Cytocompatibility with osteogenic cells and enhanced in vivo anti-infection potential of quaternized chitosan-loaded titania nanotubes

Infection is one of the major causes of failure of orthopedic implants. Our previous study demonstrated that nanotube modification of the implant surface, together with nanotubes loaded with quaternized chitosan （hydroxypropyltrimethyl ammonium chloride chitosan, HACC）, could effectively inhibit bacterial adherence and biofilm formation in vitro. Therefore, the aim of this study was to further investigate the in vitro cytocompatibility with osteogenic cells and the in vivo anti-infection activity of titanium implants with HACC-loaded nanotubes （NT-H）. The titanium implant （Ti）, nanotubes without polymer loading （NT）, and nanotubes loaded with chitosan （NT-C） were fabricated and served as controls. Firstly, we evaluated the cytocompatibility of these specimens with human bone marrow-derived mesenchymal stem cells in vitro. The observation of cell attachment, proliferation, spreading, and viability in vitro showed that NT-H has improved osteogenic activity compared with Ti and NT-C. A prophylaxis rat model with implantation in the femoral medullary cavity and inoculation with methiciUin-resistant Staphylococcus aureus was established and evaluated by radiographical, microbiological, and histopathological assessments. Our in vivo study demonstrated that NT-H coatings exhibited significant anti-infection capability compared with the Ti and NT-C groups. In conclusion, HACC-loaded nanotubes fabricated on a titanium substrate show good compatibility with osteogenic cells and enhanced anti-infection ability in vivo, providing a good foundation for clinical application to combat orthopedic implant-associated infections.

Detection of Trace Heavy Metals Ions by Arrays of Titania Nanotubes Annealed in Nitrogen

Redox response of trace heavy metals ions（THMIs） has better performance on highly ordered vertically oriented titania nanotube arrays（TNA） annealed in nitrogen. Experimental data showed that different THMIs possess different reaction peak shapes and charge and discharge capacities. Therefore, the TNA will become an important tool used for environmental protection and facilitating the rapid determination of THMIs. THMIs of 5×10^4 mol/L concentration were measured at a scan rate of 100 mV/s. The analytical utility of TNA is demonstrated in a neutral 0.5 mol/L Na2SO4 solution. The results sufficiently show that titania nanotube arrays electrodes（TNAE） will be used to measure THMIs.

Rapid inactivation of multidrug-resistant bacteria and enhancement of osteoinduction via titania nanotubes grafted with polyguanidines

The rapid in situ inhibition of bacterial contamination and subsequent infection without inducing drug resistance is highly vital for the successful implantation and long-term service of titanium(Ti)-based orthopedic implants.However,the instability and potential cytotoxicity of current coatings have deterred their clinical practice.In this study,anodic oxidized titania nanotubes(TNT)were modified with antibacterial polyhexamethylene guanidine(PG)with the assistance of 3,4-dihydroxyphenylacetic acid.Interestingly,the prepared TNT-PG coating exhibited superior in vitro antibacterial activity than flat Ti-PG coating and effectively killed typical pathogens such as Escherichia coli and superbug methicillinresistant Staphylococcus aureus with above 4-log reduction(>99.99%killed)in only 5 min.TNT-PG coating also exerted excellent hemocompatibility with red blood cells and nontoxicity toward mouse pre-osteoblasts(MC3 T3-E1)in 1 week of coculture.In addition,the efficient in vivo anti-infective property of this coating was observed in a rat subcutaneous infection model.More importantly,TNT-PG coating improved the expression of alkaline phosphatase and enhanced the extracellular matrix mineralization of pre-osteoblasts,denoting its osteoinductive capacity.This versatile TNT-PG coating with excellent antibacterial activity and biocompatibility could be a promising candidate for advanced orthopedic implant applications.

Direct Imaging of Titania Nanotubes Located in Mouse Neural Stem Cell Nuclei

Titania nanotubes(TiO2-NTs)are a potential drug vehicle for use in nanomedicine.To this end,a preliminary study of the interaction of a model cell with TiO2-NTs has been carried out.TiO2-NTs were first conjugated with a fl uorescent label,fl uorescein isothiocyanate(FITC).FITC-conjugated titania nanotubes(FITC-TiO2-NTs)internalized in mouse neural stem cells(NSCs,line C17.2)can be directly imaged by confocal microscopy.The confocal imaging showed that FITC-TiO2-NTs readily entered into the cells.After co-incubation with cells for 24 h,FITC-TiO2-NTs localized around the cell nucleus without crossing the karyotheca.More interestingly,the nanotubes passed through the karyotheca entering the cell nucleus after co-incubation for 48 h.Atomic force microscopy(AFM)and transmission electron microscopy(TEM)were also employed in tracking the nanotubes in the cell.These results will be of benefit in future studies of TiO2-NTs for use as a drug vehicle,particularly for DNA-targeting drugs.

Fabrication and Significant Photoelectrochemical Activity of Titania Nanotubes Modified with Thin Indium Tin Oxide Film

Ordered titanium dioxide nanotubes （TiOaNTs） modified with indium tin oxide （ITO） films were obtained via magnetron sputtering, in which ITO plate was used as a target, onto the as-anodized titania support followed by the calcination process. The morphology of fabricated material with deposited oxide was investigated using scanning electron microscopy. Raman and UV-Vis spectroscopies were utilized to characterize crystalline phase and optical properties of prepared samples, whereas X-ray photoelectron spectroscopy allowed determining the binding energy of present elements. In the case of titanium, three various oxidation states were identified and also the presence of indium and tin was confirmed. The electrochemical test carried out when the sample was exposed to light allows for selection of the most photoactive material. The highest photocurrent was registered when only 5-nm ITO layer was sputtered, and it equals 256 and 133 μA cm^-2 for the electrode material immersed in 0.5 M KOH and K2SO4 electrolytes, respectively, that is accordingly 3.5 and 4.4 times higher than the one observed for pristine titania. Furthermore, ITO-modified titania exhibits excellent photostability upon prolonged illumination that is of key importance for possible application in light-driven processes.

Different antibacterial mechanisms of titania nanotube arrays at various growth phases of E.coli

To clarify the antibacterial behavior at early adhesion,two titania nanotube(TNT)arrays were fabricated on polished commercially pure titanium(Ti),and the interaction mechanisms between TNT arrays and the model bacteria(Escherichia coli,E.coli)were investigated.The results show that TNT arrays exhibit a significant early antibacterial effect,which is highly related to the surface free energy and nano-topography.The underlying antibacterial mechanisms include:(1)the anti-initial-attachment effect at the lag phase(0−4 h);(2)the anti-proliferation and physical bactericidal effects at the logarithmic phase(4−12 h);(3)the reduced antimicrobial properties probably due to the overgrowth of bacteria on TNT arrays at the stationary phase(12 h and then).

Enhanced photocatalytic activity of nanotube-like titania by sulfuric acid treatment

The TiO 2 nanotube sample was prepared via a NaOH solution in a Teflon vessel at 150℃. The as-prepared nanotubes were then treated with H 2SO 4 solutions. The TiO 2 nanotube has a crystalline structure with open-ended and multiwall morphologies. The TiO 2 nanotubes before and after surface acid treatment were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and UV-VIS dispersive energy spectrophotometry(DRS). The photocatalytic activity of the samples was evaluated by photocatalytic degradation of acid orange II in aqueous solutions. It was found that the order of photocatalytic activity was as follows: TiO 2 nanotubes treated with 1.0 mol/L H 2SO 4 solution (TiO 2(1.0M H 2SO 4) nanotubes)>TiO 2 nanotubes treated with 0.2 mol/L H 2SO 4 solution (TiO 2(0.2M H 2SO 4) nanotubes)>TiO 2 nanotubes >TiO 2 powder. This was attributed to the fact that TiO 2 nanotubes treated with H 2SO 4 was composed of smaller particles and had higher specific surface areas. Furthermore, the smaller TiO 2 particles were beneficial to the transfer and separation of photo-generated electrons and holes in the inner of and on the surface of TiO 2 particles and reduced the recombination of photo-generated electrons and holes. Acid treatment was particularly effective for TiO 2 nanotubes, this increase in activity was correlated with the concentration of H 2SO 4 solution.

Influence evaluation of titania nanotube surface morphology on the performance of bioelectrochemical systems

In order to investigate the effect of the surface morphology and resistance of the TiO2 semiconductor on current output,TiO2 nanotube array bio-anodes(TNA)are synthesized at different electrolyte temperatures,thereby changing the length and surface roughness of the nanotubes.When the anodizing temperature is increased from 30 to 75℃,the length of the nanotubes increases from 1.459 to 4.183μm,which hinders the transfer of extracellular electrons to the electrodes.On the other hand,the surface roughness of TNA is significantly improved at higher temperatures,which is conducive to electron transfer.Therefore,samples processed at 45℃have the best current output performance.Compared with the treatment at 30℃under anodization,samples processed at 45℃can balance the resistance and roughness and have a higher electron transfer rate;the current output density of which is increased by 1.5 times,and the decolorization rate is increased by 0.8 times.Therefore,proper TNA surface morphology can improve the current output and the potential of wastewater treatment.

Octahedral Cu_2O-modified TiO_2 nanotube arrays for efficient photocatalytic reduction of CO_2

A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.

Photocatalytic and Photoelectronic Properties of Anatase TiO_2 Modified by Cu Ions Plasma and Its Theoretic Study by the First Principle Study

Highly oxidation. SEM analysis ordered anatase titania nanotube method was used to characterize arrays （TINT） were fabricated by anodic the morphology of the prepared samples. TiNT samples doped with Cu ions were prepared by home-made Metal Vapor Vacuum Arc ions sources （MEVVA, BNU, China） implanter. Photo-electric response and methyl orange decomposition ability of implanted samples under UV and visible light were tested, and the results indicated that the performance of Cu/TiNT enhanced significantly under visible light; it was noteworthy that the photocurrent density of A-Cu/TiNT was 0.102 mA/cm^2, which was 115 times that of pure TINT, and degradation ability of TiNT also strongly enhanced under visible light. In a word, the absorption spectrum of implanted anatase titania shifted to a longer wavelength region. Theoretic study on Cu-doped anatase based on density functional theory was carried out in this paper to validate the experiment results. The calculation results are depicted as follows： Intermittent energy band appeared around the Fermi energy after doping with Cu metal, the width of which was 0.35 eV and the location of valence and conduction bands shifted to the lower energy level by 0.22 eV; more excitation and jump routes were opened for the electrons. The narrowed band gaps allowed the photons with lower energy （at longer wavelength, such as visible light） to be absorbed, which accorded well with the experimental results.

Effect of Anodization Parameters on Morphologies of TiO2 Nanotube Arrays and Their Surface Properties

This work presents the potentiostatic anodization study of titania nanotube array films fabricated in fluoride-based organic electrolytes including DEG （diethylene glycol） and EG （ethylene glycol）. The work focuses on the effect of important anodization parameters such as applied voltage, anodization time, and electrolyte type on nanotube morphologies and corresponding surface properties. Depending upon unique nanotube formation structures obtained from each anodizing electrolyte, wettability of the nanotube array layer has been determined by means of the contact angle measurement. The EG nanotube array films with close-packing cell orientation are found to show hydrophilic behavior. While the well separated DEG nanotube array films are found to exhibit hydrophobic behavior, with the characteristics of more discrete, wider cell separation obtained through manipulating the electrolyte conditions and the fabrication techniques offering considerable prospects for developing the superhydrophobic sample surface. Such formation structures observed for the DEG fabricated nanotube is believed to play a prominent role in determining the surface wettability of the anodized nanotube array film. The achieved result in this work is anticipated to pave the way to other relevant applications, where interfacial properties are critically concerned.

Effect of Palladium Nanoparticles on Photocatalytic Characteristics of N doped Titania Catalyst

To improve the photocatalytic efficiency of TiO2nanotubular catalyst,N doped and Pd decorated titania nanotubes was successfully synthesized via anodizing,hydrazine hydrate treatment and photoreduction of Pd ions.The small Pd nanoparticles were precipitated on TiO2nanotubes through photoreduction of Pd ions,and its distribution is relatively homogeneous.From X-ray photoelectron spectrometry（XPS） result,the N 1s spectrum represents two peaks with binding energy at 399.7 and 400.7 eV,which suggests that the nitrogen elements doped by hydrazine hydrate treatment are located in interstitial sites of the TiO2crystalline structure.For N doped TiO2nanotubes with Pd particles,a high photocurrent was detected due to increase of interface charge carrier separation rate.Moreover,N doped and Pd decorated TiO2nanotubes exhibited much higher dye destruction efficiency and rate constant due to the synergistic effect of the N dopant and the Pd deposition on TiO2nanotubes.

Growing vertical aligned mesoporous silica thin film on nanoporous substrate for enhanced degradation,drug delivery and bioactivity

Mesoporous silica thin film has been widely used in various fields,particularly the medical implant coating for drug delivery.However,some drawbacks remain with the films produced by traditional method(evaporation-induced self-assembly,EISA),such as the poor permeability caused by their horizontal aligned mesochannels.In this study,the vertical aligned mesoporous silica thin film(VMSTF)is uniformly grown alongside the walls of titania nanotubes array via a biphase stratification growth method,resulting in a hierarchical two-layered nanotubular structure.Due to the exposure of opened mesopores,VMSTF exhibits more appealing performances,including rapid degradation,efficient small-molecular drug(dexamethasone)loading and release,enhanced early adhesion and osteogenic differentiation of MC3T3-E1 cells.This is the first time successfully depositing VMSTF on nanoporous substrate and our findings suggest that the VMSTF may be a promising candidate for bone implant surface coating to obtain bioactive performances.