Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer-by-layer (LbL) films to achieve surface-enhanced Raman scattering as a tool in drug interaction studies

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

The effect of porcelain thickness and surface liner application on the fracture behavior of a ceramic system

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

Opaque Layer Firing Temperature and Aging Effect on the Flexural Strength of Ceramic Fused to Cobalt-Chromium Alloy

Purpose: To evaluate the effect of the opaque layer firing temperature and mechanical and thermal cycling on the flexural strength of a ceramic fused to commercial cobalt-chromium alloy (Co-Cr). The hypotheses were that higher opaque layer temperatures increase the metal/ceramic bond strength and that aging reduces the bond strength.Materials and Methods: Metallic frameworks (25 x 3 x 0.5 mm(3); ISO 9693) (N = 60) were cast in Co-Cr and airborne-particle abraded (Al(2)O(3): 150 mu m) at the central area of the frameworks (8 x 3 mm(2)) and divided into three groups (N = 20), according to the opaque layer firing temperature: Gr1 (control)-900 degrees C; Gr2-950 degrees C; Gr3-1000 degrees C. The opaque ceramic (Opaque, Vita Zahnfabrick, Bad Sackingen, Germany) was applied, and the glass ceramic (Vita Omega 900, Vita Zahnfabrick) was fired onto it (thickness: 1 mm). While half the specimens from each group were randomly tested without aging (water storage: 37 degrees C/24 hours), the other half were mechanically loaded (20,000 cycles; 50 N load; distilled water at 37 degrees C) and thermocycled (3000 cycles; 5 degrees C to 55 degrees C, dwell time: 30 seconds). After the flexural strength test, failure types were noted. The data were analyzed using 2-way ANOVA and Tukey's test (alpha = 0.05).Results: Gr2 (19.41 +/- 5.5 N) and Gr3 (20.6 +/- 5 N) presented higher values than Gr1 (13.3 +/- 1.6 N) (p = 0.001). Mechanical and thermal cycling did not significantly influence the mean flexural strength values (p > 0.05). Increasing the opaque layer firing temperature improved the flexural bond strength values (p < 0.05). The hypotheses were partially accepted.Conclusion: Increasing of the opaque layer firing temperature improved the flexural bond strength between ceramic fused to Co-Cr alloy.

Effects of cement thickness and bonding on the failure loads of CAD/CAM ceramic crowns: Multi-physics FEA modeling and monotonic testing

Objective. To determine the influence of cement thickness and ceramic/cement bonding on stresses and failure of CAD/CAM crowns, using both multi-physics finite element analysis and monotonic testing.Methods. Axially symmetric FEA models were created for stress analysis of a stylized monolithic crown having resin cement thicknesses from 50 to 500 mu m under occlusal loading. Ceramic-cement interface was modeled as bonded or not-bonded (cement-dentin as bonded). Cement polymerization shrinkage was simulated as a thermal contraction. Loads necessary to reach stresses for radial cracking from the intaglio surface were calculated by FEA. Experimentally, feldspathic CAD/CAM crowns based on the FEA model were machined having different occlusal cementation spaces, etched and cemented to dentin analogs. Non-bonding of etched ceramic was achieved using a thin layer of poly(dimethylsiloxane). Crowns were loaded to failure at 5 N/s, with radial cracks detected acoustically.Results. Failure loads depended on the bonding condition and the cement thickness for both FEA and physical testing. Average fracture loads for bonded crowns were: 673.5 N at 50 mu m cement and 300.6 N at 500 mu m. FEA stresses due to polymerization shrinkage increased with the cement thickness overwhelming the protective effect of bonding, as was also seen experimentally. At 50 mu m cement thickness, bonded crowns withstood at least twice the load before failure than non-bonded crowns.Significance. Occlusal "fit" can have structural implications for CAD/CAM crowns; pre-cementation spaces around 50-100 mu m being recommended from this study. Bonding benefits were lost at thickness approaching 450-500 mu m due to polymerization shrinkage stresses. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effects of thickness coating on the electrochemical behaviour of thermal spray Cr3C2-NiCr coatings

Thermally sprayed HVOF coatings are increasingly being used in industrial applications where high wear and corrosion resistance are needed [1,2]. In this paper, electrochemical ac and de experiments were used in order to obtain the corrosion resistance of coated steel with different numbers of Cr3C2-NiCr layers. This work has been performed in order to determine the role of coating thickness in the corrosion behaviour of a steel protected with cermet thermally sprayed coatings. It is known that a thicker layer protects better against corrosion when a metallic coating is evaluated. But cermet coatings, such as Cr3C2-NiCr, contain higher levels of porosity and residual stresses than metallic coatings, which really could influence the corrosion resistance of the deposited layer. Electrochemical measurements, such as Open-Circuit Potential (E-Osubset of), Polarisation Resistance (RP) and Cyclic Voltammetry (CV), were performed in an aerated 3.4 NaCI media (%wt.). Electrochemical Impedance Measurements (EIS) were also done in order to obtain a mechanism that explains the corrosion process. Structural Characterisation was carried out by means of Optical and Scanning Electron Microscopes (OM, SEM) with an Energy Dispersive Spectrometry analyser (EDS). Results show that the corrosion resistance of the complete system is mainly influenced by the substrate behaviour. The application of a higher number of deposited layers did not substantially increase their anticorrosive properties. Stress generation during the spraying deposition process plays an important role in the behaviour of the coated steel against corrosion phenomena. (C) 2002 Elsevier B.V. B.V All rights reserved.

Electroactive layer-by-layer films of iron tetrasulfonated phthalocyanine

Electroactive films of iron tetrasulfonated phthalocyanine (FeTsPc) were assembled via the electrostatic layer-by-layer technique (LBL), in which FeTsPc layers were alternated with the polycationic poly(allylamine hydrochloride) (PAN). The multilayer formation was monitored via UV-Vis spectroscopy by measuring the increase in the Q Band of FeTsPc at 676 nm. Film thickness was estimated by profilometry as ca. 10 Angstrom per bilayer. Fourier transform infrared and UV-Vis absorption spectroscopy suggested specific interactions between FeTsPc and PAR Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 0.92 mV and 0.70 mV, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/AgNO3).

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Catechol biosensing using a nanostructured layer-by-layer film containing Cl-catechol 1,2-dioxygenase

dThe detection of aromatic compounds from pesticides and industrial wastewater has become of great interest, since these compounds withstand chemical oxidation and biological degradation, accumulating in the environment. In this work, a highly sensitive biosensor for detecting catechol was obtained with the immobilization of Cl-catechol 1,2-dioxygenase (CCD) in nanostructured films. CCD layers were alternated with poly(amidoamine) generation 4 (PAMAM G4) dendrimer using the electrostatic layer-by-layer (LbL) technique. Circular dichroism (CD) measurements indicated that the immobilized CCD preserved the same conformation as in solution. The thickness of the very first CCD layers in the LbL films was estimated at ca. 3.6 nm, as revealed by surface plasmon resonance (SPR). PAMAM/CCD 10-bilayer films were employed in detecting diluted catechol solutions using either an optical or electrical approach. Due to the mild immobilization conditions employed, especially regarding the pH and ionic strength of the dipping solutions, CCD remained active in the films for periods longer than 3 weeks. The optical detection comprised absorption experiments in which the formation of cis-cis muconic acid, resulting from the reaction between CCD and catechol, was monitored by measuring the absorbance at 260 nm after film immersion in catechol solutions. The electrical detection was carried out using LbL films deposited onto gold-interdigitated electrodes immersed in aqueous solutions at different catechol concentrations. Using impedance spectroscopy in a broad frequency range (1Hz-1kHz), we could detect catechol in solutions at concentrations as low as 10(-10) M. (c) 2005 Elsevier B.V. All rights reserved.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Deposition of controlled thickness ultrathin SnO2 : Sb films by spin-coating

The technological interest in transparent conductive oxide films (TCOs) has motivated several works in processing techniques, in order to obtain adequate routes to application. In this way, this work describes a new route to obtain antimony-doped tin oxide (ATO) films, based in colloidal dispersions of oxide nanocrystals. The nanoparticles were obtained by a hydrolisis method, using SnCl2 and SbCl3 in ethanolic solutions. The residual halides were removed by dyalisis, obtaining a limpid and transparent colloidal suspension. By this, the method offers the advantage of producing ultrathin films without organic contaminants. This route was employed to produce films with 5, 10, 14, and 18 mol% Sb doping, with thickness ranging from 40 to 70 nm. The physical characterization of the samples showed a uniform layer deposition, resulting in good packing density and high transmittance. A preliminar electrical study confirmed the low electrical resistivity even in the ultrathin films, in such level similar of reported data. The method described is similar in some aspects to layer-by-layer (LbL) techniques, allowing fine control of thickness and interesting properties for ultrathin films, however, with low cost when compared to similar routes.

Molecular engineering strategies to control photo-induced birefringence and surface-relief gratings on layer-by-layer films from an azopolymer

The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

Observation of tags and hybrid layer of a single bottle conventional adhesive system and a self-etching adhesive system, on sound dentin.

This experimental light microscopy study investigated the formation of a hybrid layer and resin tags on sound dentin, after utilization of conventional and self-etching adhesive systems. After restorative procedures, the specimens were decalcified in a formic acid and sodium citrate solution, embedded in paraffin, sectioned at 6-microm thickness and stained by the Brown & Brenn method for analysis and measurement by light microscopy (AXIOPHOT) (400x). The results were statistically analyzed by analysis of variance, at a significance level of 5%. Based on the results, it could be concluded that the conventional adhesive allowed the formation of a thicker hybrid layer than the self-etching adhesive, with similar penetration into the dentinal tubules (resin tags).

Cementation of fiber post: influence of the cement insertion techniques on the bond strength of the fiber post-root dentin and the quality of the cement layer.

The aim of this study was to assess the influence of resin cement insertion methods on the bond strength of a fiber post to root dentin and quality of the cement layer. Forty bovine single-roots (length =16 mm) were randomly allocated into four groups, according to the cement insertion methods (N.=10): Gr1- Lentulo drill #40, Gr2- Centrix syringe, Gr3- Explorer #5, Gr4- fiber post. The root canals were prepared at 12 mm, using preparation bur # 3 of a cylinder quartz-FRC post (Aesthet post-plus, Bisco). The fiber posts were cemented using a multi-step etch-and-rinse adhesive system (All Bond 2®, Bisco) and a dual-cured resin cement (Duolink, Bisco). Each root was cut into seven samples: four samples of 1.8 mm thickness for push-out testing, and three with 0.5 mm for cement layer quality analyzing. One-way ANOVA was used for the push-out test values and the One-Way Kruskal-Wallis (P<0.05) and Dunn (10%) tests for the cement layer analyzes. ANOVA showed that the cement layer quality was affected by the cement insertion methods (P=0.0044): Gr1 (3.8 ± 1.3a), Gr2 (3.2 ± 1.3a), Gr3 (5.2 ± 1.5a,b) and Gr4 (5.2 ± 1.5b) (Dunn test), whereas the bond strength (MPa) was not affected by cement insertion methods: G1 (4.2 ± 1.3), G2 (3.2 ± 1.8), G3 (4.5 ± 0.9), G4 (3.1 ± 1.3). The fiber posts should be cemented with the assistance of the lentulo drill or centrix syringe to promote the best cement layer results.

Influência da smear layer e da condição de tratamento da dentina (in vivo e in vitro), sobre a resistência de união

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização por espectroscopia vibracional de filmes Layer-by-Layer contendo ftalocianina, polímeros condutores e gomas naturais

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