Surface Free Energy and Composition Changes and Ob Cellular Response to CHX-, PVPI-, and ClO2-Treated Titanium Implant Materials.

The study evaluated the interaction of a titanium dental implant surface with three different antibacterial solutions: chlorhexidine, povidone-iodine, and chlorine dioxide. Implant surface decontamination is greatly challenging modern implant dentistry. Alongside mechanical cleaning, different antibacterial agents are widely used, though these could alter implant surface properties. Commercially pure (CP) grade 4 titanium (Ti) discs were treated with three different chemical agents (chlorhexidine 0.2% (CHX), povidone-iodine 10% (PVPI), chlorine dioxide 0.12% (ClO2)) for 5 min. Contact angle measurements, X-ray photoelectron spectroscopy (XPS) analysis, and cell culture studies were performed. Attachment and proliferation of primary human osteoblast cells were investigated via MTT (dimethylthiazol-diphenyl tetrazolium bromide), alamarBlue, LDH (lactate dehydrogenase), and fluorescent assays. Contact angle measurements showed that PVPI-treated samples (Θ = 24.9 ± 4.1) gave no difference compared with controls (Θ = 24.6 ± 5.4), while CHX (Θ = 47.2 ± 4.1) and ClO2 (Θ = 39.2 ± 9.8) treatments presented significantly higher Θ values. All samples remained in the hydrophilic region. XPS analysis revealed typical surface elements of CP grade 4 titanium (Ti, O, and C). Both MTT and alamarBlue cell viability assays showed similarity between treated and untreated control groups. The LDH test revealed no significant difference, and fluorescent staining confirmed these results. Although there was a difference in surface wettability, a high proliferation rate was observed in all treated groups. The in vitro study proved that CHX, PVPI, and ClO2 are proper candidates as dental implant decontamination agents.

Noble-Metal-Free Iron Nitride/Nitrogen-Doped Graphene Composite for the Oxygen Reduction Reaction.

Considerable effort has been devoted recently to replace platinum-based catalysts with their non-noble-metal counterparts in the oxygen reduction reaction (ORR) in fuel cells. Nitrogen-doped carbon structures emerged as possible candidates for this role, and their earth-abundant metal-decorated composites showed great promise. Here, we report on the simultaneous formation of nitrogen-doped graphene and iron nitride from the lyophilized mixture of graphene oxide and iron salt by high-temperature annealing in ammonia atmosphere. A mixture of FeN and Fe2N particles was formed with average particle size increasing from 23.4 to 127.0 nm and iron content ranging from 5 to 50 wt %. The electrocatalytic oxygen reduction activity was investigated via the rotating disk electrode method in alkaline media. The highest current density of 3.65 mA cm-2 at 1500 rpm rotation rate was achieved in the 20 wt % catalyst via the four-electrode reduction pathway, exceeding the activity of both the pristine iron nitride and the undecorated nitrogen-doped graphene. Since our catalysts showed improved methanol tolerance compared to the platinum-based ones, the formed non-noble-metal system offers a viable alternative to the platinum-decorated carbon black (Pt/CB) ORR catalysts in direct methanol fuel cells.

Gold Size Effect in the Thermal-Induced Reaction of CO2 and H2 on Titania- and Titanate Nanotube-Supported Gold Catalysts.

In this paper, we study the thermal activation of CO2 on the surface of small Au nanoparticles supported on TiO2 and titanate nanotube. We characterize the catalysts with high resolution transmission electron microscopy (HR-TEM) and total gold content measurement. We performed catalytic test in flow reactors then we investigate the surface of the catalysts during the adsorption and reaction processes by diffuse reflectance infrared spectroscopy (DRIFTS). The size of gold nanoparticles on the surface has been found to have the most important effect on the final activity of the studied catalysts. Significantly higher TOF values were obtained when the size of Au were smaller on both TiO2 and titanate nanotube supports. The size of the Au nanoparticles with the method of their preparation was controlled. The gold adatom promotes the adsorption and scission of CO2, but the nature of the support has got important effect, too. The explored reaction schemes may pave the way towards novel catalytic materials that can solve challenges associated with the activation of CO2 and thus contribute to a greener chemistry related to it.

Stability and Temperature-Induced Agglomeration of Rh Nanoparticles Supported by CeO2.

The effects of reduction by H2 and by heat treatment in vacuum and in O2 flow on Rh particle size changes of Rh/CeO2 samples were studied by X-ray photoelectron spectroscopy (XPS), high-resolution electron microscopy (HRTEM), and CO adsorption followed by diffuse reflectance infrared spectroscopy (DRIFTS). Low-temperature (373-423 K) reduction of Rh without agglomeration is demonstrated. An average particle size of 2.3 ± 1.1 nm was measured by HRTEM regardless of the metal loading (1-5%). On Rh/CeO2, a significant particle size increase of the Rh particles was detected on heating (773 K). In this work, we suggest that the temperature-induced surface decrease resulting from the sintering of Rh is favored only for well-dispersed particles. XP spectra revealed that the mobile oxygens of CeO2 fundamentally determine the oxidation state of the supported metals. At elevated temperature, the oxidation of the reduced support surface as well as the metal component takes place because of the segregation of ceria oxygens. When the aggregated particles were reoxidized, the redispersion of Rh was observed probably because of the formation of Rh-O-Ce bonds.

Attachment and proliferation of human osteoblast-like cells (MG-63) on laser-ablated titanium implant material.

Demand is increasing for shortening the long (3-6 months) osseointegration period to rehabilitate patients' damaged chewing apparatus in as short a time as possible. For dental implants, as for biomaterials in general, the bio- and osseointegration processes can be controlled at molecular and cellular levels by modification of the implant surface. One of the most promising of such surface modifications is laser ablation, as demonstrated by our previous results [46]. Commercially pure (CP4) sand-blasted, acid-etched titanium disks (Denti® System Ltd., Hungary) were irradiated with a KrF excimer laser (248 nm, fluence 0.4 J/cm(2), FWHM 18 ns, 2000 pulses), or with a Nd:YAG laser (532 nm, 1.3 J/cm(2), 10 ns, 200 pulses) then examined by SEM, AFM, and XPS. In vitro attachment (24 h) and proliferation (72 h) of MG-63 osteoblast cells were investigated via dimethylthiazol-diphenyl tetrazolium bromide (MTT), alamarBlue (AB) assays alkaline phosphatase quantification (ALP) and SEM. SEM and AFM revealed significant changes in morphology and roughness. XPS confirmed the presence of TiO2 on each sample; after Nd:YAG treatment a reduced state of Ti (Ti(3+)) was also observed. MTT, AB and ALP measurements detected an increase in the number of cells between the 24- and 72 hour observations; however, laser treatment did not affect cell attachment and proliferation significantly.

Hydrothermal synthesis and humidity sensing property of ZnO nanostructures and ZnO-In(OH)3 nanocomposites.

Prism- and raspberry-like ZnO nanoparticles and ZnO-In(OH)(3) nanocomposites were prepared by template free hydrothermal method. XRD investigations and microscopic studies showed that pill-like In(OH)(3) particles with body-centered cubic crystal structure formed on the surface of ZnO nanoparticles resulting in increased specific surface area. TEM-EDX mapping images demonstrated that not only nanocomposite formation took place in the course of the synthesis, but zinc ions were also built into the crystal lattice of the In(OH)(3). However, only undoped In(OH)(3) was found on the surface of the pill-like particle aggregates by XPS analyses. The raspberry- and prism-like ZnO particles exhibit strong visible emission with a maximum at 585 and 595 nm, respectively, whose intensity significantly increase due to nanocomposite formation. Photoelectric investigations revealed that photocurrent intensity decreased with increasing indium ion concentration during UV light excitation, which was explained by increase in visible fluorescence emission. QCM measurements showed that morphology of ZnO and concentration of In(OH)(3) had an influence on the water vapor sensing properties.

[Effect of decontaminating solutions on titanium surface: an in vitro study of human epithelial cell culture]. / Dekontamináló anyagok hatása a titánfelszín biointegrációs tulajdonságaira: in vitro humán epithel sejtkultlúra vizsgálatok.

INTRODUCTION: The effects of three different decontaminating solutions in clinical use for peri-implantitis therapy on the chemical structure and surface roughness of commercially pure (CP) Ti were investigated. A further aim was to survey the response of the biological environment to these changes, by examining the attachment and proliferation of human epithelial cells after treatment of the Ti surfaces with these solutions. MATERIALS AND METHODS: CP (grade 4) machined titanium discs (CAMLOG Biotechnologies AG, Switzerland) were treated with 3% H2O2 (5 min), saturated citric acid (pH = 1; 1 min) or chlorhexidine gel (CHX, 5 min). The surface properties were followed through the use of X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The epithelial cell attachment and proliferation was examined by means of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and bicinchoninic acid (BCA) protein-content assays. RESULTS: XPS showed an intact TiO2 layer on each sample and CHX was adsorbed by the surface, as C-O and/or C=O bond formation was revealed. AFM results gave no significant changes in the roughness after treating the surfaces with the cleaning solutions. While MTT and BCA assays did not show significant differences in epithelial cell attachments, the cell proliferation was significantly increased after H2O2 treatment as compared to CHX (not shown by BCA assays). CONCLUSIONS: The applied decontaminating agents do not damage the Ti surface. H2O2 can be used effectively in decontaminating the implants affected by peri-implantitis, as the human epithelial cell growth was improved, in contrast with CHX.

Effects on titanium implant surfaces of chemical agents used for the treatment of peri-implantitis.

The treatment of peri-implantitis, which causes tissue deterioration surrounding osseointegrated implants, involves surface decontamination and cleaning. However, chemical cleaning agents may alter the structure of implant surfaces. We investigated three such cleaning solutions. Commercially pure (grade 4) machined titanium discs (CAMLOG Biotechnologies AG, Switzerland) were treated with 3% H(2)O(2) (5 min), saturated citric acid (pH = 1) (1 min) or chlorhexidine gel (5 min), and their surface properties were examined by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Human epithelial cell attachment (24-h observation) and proliferation (72-h observation) were investigated via dimethylthiazolyl-diphenyltetrazolium bromide (MTT) and bicinchoninic acid (BCA) protein content assays. AFM revealed no significant difference in roughness of the three treated surfaces. XPS confirmed the constant presence of typical surface elements and an intact TiO(2) layer on each surface. The XPS peaks after chlorhexidine gel treatment demonstrated C-O and/or C=O bond formation, due to chlorhexidine digluconate infiltrating the surface. MTT and BCA assays indicated similar epithelial cell attachments in the three groups; epithelial cell proliferation being significantly higher after H(2)O(2) than after chlorhexidine gel treatment (not shown by BCA assays). These agents do not harm the Ti surface. Cleaning with H(2)O(2) slightly enhances human epithelial cell growth, in contrast to chlorhexidine gel.

Corrosive effects of fluoride on titanium: investigation by X-ray photoelectron spectroscopy, atomic force microscopy, and human epithelial cell culturing.

High fluoride (F(-)) concentrations and acidic pH impair the corrosion resistance of titanium (Ti). Effects of F(-)-containing caries-preventive prophylactic rinses, and gels on Ti were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Human epithelial cell attachment and proliferation were investigated by dimethylthiazol-diphenyl tetrazolium bromide (MTT) and protein content assays. Aqueous 1% NaF solution (3800 ppm F(-), pH 4.5) or high (12,500 ppm) F(-) content gel (pH 4.8) strongly corroded the surface and modified its composition. XPS revealed formation of a strongly bound F(-)-containing complex (Na(2)TiF(6)). AFM indicated an increase in roughness (R(a)) of the surfaces: 10-fold for the NaF solution and smaller for the gel or a mouthwash (250 ppm F(-), pH 4.4). MTT revealed that cell attachment was significantly increased by the gel, but was not disturbed by either the mouthwash or the NaF. Cell proliferation determined by MTT decreased significantly only for the NaF-treated samples; protein content assay experiments showed no such effect. This study indicates that epithelial cell culturing results can depend on the method used, and the adverse effects of a high F(-) concentration and low pH should be considered when prophylactic gels are applied by patients with Ti implants or other dental devices.

[The effect of fluorides on the surface structure of titanium implants]. / Fluoridok hatása titán implantátumok felületi szerkezetére.

The high fluoride concentration and the acidic pH in tooth-paste used to prevent caries may modify the surface structure of implants made of titanium. Oxidative agents thicken and condense the titanium-dioxid layer on the surface of titanium and improve its stability against corrosion effects, while reductive agents like fluoride may have the opposite effect and attack this layer. The aim of the present work was to study the effects of fluoride containing toothpaste and gel on the titanium dioxid layer of titanium. The surfaces of the titanium (commercial pure grade I.) discs were treated with toothpaste and gel containing 0.125 % and 1.25 % fluoride, respectively. The changes in the surface structure were analyzed by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). Our results demonstrated that fluoride strongly binds to the titanium surface and modifies its structure in case of fluoride containing gels.