that during triboelectrochemical solicitations, the formation of a P-rich tribofilm takes place, which grants both electrochemical protection and resistance to mechanical wear. This study provides fundamental and new insights for the development of multifunctional TiO2 NTs with long-term biomechanical stability and improved clinical outcomes.This work was supported by FCT with the reference project UID/ EEA/04436/2013 and by FEDER funds through the COMPETE 2020 – Programa Operacional Competitividade e Internacionalização (POCI) with the reference project POCI-01–0145-FEDER-006941. Theauthors alsoacknowledge the financial support fromFCTbythe doctoral grant (Ref. SFRH/BD/88517/2012), CAPES (Proc. 99999.008666/2014-08), CNPq (Proc. 490761/2013-5) and UNESP. Moreover, the authors are grateful to LABNANO/CBPF (Brazilian Center for Research in Physics) for all the support provided in electron microscopy analyses. Finally, Tolou Shokuhfar is also thankful to US National Science Foundation NSF-DMR CAREER award # 1564950.info:eu-repo/semantics/publishedVersio

Tribo-electrochemical behavior of bio-functionalized TiO2 nanotubes in artificial saliva: Understanding of degradation mechanisms

It has been shown that the synthesis of TiO2 nanotubes by anodization provides outstanding properties to Ti surfaces intended for dental and orthopedic implants applications. Beyond the very well-known potential of these surfaces to improve osseointegration and avoid infection, the knowledge on the adhesion and degradation behavior of TiO2 nanotubes under the simultaneous action of wear and corrosion is still poorly understood and these are issues of tremendous importance. The main aim of this work is to investigate, for the first time, the tribo-electrochemical degradation behavior of Ti surfaces decorated with TiO2 nanotubes before and after bio-functionalization treatments.Well-aligned TiO2 nanotubes (NTs) were produced containing elements natively present in bone such as calcium (Ca) and phosphorous (P), in addition of zinc (Zn) as an antimicrobial agent and stimulator of bone formation. The synthesis of Ca/P/Zn-doped nanotubes (NT-Ca/P/Zn) was achieved by reverse polarization and anodization treatments applied to conventional TiO2 nanotubes grown by two-step anodization. The nanotube surfaces were analyzed by scanning electron microscopy (SEM) while dark-field scanning transmission electron microscopy (STEM-DF) was used to characterize the Ti/TiO2 nanotubular films interfaces. Tribo-electrochemical tests were conducted under reciprocating sliding conditions in artificial saliva. The open circuit potential (OCP) was monitored before, during and after sliding tests, and the coefficient of friction (COF) values were registered during rubbing action. The wear tracks resulting from sliding tests were characterized by SEM and wear volume measurements were carried out by 2D profilometry.The results show that the tribo-electrochemical behavior of TiO2 nanotubes was significantly improved after bio-functionalization treatments. The higher electrochemical stability and lower mechanical degradation of these films was correlated with their improved adhesion strength to Ti substrate, which is granted by the nano-thick oxThis work was supported by FCT with the reference project UID/EEA/04436/2013 and by FEDER funds through the COMPETE 2020 - Programa Operacional Competitividade e Internacionalizacao (POCI) with the reference project POCI-01-0145-FEDER-006941.The authors also acknowledge the financial support from FCT by the doctoral grant (Ref. SFRH/BD/88517/2012), CAPES (Proc. 99999.008666/2014-08), CNPq (Proc. 490761/2013-5) and UNESP. Also, the authors would like to thank LABNANO/CBPF (Brazilian Center for Research in Physics) for all the support in electron microscopy analyses. Tolou Shokuhfar is especially thankful to US National Science Foundation NSF-DMR CAREER award # 1564950.info:eu-repo/semantics/publishedVersio

Facile electrochemical synthesis of antimicrobial TiO2 nanotube arrays

Infection-related complications have been a critical issue for the application of titanium orthopedic implants. The use of Ag nanoparticles offers a potential approach to incorporate antimicrobial properties into the titanium implants. In this work, a novel and simple method was developed for synthesis of Ag (II) oxide deposited TiO2 nanotubes (TiNTs) using electrochemical anodization followed by Ag electroplating processes in the same electrolyte. The quantities of AgO nanoparticles deposited in TiNT were controlled by selecting different electroplating times and voltages. It was shown that AgO nanoparticles were crystalline and distributed throughout the length of the nanotubes. Inductively coupled plasma mass spectrometry tests showed that the quantities of released Ag were less than 7 mg/L after 30 days at 37°C. Antimicrobial assay results show that the AgO-deposited TiNTs can effectively kill the Escherichia coli bacteria. Although the AgO-deposited TiNTs showed some cytotoxicity, it should be controllable by optimization of the electroplating parameters and incorporation of cell growth factor. The results of this study indicated that antimicrobial properties could be added to nanotextured medical implants through a simple and cost effective method

Surfactant-assisted hydrothemial synthesis of fluoridated hydroxyapatite nanorods

Fluoridated Hydroxyapatite (FHA) nanorods were synthesized using Apricot Tree Gum (ATG) as a novel surfactant and then compared with Ethylenediaminetetraacetic acid disodium salt dihydrate (EDTA) and Sodium Dodecyl Sulfate (SDS) as conventional surfactant agents under hydrothermal condition (70 degrees C and 1 atm). The effects of pH values and various types of surfactants on the formation of the FHA nanorods, crystalline phase, and chemical compositions were investigated using Field Emission Scanning Electron Microscopy (FESEM) equipped by Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). The findings indicated application of the presented ATG as surfactant is able to produce the hexagonal nanorods of FHA along their c-axis direction. Moreover, it is illustrated that diameter and length of nanorods which is obtained by ATG surfactant are bigger than EDTA and SDS. In addition, it is demonstrated that pH values can play a major role on formation of hexagonal FHA nanorods. The increase of pH transformed the shape of synthesized FHA from particles to rods. Ultimately, based on the similarity of synthesized FHA nanorods to the shape, structure, and composition of enamel; it is suggested for its potential to be used for dental applications

Hydrophilic nanotube coating of Ti implant materials for potential rapid bone regeneration

The properties of implant materials used in humans may have important influences on the outcomes of clinical treatments. Recently, titanium and titanium alloys have been extensively employed as in-vivo implant materials, due to their generally favorable biocompatibility, high resistance to corrosion, and relatively low cost. On the other hand, even when using chemically identical materials, the biocompatibility of an implant or its stability depends heavily on its surface structure, as well as the thickness and properties of the surface oxide film. As the characteristics of the implant surface have been reported to play an important role in the in-vivo reactions of implants, a great deal of interest has recently been focused on different surface treatment methods. Currently, there are a variety of methods with which titanium implant surfaces are treated. The anodizing method is an electrochemical technique, which forms a rough, thick oxidized capsule with nanotubular structures on the implant surface. To increase the biocompatibility and bone regeneration and to improve the current shortcomings of Ti and Ti alloy (Ti6Al4V)implants, we applied a uniquely fabricated nanotubular coating over the surface of such implants