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Probing M-O Bond Cleavage in Silicon and Titanium Bisenolate Radical Cations.

In this study, several novel sterically congested silicon and titanium bisenolates of exceptional hydrolytic stability have been synthesized and characterized. The structure of the titanium bisenolate T2 could be determined by X-ray structure analysis. Preparative one-electron oxidation of the sterically shielded metal bisenolates S1-S4 and T1-T2 led to formation of the benzofurans B1 and B2. As the benzofuran formation is strong evidence for an initial M-O bond cleavage process at the stage of the initial radical cation we were able to measure the kinetics of this scission process using cyclic voltammetry techniques (first-order rate constants range at k(f) = 0.1-90 s(-)(1)). These data indicate that both silicon and titanium bisenolates are interesting candidates for oxidative intramolecular carbon-carbon bond formation processes.

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Electronic structure and spectra of catechol and alizarin in the gas phase and attached to titanium.

Ab initio electronic structure calculations elucidate the dramatic differences observed in the electronic spectra of the catechol and alizarin molecules upon binding to titanium. Catechol and alizarin are similar chromophores with analogous electronic spectra in the free state. Binding alizarin to titanium red-shifts the spectrum. The binding of catechol to titanium produces a new optically active transition, at the same time preserving the features of the free catechol spectrum. By examining the details of the calculations, we can rationalize the spectral differences in the catechol and alizarin systems by the positioning of the catechol and alizarin pi molecular orbitals relative to the conduction band of TiO(2).

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Characterization of vanadium and titanium oxide supported SBA-15.

Supported vanadium and titanium oxide catalysts were prepared by adsorption and subsequent calcination of the vanadyl and titanyl acetylacetonate complexes, respectively, on mesoporous SBA-15 by the molecular designed dispersion (MDD) method. Liquid and gas phase depositions at different temperatures were carried out with vanadyl acetylacetonate, and the different results together with those of titanyl acetylacetonate in the liquid phase deposition were discussed. The bonding mechanism, the influence of the metal interaction with the support material, and differences due to the way of deposition and the temperature were investigated by TGA, chemical analysis, FTIR, and Raman spectroscopy. Elevated dissolving temperatures in the liquid phase led to higher final loadings on the SBA-15 without the formation of clusters, even at high loadings. The decomposition of the anchored vanadium and titanium complexes, their thermal stability, and the conversion to the covalently bound VO(x) and TiO(x) species on SBA-15 were studied and investigated by in situ transmission IR spectroscopy. In general, the titanium complex is more reactive than the vanadium complex toward the surface of SBA-15 and has a higher thermal stability. The MDD method of the VO(acac)2 and TiO(acac)2 enables to create a dispersed surface of supported VO(x) and TiO(x), respectively. The structure configurations of VO(x) and TiO(x) oxide catalysts obtained at different metal loadings were studied by Raman spectroscopy. Pore size distributions, XRD, and N2 sorption confirmed the structural stability of these materials after grafting. VO(x)/SBA-15 and TiO(x)/SBA-15 samples, with different metal loadings, were also catalytically tested for the selective catalytic reduction (SCR) of NO with ammonia.

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Analysis of titanium nanoparticles created by laser irradiation under liquid environments.

The results of studies of the formation of various titanium-based nanoparticles by laser ablation of a titanium rod in liquid environments comprised of water, ethanol, 2-propanol, and n-hexane are reported. The effect of fluence on nanoparticle characteristics was studied by ablation with a 532 nm Nd:YAG operating at 10 Hz, showing that mean particle size and the size distribution increase with increasing laser intensity. The solvent plays a crucial role in the nature of the nanoparticles, as solvent components are incorporated into the nanoparticles during formation. Titanium nanoparticles formed in oxygen-rich solvents incorporate oxygen, while those formed in a carbon-rich environment are found to contain carbon. The nanoparticles created in their respective liquid environments are very stable, maintain their character over time, and remain in solution for months after creation.

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The catalytic nanodiode: gas phase catalytic reaction generated electron flow using nanoscale platinum titanium oxide Schottky diodes.

Forty microampere current was generated on a platinum-titanium dioxide Schottky diode during the platinum catalyzed steady-state oxidation of carbon monoxide at 80 degrees C. For reaction events that produced four CO(2) molecules, three injected electrons were collected in a diode comprising a 5 nm thick platinum and a 150 nm titanium dioxide film. The electron injection flux depends on the thickness of the platinum and the titanium dioxide diode properties as well as the conditions of the catalytic reactions.

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Evaluation of the tissue reaction to a percutaneous access device using titanium fibre mesh anchorage in goats.

The tissue reaction to a percutaneous access device, applicable as a carrier for an implantable glucose sensor, was evaluated in goats. Titanium fibre mesh structures were used for anchorage of the device in superficial as well as deeper soft-tissue locations. The percutaneous part was subcutaneously anchored with a fibre mesh sheet. The distal part was placed intraperitoneally and anchored in deeper soft-tissue layers using a fibre mesh cuff. All implants showed good healing with the surrounding tissue. Histological evaluation showed that the subcutaneous fibre mesh sheets and peritoneal fibre mesh cuffs were filled with immature connective tissue, generally free of inflammation. Problems concerning disconnection of the silicone catheter from the titanium holding element and filling of part of the peritoneal fibre mesh cuff with silicone glue have to be overcome by more appropriate preclinical testing and improved implant design. Our results demonstrate that titanium fibre mesh structures can be used effectively for soft-tissue anchorage of percutaneous access devices. A sufficient ingrowth of connective tissue was obtained in superficial as well as in deeper soft-tissue layers. The access device could have application as a carrier for an implantable glucose sensor for glucose monitoring in different tissue compartments.

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Healing of titanium implants in onlay bone grafts: an experimental rabbit model.

An experimental rabbit bone graft model for the study of bone formation and remodeling around titanium implants is described. A 2.5-cm long radius bone segment served as an onlay graft. Two commercially pure (c.p.) titanium implants were inserted into the bone graft prior to fixation to the inferior border of the mandibular base with osteosynthesis titanium screws. Each animal was operated twice, allowing follow-up periods of 6 weeks on one side and 6 months on the contralateral side. In order to study bone remodeling by means of fluoroscopy the animals received single injections of tetracyclin and alizarine complexone 2 weeks and 1 week, respectively, prior to sacrifice by perfusion fixation with glutaraldehyde. The bone and implants were excized en bloc, postfixed and embedded in plastic resin. Stained and unstained thin ground sections as well as microradiographed thick sections were produced for light microscopic morphometry and fluoroscopy. After 6 weeks, osteoclastic/osteoblastic activity was primarily observed in the graft-recipient contact area and in the intracortical compartment of the graft bone. New bone formation observed on the implant surface originated from the recipient site. The bone formation was evident also in the implant-graft interface. At 6 weeks the average bone fill of the implant threads was 28.4% which increased to 36.4% after 6 months as measured by morphometry. An average of 17.6% bony contact was measured after 6 weeks which increased to 29.7% 6 months after surgery. The graft bone had reduced in size from an average of 39.5% after 6 weeks down to 24.8% after 6 months (P \lt 0.05). It is concluded that the described experimental model can serve as a useful method for the study of implant healing in onlay grafts.

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Microstructure of ceramic coating on titanium surface as a result of hydrothermal treatment.

Hydroxyapatite coating on commercially pure titanium has been produced by a biomimetic method in order to improve osteointegration for medical implant purposes. A specific chemical treatment by etching titanium substrate with different concentrations of NaOH aqueous solution at 130 degrees C in an autoclave, followed by heat treatment at 600 degrees C was selected to obtain an activated titanium substrate. The microporous surface obtained has allowed the nucleation and growth of a calcium phosphate layer by soaking the substrate in a simulated body fluid (SBF). Scanning electron microscopy (SEM) together with energy dispersive analyzer for X-ray (EDS), X-ray diffraction (XRD) as well as Fourier transform infrared spectroscopy (FT-IR) were employed to evaluate the hydroxyapatite coating. A homogeneous structure coating without cracks defined the chemical treatment condition of the substrate.

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On the formation of fibrous capsule and fluid space around machined and porous blood plasma clot coated titanium.

Machined and machined submicron porous titanium, with and without a thin blood plasma coating (100 nm), were implanted for 7 or 28 days in subcutaneous pockets on the back of the rat. After explantation the specimens were analyzed by light microscopy with respect to thickness of the fibrous capsule, the fluid space width between implants and fibrous capsule, and formation of blood vessels. The results at 7 days indicate a thinnest fluid space for the plasma clot coated porous titanium surface, and the spaces vanished at the light microscopic level after 28 days outside all the analyzed surfaces. The thickness of the fibrous capsule increased outside the different surfaces at 7-28 days, and in this respect no significant differences were observed between the different surfaces at any time. Analysis of neovascularization showed that the number of vessels and proportion of vessels in the fibrous capsule increased with time at all surfaces, except machined Ti where the number instead decreased from 7 to 28 days. The average distance between the blood vessels and the fluid space increased with time for all types of surfaces. The results in the present study indicate that the healing process around titanium can be modulated by porosity and thin pre-prepared plasma coatings.

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Comparative investigation of the surface properties of commercial titanium dental implants. Part I: chemical composition.

The surfaces of five commercially available titanium implants (Brånemark Nobel Biocare, 3i ICE, 3i OSSEOTITE, ITI-TPS, and ITI-SLA) were compared by scanning electron microscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectroscopy. All five implant types were screw-shaped and fabricated from commercially pure (cp) titanium, but their surface properties differed both as regards surface morphology and surface chemical composition. The macro- and microstructure of the implant surfaces were investigated by scanning electron microscopy. The surfaces chemical composition was determined using the surface-sensitive analytical techniques of X-ray photoelectron spectroscopy and time-of-flight secondary ion spectrometry. Surface topographies were found to reflect the type of mechanical/chemical fabrication procedures applied by the manufacturers. The titanium oxide (passive) layer thickness was similar (5-6 nm) and typical for oxide films grown at or near room temperature. A variety of elements and chemical compounds not related to the metal composition were found on some implant types. They ranged from inorganic material such as sodium chloride to specific organic compounds believed to be due to contamination during fabrication or storage. The experimental findings are believed to make a contribution to a better understanding of the interplay between industrial fabrication procedure and physico-chemical implant surface properties.

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Hydroxyapatite coating of titanium by biomimetic method.

The biomimetic method was used in order to deposit, on titanium substrates, an hydroxyapatite (HA) coating. The bioactive HA layer was obtained by using, in the first stage of the process, a glass having the composition 2.5CaO.2SiO(2) different from the one proposed for the application of the biomimetic method. This glass can be obtained via sol-gel, a method that allows one to obtain, easily, very pure products. The growth of HA crystals was confirmed by Fourier transform infrared, SEM, EDS and X-ray photoelectron spectroscopy (XPS) results. The experimental results suggest that, as reported in the literature for other supports, the silicate ions released from the glass in the first stage bind themselves to the titanium support. In particular, from XPS analysis it is evident that the titanium substrate is well covered by a calcium phosphate layer of the type of HA.

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Topographical characterization and microstructural interface analysis of vacuum-plasma-sprayed titanium and hydroxyapatite coatings on carbon fibre-reinforced poly(etheretherketone).

In the present study, topographical characterization and microstructural interface analysis of vacuum-plasma-sprayed titanium and hydroxyapatite (HA) coatings on carbon fibre-reinforced polyetheretherketone (CF/PEEK) was performed. VPS-Ti coatings with high roughness values (Ra=28.29+/-3.07 microm, Rz=145.35+/-9.88 microm) were obtained. On this titanium, intermediate layer HA coatings of various thicknesses were produced. With increasing coating thickness, roughness values of the HA coatings decreased. A high increase of profile length ratio, Lr, of the VPS-Ti coatings (Lr=1.45) compared to the grit-blasted CF/PEEK substrate (Lr=1.08) was observed. Increasing the HA coating thickness resulted in a reduction of the Lr values similar to the roughness values. Fractal analysis of the obtained roughness profiles revealed that the VPS-Ti coatings showed the highest fractal dimension of D=1.34+/-0.02. Fractal dimension dropped to a value of 1.23-1.25 for all HA coatings. No physical deterioration of the CF/PEEK substrate was observed, indicating that substrate drying and the used VPS process parameter led to the desired coatings on the composite material. Cross-section analysis revealed a good interlocking between the titanium intermediate layer and the PEEK substrate. It is therefore assumed that this interlocking results in suitable mechanical adhesive strength. From the results obtained in this study it is concluded that VPS is a suitable method for manufacturing HA coatings on carbon fibre-reinforced PEEK implant materials.

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Structure of the interface between rabbit cortical bone and implants of gold, zirconium and titanium.

The role of surface properties (chemical and structural) for the interaction between biomaterials and tissue is not yet understood. In the present study, implants made of titanium, zirconium (transition metals with surface oxides) and gold (metallic surface) were inserted into the rabbit tibia. Light microscopic (LM) morphometry showed that after 1 and 6 mo the gold implants had less amount of bone within the threads and a lower degree of bone-implant contact than the titanium and zirconium implants, which did not differ from each other. These quantitative differences were supported by LM and ultrastructural observations of the interface. The ultrastructural observations in addition demonstrated that the layer of non-collagenous amorphous material located between the implant and the calcified bone was appreciably thicker around zirconium than around titanium implants. The factors potentially responsible for the observed morphological differences in the bone around the different material surfaces are discussed.

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Does sodium fluoride in bone cement affect implant fixation. Part II: evaluation of the effect of sodium fluoride additions to acrylic bone cement and the fixation of titanium implants in ovariectomized rabbits.

Bone integration of threaded implants made of cured polymethylmethacrylate containing sodium fluoride or commercially pure (c.p.) titanium were studied in normal and estrogen deficient New Zealand white rabbits. Nine had been ovariectomized through laparoscopy and nine served as controls. Four weeks after the ovariectomy two threaded implants made of cured bone cement with or without sodium fluoride addition were inserted in each tibia. One threaded commercially pure titanium implant was inserted in each patello-femoral joint flush to the cartilage. Six weeks after implant insertion measurement of the peak removal torque necessary to loosen the implants and light microscopical histomorphometrical investigations of tissue integration were performed. In the ovariectomized rabbits addition of sodium fluoride to the cement resulted in increased area of bone in the threads (p=0.04), but no corresponding effect could be noted in the controls. The removal torque was lower in the ovariectomized rabbits compared to the non-ovariectomized when comparing implant with sodium fluoride addition (p=0.02). The bone tissue response and the removal torque of the titanium implants were not influenced by ovariectomy in these rabbits.

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Titanium implants and BMP-7 in bone: an experimental model in the rabbit.

This study evaluates the effect of rhBMP-7/OP-1 on the osseointegration of commercially pure titanium implants in an experimental implant model in rabbits. Threaded titanium implants with two transverse parallel canals were inserted in the femur and tibia of rabbits. The canals were filled with, 10 microg of BMP-7/collagen carrier, pure collagen carrier or were left empty as a control. The stiffness of the implant fixation was evaluated by Resonance Frequency Analysis (RFA) at baseline and four weeks postoperatively. Percentage of bone ingrowth in the canals was measured on microradiographs. Histomorphometry along the threaded part of the implants was performed on 15 microm thin sections. The results from the RFA demonstrated a higher mean value for the BMP-7 treated implants in the tibia than the carrier treated implants but not compared to the control implants. The control implants in the tibia demonstrated more bone ingrowth in the upper canal than to the carrier or the BMP-7 treated implants. Apart from these differences there were no significant effects of BMP. In this study BMP-7 did not contribute to any substantially improved bone anchorage of titanium implants.

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Calcium phosphate interactions with titanium oxide and alumina substrates: an XPS study.

Besides the excellent mechanical properties of titanium and alumina (Al(2)O(3)) in the case of load bearing applications, their bone-bonding properties are very different. In osseous environment, Al(2)O(3) ceramic is encapsulated by fibrous tissues, whereas bone can bind directly to titanium, via its natural titanium dioxide (TiO(2)) passivation layer. So far, this calcification dissimilarity between TiO(2) and Al(2)O(3) was attributed to respectively their negative and positive surface charge under physiological conditions. The present study aims at studying the chemical interactions between TiO(2) and Al(2)O(3) (phase alpha) with the diverse ions contained in simulated body fluids (SBFs) buffered with trishydroxymethyl aminomethane (TRIS) at pH=6.0 and pH=7.4. After 1 h of immersion, TiO(2) and alpha-Al(2)O(3) powders were analyzed by X-ray photoelectron spectroscopy (XPS). The results indicated that Ca and HPO(4) groups were present on TiO(2) surface. In addition, HPO(4) groups were found to be in a higher amount than Ca on TiO(2), which does not comply with the surface charge theory. With regard to Al(2)O(3), little HPO(4) but no Ca was detected on its surface, and TRIS bound to Al(2)O(3) substrate in all of the immersion experiments. The fact that both Ca and HPO(4) were present at the vicinity of TiO(2) might be at the origin of its calcification ability. On the other hand, Al(2)O(3) did not show any affinity towards Ca and HPO(4) ions. This might explain the inability of Al(2)O(3) substrate to calcify.

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Effect of membranes and porous hydroxyapatite on healing in bone defects around titanium dental implants. An experimental study in monkeys.

The purpose of the present study was to examine the effect of treating bony craters around titanium dental implant with polytetrafluoroethylene membranes (PTFE), with and without grafting of hydroxyapatite (HA), and with HA alone. 4 standardized bone defects were prepared in the alveolar ridge of edentulous areas in each of 7 monkeys. A titanium implant was then placed centrally in each defect, and in each monkey, the defects were treated with 1 of the following 4 treatment modalities: (1) coverage with PTFE membrane; (2) grafting of HA and covering with a PTFE membrane; (3) HA grafting; (4) no treatment. Following a healing period of 12 weeks, all animals were sacrificed and mesio-distal ground sections of the treated areas were prepared. The histological analysis showed that all bone defects around the implants treated with PTFE membranes and 5 of the defects treated with HA and PTFE membranes were completely filled with new bone. The defects treated with HA alone and thecontrol defects with no treatment only demonstrated new bone formation in the bottom of the defects. The results suggest that bone defects around titanium implants can be treated wuccessfully with PTFE membranes.

Alveolar Bone Loss↗