Zinc (Zn) Doping by Hydrothermal and Alkaline Heat-Treatment Methods on Titania Nanotube Arrays for Enhanced Antibacterial Activity.

Titanium (Ti) is a popular biomaterial for orthopedic implant applications due to its superior mechanical properties such as corrosion resistance and low modulus of elasticity. However, around 10% of these implants fail annually due to bacterial infection and poor osseointegration, resulting in severe pain and suffering for the patients. To improve their performance, nanoscale surface modification approaches and doping of trace elements on the surfaces can be utilized which may help in improving cell adhesion for better osseointegration while reducing bacterial infection. In this work, at first, titania (TiO2) nanotube arrays (NT) were fabricated on commercially available pure Ti surfaces via anodization. Then zinc (Zn) doping was conducted following two distinct methods: hydrothermal and alkaline heat treatment. Scanning electron microscopic (SEM) images of the prepared surfaces revealed unique surface morphologies, while energy dispersive X-ray spectroscopy (EDS) revealed Zn distribution on the surfaces. Contact angle measurements indicated that NT surfaces were superhydrophilic. X-ray photoelectron spectroscopy (XPS) provided the relative amount of Zn on the surfaces and indicated that hydrothermally treated surfaces had more Zn compared to the alkaline heat-treated surfaces. X-ray crystallography (XRD) and nanoindentation techniques provided the crystal structure and mechanical properties of the surfaces. While testing with adipose-derived stem cells (ADSC), the surfaces showed no apparent cytotoxicity to the cells. Finally, bacteria adhesion and morphology were evaluated on the surfaces after 6 h and 24 h of incubation. From the results, it was confirmed that NT surfaces doped with Zn drastically reduced bacteria adhesion compared to the Ti control. Zn-doped NT surfaces thus offer a potential platform for orthopedic implant application.

TiO2NTs bio-inspired coatings: revisiting electrochemical, morphological, structural, and mechanical properties.

By altering some synthesis variables, the morphology and structural properties of anodic TiO2nanotube arrays (TiO2NTs) can be tailored to a specific application. This study aims to investigate the effect of electrolyte-containing ions from human plasma and annealing temperature on structural, morphological, and mechanical parameters of TiO2NTs films, targeting its potential biomedical applications. Bio-inspired TiO2NTs were grown from Ticpand its Ti6Al4V alloy by potentiostatic anodization in the recently developed SBF-based electrolyte, maintained at 10 °C and 40 °C. The thermal investigation was performed by TGA/DSC and used to define the phase transition temperatures used for annealing (450 °C and 650 °C). Morphological and structural parameters were evaluated by FE-SEM, XRD, contact angle measurements, and nanoindentation. Results show that self-organized as-formed TiO2NTs were grown under all synthesis conditions with different wettability profiles for each substrate group. At 450 °C annealing temperature, the beginning of nanostructures collapse starts, becoming evident at 650 °C. The nanoindentation characterization reveals that both electrolyte and thermal annealing exhibited low effects on the hardness and Young's modulus. The tailoring of specific properties by different synthesis conditions could allow the individualization of treatments and better performancein vivo.

Effect of cellulose size-concentration on the structure of polyvinyl alcohol hydrogels.

Microfibrillated cellulose as a reinforcement agent has been investigated extensively due to their unique characteristics, which can reorder the structure of polymers and hydrogels leading to improved mechanical properties with minimal disadvantages in terms of the targeted original applications. However, effect of using a macro- to a micro-fibrillated cellulose onto polyvinyl alcohol hydrogels is still unknown, because of the unique ability for both to be produced as hydrogels from freeze-thawing mechanisms - hydrogen bonding - there is a potential synergism. Therefore, macro and microfibrillated kraft bleached paper was synthesised at various concentrations on polyvinyl alcohol hydrogels. The overall effect presented a strong interaction between both compounds but it was increased with macrofibrillated cellulose. Increase in crystallinity was also observed with a macro-sized fibre without variation on tensile elastic modulus but an overall improvement was perceived on thermal properties and a slower swelling rate with a microfibrillated cellulose.

Niobium treated by Plasma Electrolytic Oxidation with calcium and phosphorus electrolytes.

Niobium plates were electrochemically treated by Plasma Electrolytic Oxidation (PEO) with electrolytes containing phosphorous and/or calcium. Three different electrolyte and experimental parameters were used forming three different surfaces. Film morphology, thickness, and chemical composition were analyzed by scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A profilometer and the sessile drop technique measured the average surfaces roughness (Ra) and contact angles respectively. X-ray diffraction technique (XRD) analyzed the oxide crystallinity, and scratch tests evaluated the film adhesion. All oxidized surfaces presented pores, without observed cracks. Comparing the different experimental conditions, films obtained with phosphoric acid (P100) show superficial pores, phosphorus incorporation, high hydrophilicity, non-crystalline oxide formation, and good scratch resistance. Films treated with calcium acetate electrolyte (Ca100), compared to P100 exhibit smaller size pores and film thickness, smaller hydrophilicity, and lower scratch resistance. They also demonstrated higher oxide crystallinity, calcium incorporation, and pores interconnections. When the PEO was executed with a blended electrolyte containing calcium acetate and phosphoric acid (Ca50P50) the formed films presented the highest thickness, high phosphorus incorporation, and the lowest contact angle compared with other films. In addition, the pores size, the scratch resistance, calcium incorporation, and oxide crystallinity present intermediate values compared to P100 and Ca100 films. Film crystallinity seems to be influenced by calcium incorporation, whereas, hydrophilicity is phosphorus amount dependent. The pores amount and their interconnections reduced the scratch resistance. Surface features obtained in this work are largely mentioned as positive characteristics for osseointegration processes.

Apatite grown in niobium by two-step plasma electrolytic oxidation.

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1µL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb2O5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition.