A envergadura constitucional da posse qualificada na desapropriação privada

The constitutionalisation of private relations is the central theme of this work. Approached him overcome the dichotomy between public and private, through functionalization to the constitutionalization of civil law. Research on the effectiveness of horizontal rights. Constitutional under the lens, we analyzed the tense relationship between possession and ownership desfuncionalizada functionalized. We realize that having qualified and gained autonomy, and mechanism of access to goods, in view of the status sheet minimum, and of accomplishment, materializing human dignity. Then, we investigated the expropriation of private ownership qualified as legislative intervention that ensures the enforcement of fundamental rights through the state-court. We face the legal, the constitutionality and the burden of this institute. Also operability that it gives the judge, the process of exercise, the object, issues related to the burden and assessment of damages, as well as the nature, timing and costs of transferring property. At the end, we point to the scarcity palace, as well as the need to repair lege ferenda. The methodological approach has been championed by legal dogmatics in its analytical aspect, as we explore concepts and correlate with our planning. In empirical connotation, we evaluated the normativity and applicability of our law courts. For the ultimate in normative vision, answers to the problems faced and perform the necessary propositions, based on the results from the conceptual and empirical analysis

Síntese de Fischer-Tropsch sobre perovskitas LayCu0,4Fe0,6O3

The current natural gas production of 52 Mm3d-1 and the large projects for its expansion has been setting new boundaries for the Brazilian industry of oil and gas. So far, one of the biggest challenges regards to the logistics for gas transportation from offshore fields. Therefore, the transformation of natural gas into gasoline, diesel and/or olefins via Fischer-Tropsch synthesis would be an alternative to this matter. In this work, the production of hydrocarbons by Fischer-Tropsch synthesis in a slurry reactor was investigated and a perovskite-type catalyst (LayCu0,4Fe0,6O3 ± d) was used with y varying from 0 to 1 on a molar basis. In addition, Nb2O5 support was also applied in order to observe the selectivity of the produced hydrocarbons by the Fischer-Tropsch process. It is shown that the hydrogen conversion was influenced by the support as well as the different phases of the samples. The kinetic results for the CO2 production suffered great influence with the introduction of the Nb2O5 support throughout the series of samples studied. The catalysts allowed obtaining welldefined cuts of hydrocarbons in the range of C1-C6 and C17-C28, and these results were clearly influenced by the support and the lanthanum content. The higher olefin/paraffin ratio obtained was 1.8 when using a non-supported perovskite with y equal to 0.8. This would indicate the suitability of using this material for the production of olefins

3,5-Dimethyl-1-thiocarbamoylpyrazole and its Pd(II) complexes: Synthesis, spectral studies and antitumor activity

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

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

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

Estudo de materiais mesoporosos funcionalizados com diferentes aminas para captura do dióxido de carbono através do processo de adsorção

Intensive use of machinery and engines burning fuel dumps into the atmosphere huge amounts of carbon dioxide (CO2), causing the intensification of the greenhouse effect. Climate changes that are occurring in the world are directly related to emissions of greenhouse gases, mainly CO2, gases, mainly due to the excessive use of fossil fuels. The search for new technologies to minimize the environmental impacts of this phenomenon has been investigated. Sequestration of CO2 is one of the alternatives that can help minimize greenhouse gas emissions. The CO2 can be captured by the post-combustion technology, by adsorption using adsorbents selective for this purpose. With this objective, were synthesized by hydrothermal method at 100 °C, the type mesoporous materials MCM - 41 and SBA-15. After the synthesis, the materials were submitted to a calcination step and subsequently functionalized with different amines (APTES, MEA, DEA and PEI) through reflux method. The samples functionalized with amines were tested for adsorption of CO2 in order to evaluate their adsorption capacities as well, were subjected to various analyzes of characterization in order to assess the efficiency of the method used for functionalization with amines. The physic-chemical techniques were used: X- ray diffraction (XRD), nitrogen adsorption and desorption (BET/BJH), scanning electron microscopy (SEM), transmission electron microscopy (TEM), CNH Analysis, Thermogravimetry (TG/DTG) and photoelectron spectroscopy X-ray (XPS). The CO2 adsorption experiments were carried out under the following conditions: 100 mg of adsorbent, at 25 °C under a flow of 100 ml/min of CO2, atmospheric pressure and the adsorption variation in time 10-210 min. The X-ray diffraction with the transmission electron micrographs for the samples synthesized and functionalized, MCM-41 and SBA-15 showed characteristic peaks of hexagonal mesoporous structure formation, showing the structure thereof was obtained. The method used was efficient reflux according to XPS and elemental analysis, which showed the presence of amines in the starting materials. The functionalized SBA -15 samples were those that had potential as best adsorbent for CO2 capture when compared with samples of MCM-41, obtaining the maximum adsorption capacity for SBA-15-P sample

Iron Oxide Versus Fe55Pt45/Fe3O4: Improved Magnetic Properties of Core/Shell Nanoparticles for Biomedical Applications

In this paper, synthesis of the Fe55Pt45/Fe3O4 core/shell structured nanoparticles using the modified polyol process combined with the seed-mediated growth method is reported. Iron oxide shell thickness was tuned controlling the Fe(acac)(3)/FePt seeds in the reaction medium. Annealing of the core/shell structure leads to iron-rich layer formation around the hard FePt phase in the nanoparticle core. However, the 2 nm Fe3O4 shell thickness seems to be the limit to obtain the enhanced magnetization close to the alpha-Fe and preserving an iron oxide shell after annealing at 500 degrees C for 30 min in a reducing atmosphere. The presence of both the oxide layer on nanoparticle surface and an intermediate iron-rich FePt layer after annealing promote strong decreases in the coercive field of the 2-nm-oxide shell thickness. These annealed nanoparticles were functionalized with dextran, presenting the enhanced characteristics for biomedical applications such as higher magnetization, very low coercivity, and a slightly iron oxide passivated layer, which leads an easy functionalization and decreases the nanoparticle toxicity.

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Thallium-arene contacts in a rare yttrium tris(pyrazolyl)hydroborate ate complex

A salt elimination reaction between [YCl3(THF)(3.5)] and 1 or 2 equiv. of Tl(Tp(Ms*)) [Tp(Ms*) = HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)(-)] leads in both cases to single metathesis, giving a mixture of the mono-Tp(Ms*) complex [YCl3(Tp(Ms*))Tl] (1) and another complex, [YCl2(Tp(Ms* *))] (2) [Tp(Ms* *) = HB(3-mesitylpyrazolyl)(5-mesitylpyrazolyl)(2)(-)], that results from the transfer of a second mesityl group to the 5-position of the pyrazolyl ring. The solid-state structure of 1 shows a unique ate dimeric structure with the TV cations coordinated by two mu(2)- and two mu(3)-bridging Cl atoms as well as two eta(3)-mesityl ligands. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Synthesis and structural characterization of dichlorobis (1-phenyl-3-methylpyrazole) palladium(II) and diazidobis (1-phenyl-3-methylpyrazole) palladiium(II)

Mononuclear pyrazolyl Pd(II) complexes of the type [PdX2(phmPz)(2)] (X = Cl-, N-3(-)) have been prepared. The 1-phenyl-3-methylpyrazole displaces acetonitrile from [PdCl2(CH3CN)(2)] to form [PdCl2(PhMPz)(2)] (phmPz = 1-phenyl-3-methylpyrazole) (1). [Pd(N-3)(2)(PhmPz)(2)] (2) could be obtained by metathesis from [PdCl2(CH3CN)(2)] or by substitution of the chloride in (1) by the azide ion. Both complexes were characterized by elemental analysis, infrared spectroscopy, H-1 and C-13 NMR and by single crystal X-ray diffraction. The coordination geometry around Pd(II) in these complexes is nearly square-planar, with the ligands in a trans configuration.

2-Mercaptoimidazole covalently bonded to a silica gel surface for the selective separation of mercury(II) from an aqueous solution

Silica gel with a specific surface area of 365 m(2).g(-1) and an average pore diameter of 60 Angstrom was chemically modified with 2-mercaptoimidazole. The degree of functionalization of the covalently attached molecule, (drop SiO)(3)(CH2)(3) - MI, where MI is the 2-mercaptoimidazole bound to the silica surface by a propyl group, was 0.58 mmolg.(-1). In individual metal adsorption experiments from aqueous solutions by the batch procedure, the affinity order was Hg(II)much greater than Cd-II > Cu-II approximate to Zn-II approximate to Pb-II > Mn-II at solution pHs between 4 and 7. Due to the high affinity by the sulfur atom, Hg-II is strongly bound to the functional groups. When solution containing a mixture of Hg-II, Cd-II, Cu-II, Zn-II, Pb-II, and Mn-II ions was passed through a column packed with the adsorbent, Hg-II was the only one whose adsorption and elution was not affected by the presence of other ions.

Linear low density polyethylene (LLDPE) from ethylene using Tp(Ms)NiCl (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and CP2ZrCl2 as a tandem catalyst system

Linear low density polyethylene (LLDPE) with different branching contents were prepared from ethylene, without the addition of alpha-olefin comonomer, using a combination of catalyst precursors {Tp(Ms)}NiCl (1) (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2 (2) activated with MAO/TMA (1:1) in toluene at 0degreesC and by varying the nickel loading mole fraction (x(Ni)). The polymerization results showed that the turnover frequencies are strongly dependent on the x(Ni) varying from 6.6 x 10(3) to 32.1 x 10(3) mol[C2H4]/mol[Zr] h. The C-13 NMR spectra of the copolymers showed that the branch contents of the polymers increase as the x(Ni) increase in the medium promoting the production of polymers with a wide range of melting point (T-m) (C) 2004 Elsevier B.V. All rights reserved.

Adsorption of MX2 (M = Mn, Ni, Cu, Zn, and Cd; X = Cl, Br, and I) and FeCl3 by modified silica surface with imidazolylpropyl group

Silica gel surface modified with imidazolylpropyl group was used to adsorb MX2 (M = Mn, Ni, Cu, Zn, and Cd; X = Cl, Br, and I) and FeCl3 from ethanol and acetone solution. The adsorption capacity and the intensity of the adsorption were determined by using the Langmuir equation. The influences of the solvent, temperature, and degree of functionalization on the adsorption were also studied. The infrared spectra of the functionalized silica were recorded between 1700-1300 cm-1. The bands of the imidazole skeletal vibrations are shifted to higher frequencies upon metal-to-base nitrogen interaction. © 1985.

On the existence of ordered phases of encapsulated diamondoids into carbon nanotubes

We have investigated some diamondoids encapsulation into single walled carbon nanotubes (with diameters ranging from1.0 up to 2.2 nm) using fully atomistic molecular dynamics simulations. Diamondoids are the smallest hydrogen-terminated nanosized diamond-like molecules. Diamondois have been investigated for a large class of applications, ranging from oil industry to pharmaceuticals. Molecular ordered phases were observed for the encapsulation of adamantane, diamantane, and dihydroxy diamantanes. Chiral ordered phases, such as; double, triple, 4- and 5-stranded helices were also observed for those diamondoids. Our results also indicate that the modification of diamondoids through chemical functionalization with hydroxyl groups can lead to an enhancement of the molecular packing inside the carbon nanotubes in comparison to non-functionalized molecules. For larger diamondoids (such as, adamantane tetramers), we have not observed long-range ordering, but only a tendency of incomplete helical structural formation. © 2012 Materials Research Society.

Graphene to fluorographene and fluorographane: A theoretical study

We report here a fully reactive molecular dynamics study on the structural and dynamical aspects of the fluorination of graphene membranes (fluorographene). Our results show that fluorination tends to produce defective areas on the graphene membranes with significant distortions of carbon-carbon bonds. Depending on the amount of incorporated fluorine atoms, large membrane holes were observed due to carbon atom losses. These results may explain the broad distribution of the structural lattice parameter values experimentally observed. We have also investigated the effects of mixing hydrogen and fluorine atoms on the graphene functionalization. Our results show that, when in small amounts, the presence of hydrogen atoms produces a significant decrease in the rate of fluorine incorporation onto the membrane. On the other hand, when fluorine is the minority element, it produces a significant catalytic effect on the rate of hydrogen incorporation. We have also observed the spontaneous formation of new hybrid structures with different stable configurations (chair-like, zigzag-like and boat-like) which we named fluorographane. © 2013 IOP Publishing Ltd.