193 resultados para Knoevenagel condensation


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We contrast four distinct versions of the BCS-Bose statistical crossover theory according to the form assumed for the electron-number equation that accompanies the BCS gap equation. The four versions correspond to explicitly accounting for two-hole-(2h) as well as two-electron-(2e) Cooper pairs (CPs), or both in equal proportions, or only either kind. This follows from a recent generalization of the Bose-Einstein condensation (GBEC) statistical theory that includes not boson-boson interactions but rather 2e- and also (without loss of generality) 2h-CPs interacting with unpaired electrons and holes in a single-band model that is easily converted into a two-band model. The GBEC theory is essentially an extension of the Friedberg-Lee 1989 BEC theory of superconductors that excludes 2h-CPs. It can thus recover, when the numbers of 2h- and 2e-CPs in both BE-condensed and non-condensed states are separately equal, the BCS gap equation for all temperatures and couplings as well as the zero-temperature BCS (rigorous-upper-bound) condensation energy for all couplings. But ignoring either 2h- or 2e-CPs it can do neither. In particular, only half the BCS condensation energy is obtained in the two crossover versions ignoring either kind of CPs. We show how critical temperatures T-c from the original BCS-Bose crossover theory in 2D require unphysically large couplings for the Cooper/BCS model interaction to differ significantly from the T(c)s of ordinary BCS theory (where the number equation is substituted by the assumption that the chemical potential equals the Fermi energy). (c) 2007 Published by Elsevier B.V.

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Here we describe the application of microparticles (MPs) for the delivery and release of the drug a benzopsoralen. We also evaluated the intracellular distribution and cellular uptake of the drug by using an encapsulation technique for therapeutic optimization. MPs containing the compound 3-ethoxycarbonyl-2H-benzofuro[3,2-f]-1-benzopyran-2-one (psoralen A) were prepared by the solvent evaporation technique, and parameters such as particle size, drug encapsulation efficiency, effect of the encapsulation process on the drug's photochemistry, zeta potential, external morphology, and < i > in vitro release behavior were evaluated. The intracellular distribution of MPs as well as their uptake by tissues were monitored. Size distribution studies using dynamic ligh scattering and scanning electron microscopy revealed that the MPs are spherical in shape with a diameter of 1.4 mu m. They present low tendency toward aggregation, as confirmed by their zeta potential (+10.6 mV). The loading efficiency obtained was 75%. As a consequence of the extremely low diffusivity of the drug in aqueous medium, the drug release profile of the MPs in saline phosphate buffer (pH 7.4) was much slower than that obtained in the biological environment. Among the population of peritoneal phagocytic cells, only macrophages were able to phagocytose poly-d,l-lactic-co-glycolic acid (PLGA) MP. The use of psoralen A in association with ultraviolet light (360 nm) revealed morphological characteristics of cell damage such as cytoplasmic vesiculation, mitochondria condensation, and swelling of both the granular endoplasmatic reticulum and the nuclear membrane. These results indicate that PLGA MP could be a promising delivery system for psoralen in connection with ultraviolet irradiation therapy (PUVA).

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Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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This paper reviews the influence of particle size distribution, agglomerates, rearrangement, sintering atmospheres and impurities on the pore evolution of some commonly studied oxides. These factors largely affect sintering mechanisms due to modifications of diffusion coefficients or evaporation-condensation. Very broad particle size distribution leads to grain growth and agglomerates densify first. Rearrangement of particles due to neck asymmetry mainly in the early stage of sintering is responsible for a high rate of densification in the first minutes of sintering by collapse of large pores. Sintering atmospheres play an important role in both densification and pore evolution. The chemical interaction of water molecules with several oxides like MgO, ZnO and SnO2 largely affects surface diffusion. As a consequence, there is an increase in the rates of pore growth and densification for MgO and ZnO and in the rate of pore growth for SnO2. Carbon dioxide does not affect the rate of sintering of MgO but greatly affects both rates of pore growth and densification of ZnO. Oxygen concentration in the atmosphere can especially affect semiconductor oxides but significantly affects the rate of pore growth of SnO2. Impurities like chlorine ions increase the rate of pore growth in MgO due to evaporation of HCl and Mg(OH)Cl, increasing the rate of densification and particle cuboidization. CuO promotes densification in SnO2, and is more effective in dry air. The rate of densification decrease and pore widening are promoted in argon. An inert atmosphere favors SnO2 evaporation due to reduction of CuO. © 1990.

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Some endodontists use iodoform in Sealapex in order to rend it more radiopac. This procedure is empiric and for this reason we decided to observe, histologically, if the iodoform introduces some modification in the biological properties of Sealapex. Thirty root canals of dogs' teeth were overinstrumented and filled, by lateral condensation technique, with gutta percha points and Sealapex, with or without iodoform. The iodoform was added in two different proportions: 30 mg or 112 mg for one centimeter of the base and one centimeter of the catalyst of Sealapex. The pieces were removed for histological studies, 6 months after the treatment. The histological results showed that Sealapex encourages apical closure by cementum deposition and that the addition of iodoform does not change that biological property.

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The subject of this work is to observe if the employment of a cream (ENDO-PTC) during the root canal preparation contributes or not to the condensation of debris in the apical region. Twenty root canals of dogs teeth were divided into two experimental groups: in the first one, the biomechanical preparation was carried out up to the n. 50 Kerr file by using irrigation and aspiration with sodium hypochlorite. In the second experimental group the canal negotiation was done in the same way but using a cream (ENDO-PTC) with sodium hypochlorite as a lubrication substance. A final irrigation and aspiration with sodium hypochlorite was also done in this group. The animal was killed and the pieces prepared for histological analysis. The histological results show us that the employment of a cream during the negotiation of the root canal contributes to a higher condensation of debris in the apical area.

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Electrolytes may modify the physical-chemical characteristics of colloidal particle interfaces in suspension, which can favour gel or aggregate formation. The influence of NH4Cl loading on the aggregation and gelation of SnO2 colloidal suspensions was investigated using measurements of rheology, turbidity and infrared spectra. A rapid aggregate growth for samples with Cl- > 20 mM was observed. With increasing age, gelation was observed due to formation of interaggregate bonds. For concentration of Cl- between 20 and 9 mM, the aggregation process was slower allowing the formation of gel with a network which was not destroyed as the gel was submitted to a small rate of shear. As aging continues, the condensation reaction between OH groups gave rise to the formation of Sn-O bonds, irrespective of the electrolyte loading. © 1992 Elsevier Science Publishers B.V. All rights reserved.

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The effect of the electrolyte (NH+ 4, Cl-) on the drying of SnO2 hydrogels was investigated by linear shrinkage, mass loss, gravimetric thermal analysis and infrared spectroscopy. Results show that the drying mechanism for monolithic SnO2 gels is highly dependent on the concentration of the electrolyte solution inside the pores. For higher concentrations, the drying process is governed by capillary forces while for the smaller ones (≤20 mM) syneresis shrinkage becomes predominant just before the end of the first drying period. This phenomenon is related to condensation reaction among the superficial OH groups and may hamper formation of monolithic SnO2. © 1992 Elsevier Science Publishers B.V. All rights reserved.

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Excitation and dynamic emission spectra of Eu3+ ions were simultaneously used with FTIR and Raman spectroscopy to study the structural evolution during SnO2 sol → gel → xerogel conversion. Results make evident an increase of the surroundings symmetry for the Eu3+ ions dissolved in SnO2 matrix and a decrease of the amount of hydroxo groups (Sn-OH) during drying. These phenomena were associated to the pursuit of the condensation reaction after gelation. © 1994 Kluwer Academic Publishers.

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The purpose of this study was to observe the quality of seal of the glass ionomer cement, Ketac-Endo, after treatment of the root canal wall. The root canals of 140 extracted human teeth were prepared biomechanically. The root canals were treated with either EDTA or received an intracanal dressing of calcium hydroxide or camphorated paramonochlorphenol. The root canals were filled by the lateral condensation technique with gutta-percha points and the sealer Ketac-Endo, or zinc oxide-eugenol cement or Sealapex. The teeth were placed into a 2% methylene blue dye solution inside a flask, which was attached to a vacuum pump. Leakage was measured linearly. Sealapex exhibited significantly less leakage than Ketac-Endo or zinc oxide-eugenol cement (P<0.01). The use of EDTA and intermediary dressings reduced significantly (P<0.01) the leakage observed with the zinc oxide-eugenol sealer and Ketac-Endo.