Preparation and characterization of spherical silica-porphyrin catalysts obtained by the sol-gel methodology

This work describes the synthesis of a first-generation iron porphyrin catalyst entrapped in a silica matrix by the sol-gel route, leading to spherical particles. The catalyst was synthesized by the method of Stober, through hydrolysis and condensation of the alkoxysilane TEOS in a mixture of alcohol, water and ammonia, in the presence of the iron porphyrin Fe(TPP)Cl. The relation between particle morphology and catalytic activity of the different Fe(TPP)-SiO2, obtained using different H2O/silane molar ratios and ammonia concentrations in the xerogel syntheses, was studied.The obtained catalysts were characterized by UV-vis spectroscopy, NMR Si-29. thermogravimetric analysis and transmission electron microscopy. Their ability to catalyze (Z)-cyclooctene epoxidation and cyclohexane oxidation was tested using iodosylbenzene as oxygen donor; the oxidation products were analyzed by gas chromatography and the catalysts obtained in a form of particles spherical and monodispersed showed to be a promising catalytic system for selective oxidation. (c) 2005 Elsevier B.V. All rights reserved.

Small angle X-ray scattering study of surface modified tin oxide nanoparticles prepared by sol-gel route

The surface properties of SnO2 nanoparticles were modified by grafting ionic (Tiron (R). (OH)(2)C6H2(SO3Na)(2)(H2O)-H-.) or non-ionic (Catechol (R). C6H4-1,2-(OH)(2)) capping Molecules during aqueous sol-gel processing to improve the redispersibility of powdered xerogel. The effect of the amount of grafted organic molecules on the redispersibility of powders in aqueous solution at several basic pH values was Studied. The nanostructural features of the colloidal suspensions were analyzed by small angle X-ray scattering (SAXS) measurements. Irrespective of the nature and amount of grafted molecules, complete redispersion was obtained in aqueous solution at pH = 13. The redispersion at pH = 11 results in a mixture of dispersed primary particles and aggregates. The proportion of well dispersed nanoparticles and aggregates (and their average size) can be tuned by the quantity of grafted ionic molecules.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

Repair bond strength of a resin composite to alumina-reinforced feldspathic ceramic

This study compared the microtensile bond strength of a repair resin to an alumina-reinforced feldspathic ceramic (Vitadur-alpha, Vita) after 3 surface conditioning methods: Group 1, etching with 9.6% hydrofluoric acid for 1 minute plus rinsing and drying, followed by application of silane for 5 minutes; group 2, airborne particle abrasion with 110-mm aluminum oxide using a chairside air-abrasion device followed by silane application for 5 minutes; group 3, chairside tribochemical silica coating with 30-mu m SiOx followed by silane application for 5 minutes (N = 30). Group 1 presented the highest mean bond strength (19.7 +/- 3.8 MPa), which was significantly higher than those of groups 2 (10 +/- 2.6 MPa) and 3 (10.4 +/- 4 MPa) (P <.01). Scanning electron microscope analysis of the failure modes demonstrated predominantly mixed types of failures, with adhesive and/or cohesive failures in all experimental groups.

An investigation of cadmium(II) and nickel(II) adsorption by chitin graft covolymer

Chitin hydrogels of poly(vinylpyrrolidone) (VP) were prepared by means of the hydrogen peroxide graft copolymerization process. The effect of the VP grafted chain on water diffusion through the biopolymer was studied. Fourier transform infrared spectra of the VP-g-Ch showed an increase in the intensities of the hydroxyl and carbonyl stretching bands indicating a reduction in the hydrogen bonding of chitin. An investigation was undertaken regarding the adsorption of nickel(II) and cadmium(II) ions from aqueous solutions by the VP grafted chitin and the effects of the grafting degree on the Cd2+ and Ni2+ sorption were studied. The Cd2+ and Ni2+ adsorption equilibrium data correlate well with the Freundlich equation. The results indicate that the Ch-g-VP graft copolymer under investigation is a potentially powerful chelating material that can be employed for Ni2+ and Cd2+ ion removal from wastewater effluents. (C) 2004 Wiley Periodicals, Inc.

Evaluation of Philips and Ziegler-Natta high-density polyethylene degradation during processing in an internal mixer using the chain scission and branching distribution function analysis

The oxidative and thermo-mechanical degradation of HDPE was studied during processing in an internal mixer under two conditions: totally and partially filled chambers, which provides lower and higher concentrations of oxygen, respectively. Two types of HDPEs, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturations were analyzed. Materials were processed at 160, 200, and 240 degrees C. Standard rheograrns using a partially filled chamber showed that the torque is much more unstable in comparison to a totally filled chamber which provides an environment depleted of oxygen. Carbonyl and transvinylene group concentrations increased, whereas vinyl group concentration decreased with temperature and oxygen availability. Average number of chain scission and branching (n(s)) was calculated from MWD curves and its plotting versus functional groups' concentration showed that chain scission or branching takes place depending upon oxygen content and vinyl groups' consumption. Chain scission and branching distribution function (CSBDF) values showed that longer chains undergo chain scission easier than shorter ones due to their higher probability of entanglements. This yields macroradicals that react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the oxygen concentration, temperature, and vinyl end groups' content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than the Ziegler-Natta's type at the same processing condition. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of surface conditioning methods on the microtensile bond strength of resin composite to composite after aging conditions

Objectives. This study evaluated the effect of two different surface conditioning methods on the repair bond strength of a bis-GMA-adduct/bis-EMA/TEGDMA based resin composite after three aging conditions.Methods. Thirty-six composite resin blocks (Esthet X, Dentsply) were prepared (5 mm x 6 mm x 6 mm) and randomly assigned into three groups for aging process: (a) immersion in citric acid (pH 3.0 at 37 degrees C, 1 week) (CA); (b) boiling in water for 8h (BW) and (c) thermocycling (x5000, 5-55 degrees C, dwell time: 30s) (TC). After aging, the blocks were assigned to one of the following surface conditioning methods: (1) silica coating (30 mu m SiOx) (CoJet, 3M ESPE) + silane (ESPE-Sil) (CJ), (2) phosphoric acid + adhesive resin (Single Bond, 3M ESPE) (PA). Resin composite (Esthet.X (R)) was bonded to the conditioned substrates incrementally and light polymerized. The experimental groups formed were as follows: Gr1:CA + PA; Gr2:CA + CJ Gr3:BW + PA; Gr4: BW + CJ; Gr5:TC + PA; Gr6: TC + CJ. The specimens were sectioned in two axes (x and y) with a diamond disc under coolant irrigation in order to obtain non-trimmed bar specimens (sticks, 10 mm x 1 mm x 1 mm) with 1 mm(2) of bonding area. The microtensile test was accomplished in a universal testing machine (crosshead speed: 0.5 mm min(-1)).Results. The means and standard deviations of bond strength (MPa +/- S.D.) per group were as follows: Gr1: 25.5 +/- 10.3; Gr2: 46.3 +/- 10.1; Gr3: 21.7 +/- 7.1; Gr4: 52.3 +/- 15.1; GrS: 16.1 +/- 5.1; Gr6, 49.6 +/- 13.5. The silica coated groups showed significantly higher mean bond values after all three aging conditions (p < 0.0001) (two-way ANOVA and Tukey tests, alpha = 0.05). The interaction effect revealed significant influence of TC aging on both silica coated and acid etched groups compared to the other aging methods (p < 0.032). Citric acid was the least aggressive aging medium.Significance. Chairside silica coating and silanization provided higher resin-resin bond strength values compared to acid etching with phosphoric acid followed by adhesive resin applications. Thermocycling the composite substrates resulted in the lowest repair bond strength compared to citric acid challenge or boiling in water. (C) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Microtensile bond strength of a resin cement to feldpathic ceramic after different etching and silanization regimens in dry and aged conditions

Objectives. This study evaluated the durability of bond strength between resin cement and a feldspathic ceramic submitted to different etching regimens with and without silane coupling agent application.Methods. Thirty-two blocks (6.4 mm x 6.4 mm x 4.8 mm) were fabricated using a microparticulate feldspathic ceramic (Vita VM7), ultrasonically cleaned with water for 5 min and randomly divided into four groups, according to the type of etching agent and silanization method: method 1, etching with 10% hydrofluoric (HF) acid gel for I min + silanization; method 2, HF only; method 3, etching with 1.23% acidulated phosphate fluoride (APF) for 5 min + silanization; method 4, APF only. Conditioned blocks were positioned in their individual silicone molds and resin cement (Panavia F) was applied on the treated surfaces. Specimens were stored in distilled water (37 degrees C) for 24 h prior to sectioning. After sectioning the ceramic-cement blocks in x- and Y-axis with a bonded area of approximately 0.6 mm(2), the microsticks of each block were randomly divided into two storage conditions: Dry, immediate testing; TC, thermal cycling (12,000 times) + water storage for 150 d, yielding to eight experimental groups. Microtensile bond strength tests were performed in universal testing machine (cross-head speed: 1 mm/min) and failure types were noted. Data obtained (MPa) were analyzed with three-way ANOVA and Tukey's test (alpha = 0.05).Results. Significant influence of the use of silane (p < 0.0001), storage conditions (p = 0.0013) and surface treatment were observed (p = 0.0014). The highest bond strengths were achieved in both dry and thermocycled conditions when the ceramics were etched with HF acid gel and silanized (17.4 +/- 5.8 and 17.4 +/- 4.8 MPa, respectively). Silanization after HF acid gel and APT treatment increased the results dramatically (14.5 +/- 4.2-17.4 +/- 4.8 MPa) compared to non-silanized groups (2.6 +/- 0.8-8.9 +/- 3.1 MPa) where the failure type was exclusively (100%) adhesive between the cement and the ceramic.Significance. Silanization of the feldspathic ceramic surface after APF or HF acid etching increased the microtensile bond strength results significantly, with the latter providing higher results. Long-term thermocycling and water storage did not decrease the results in silanized groups. (C) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

PREPARATION AND CHARACTERIZATION OF TI(IV) OXIDE GRAFTED ONTO SILICA ON A SILICA-GEL SURFACE

Silica gel with a surface area of 500 m2g-1 and an average pore diameter of 60 angstrom was chemically modified with Ti(IV) oxide using the grafting method. The amount of metal oxide attached to the surface was 1.8.10(-3) mol g-1. The X-ray photoelectron spectra showed that the metal ion species on the surface are Ti(IV) in TiO2 and MTiO3 (M = Ca2+, Sr2+, Ba2+ and Pb2+), i.e. they have the binding energy of Ti2p3/2 = 458.7 eV. The dehydration of the solid at higher temperature increased the O(II)/Ti (O(II) = oxygen bound to titanium atom) ratio, presumably due to a reticulation of the hydrous Ti(IV) oxide on the silica surface at higher temperatures. Migration of Ti(IV) into the silica gel matrix was observed but the specific surface area was not significantly changed.

Titania-based organic-inorganic hybrid planar waveguides

Eu3+ -doped titania-silica planar waveguides were prepared from tetraethylorthotitanate (TEOT) and modified silane 3-amino-propyltriethoxysilane (APTS). Films were deposited on borosilicate glass substrates by a dip-coating technique. The refractive index, the thickness and the total attenuation coefficient of the waveguides were measured at 632.8 and 1550 nm by prism coupling technique. Starting from pure titania films, the addition of modified silane leads to a decrease in the refractive index and an increase in thickness. Squared electric field simulation has shown that the light confinement in the waveguide increases with the silane content of the so]. Emission spectra present a broad emission band due to the modified silane and EU emission transitions arising mainly from the D-5(0) level to the F-7(J) (J = 0-4) manifolds. The dependence of transition intensities and excited state lifetimes on the initial composition and also on the heat treatment performed was interpreted in terms of structural changes occurring during the preparation process. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Bone regeneration at implants placed into extraction sockets of maxillary incisors in dogs

AimTo compare the influence of autologous or deproteinized bovine bone mineral as grafting material on healing of buccal dehiscence defects at implants installed immediately into the maxillary second incisor extraction socket in dogs.Material and methodsIn the maxillary second incisor sockets of 12 Labrador dogs, implants were installed immediately following tooth extraction. A standardized buccal defect was created and autologous bone particles or deproteinized bovine bone mineral were used to fill the defects. A collagen membrane was placed to cover the graft material, and the flaps were sutured to fully submerge the experimental areas. Six animals were sacrificed after 2 months, and six after 4 months of healing. Ground sections were obtained for histological evaluation.ResultsAfter 2 months of healing, all implants were osseointegrated. All buccal dehiscence defects were completely filled after 2 months irrespective of the augmentation material (autologous bone or Bio-Oss (R)) applied. Bone-to-implant contact (BIC) on the denuded implant surfaces was within a normal range of 30-40%. However, the newly formed tissue at 2 months was partially resorbed (> 50% of the area measurements) after 4 months.ConclusionsApplying either autologous bone or deproteinized bovine bone mineral to dehiscences at implants installed immediately into extraction sockets resulted in high degree of regeneration of the defects with satisfactory BIC on the denuded implant surface.To cite this article:De Santis E, Botticelli D, Pantani F, Pereira FP, Beolchini M, Lang NP. Bone regeneration at implants placed into extraction sockets of maxillary incisors in dogs.Clin. Oral Impl. Res. 22, 2011; 430-437.

Composite Resin to Yttria Stabilized Tetragonal Zirconia Polycrystal Bonding: Comparison of Repair Methods

Purpose: The purpose of the current study was to evaluate different approaches for bonding composite to the surface of yttria stabilized tetragonal zirconia polycrystal (Y-TZP) ceramics.Methods: One hundred Y-TZP blocks were embedded in acrylic resin, had the free surface polished, and were randomly divided into 10 groups (n=10). The tested repair approaches included four surface treatments: tribochemical silica coating (TBS), methacryloxydecyldihidrogenphosphate (MDP)-containing primer/silane, sandblasting, and metal/zirconia primer. Alcohol cleaning was used as a "no treatment" control. Surface treatment was followed by the application (or lack thereof) of an MDP-containing resin cement liner. Subsequently, a composite resin was applied to the ceramic surface using a cylindrical mold (4-mm diameter). After aging for 60 days in water storage, including 6000 thermal cycles, the specimens were submitted to a shear test. Analysis of variance and the Tukey test were used for statistical analyses (alpha=0.05).Results: Surface treatment was a statistically significant factor (F=85.42; p<0.0001). The application of the MDP-containing liner had no effect on bond strength (p=0.1017). TBS was the only treatment that had a significantly positive effect on bond strength after aging.Conclusion: Considering the evaluated approaches, TBS seems to be the best surface treatment for Y-TZP composite repairs. The use of an MDP-containing liner between the composite and Y-TZP surfaces is not effective.

Structural and Luminescence Properties of Silica-Based Hybrids Containing New Silylated-Diketonato Europium(III) Complex

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Healing outcomes at implants installed in grafted sites: an experimental study in dogs

Aim: To evaluate the integration of implants installed using a surgical guide in augmented sites with autologous bone or deproteinized bovine bone mineral (DBBM) blocks, concomitantly with a collagen membrane.Material and methods: Mandibular molars were extracted bilaterally in six Labrador dogs, the buccal bony wall was removed, and a box-shaped defect was created. After 3 months, flaps were elevated, a bony graft was harvested from the ascending ramus, and secured to the lateral wall of the defect by means of screws. In the left mandibular side, a DBBM block was fixed into the defect. A resorbable membrane was applied at both sides, and the flaps were sutured. After 3 months, flaps were elevated, and a customized device was used as surgical guide to prepare the recipient sites in the interface between grafts and parent bone. One implant was installed in each side of the mandible. After 3 months, biopsies were harvested, and ground sections were prepared for histologic evaluation.Results: One autologous bone block graft was lost before implant installation. The width of the alveolar crest at the test sites (DBBM) was 5.4 +/- 1.2 mm before, 9.4 +/- 1.2 mm immediately after grafting, and 9.3 +/- 1 mm at implant installation. At the control sites (autologous bone), the corresponding values were: 5.2 +/- 1, 9 +/- 1.2, and 8.7 +/- 0.9 mm, respectively. All implants installed were available for histologic evaluation (n = 5). The autologous bone grafts, rich in vessels and cells, were integrated in the parent bone, and only little non-vital bone was found. The BIC% was 56.7 +/- 15.6% and 54.2 +/- 13.2% at the buccal and lingual aspects, respectively. At the test sites, the DBBM appeared to be embedded into connective tissue, and very little newly formed bone was encountered within the grafts. The BIC% was 5.8 +/- 12.3% and 51.3 +/- 14.2% at the buccal and lingual aspects, respectively.Conclusions: Autologous bone blocks used to augment the alveolar bony crest horizontally allowed the complete osseointegration of implants installed after 3 months of healing. However, similar blocks of DBBM did not promote osseointegration, although the installed implants were stable owing to the osseointegration in the sites of the parent bone.

Distribution of Xylella fastidiosa in citrus rootstocks and transmission of citrus variegated chlorosis between sweet orange plants through natural root grafts

To study translocation of Xylella fastidiosa to citrus rootstocks, budsticks from citrus variegated chlorosis (CVC)-affected cv. Pera sweet orange (Citrus sinenesis (L.) Osb.) were top grafted on 15 citrus rootstocks. Disease symptoms were conspicuous 3 months later on all 15 rootstocks tested. The presence of X. fastidiosa was confirmed by light microscopy, double-antibody sandwich enzyme-linked immunosorbent assays, and polymerase chain reaction in rootlets and main roots of CVC-symptomatic Pera sweet orange in 11 of the 15 rootstocks tested. These results suggest that bacterial translocation from the aerial plant parts to the root system occurs but is not essential for X. fastidiosa to induce symptoms in the aerial parts. Bacterial translocation to the roots was not correlated with CVC leaf-symptom severity in the Pera scion. To determine if CVC disease could be transmitted by natural root grafts, two matched seedlings of each of four sweet orange cultivars (Pera, Natal, Valencia, and Caipira) were transplanted into single pots. One seedling rootstock of each pair was inoculated by top grafting with a CVC-contaminated budstick while the other seedling rootstock was cut but not graft inoculated. Transmission of X. fastidiosa from an inoculated plant to a noninoculated plant sharing the same pot was observed in all four sweet orange cultivars tested. Transmission was confirmed by observation of natural roots grafts between the two plants, presence of X. fastidiosa in the root grafts, and disease development in the uninoculated plants. This is the first report of transmission of CVC disease through natural root grafts.