Low-altitude, near-polar and near-circular orbits around Europa

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

Nonsphericity of the Moon and Near Sun-Synchronous Polar Lunar Orbits

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

Estudo do equilíbrio e cinética de adsorção de um corante aniônico em quitosana

The phenomenon of adsorption is of fundamental importance for the treatment of textile effluents and removal of dyes. Chitosan is characterized as an excellent adsorbent material, not only for its adsorption capacity but also the low cost production. Equilibrium and kinetic studies were developed in this study to describe the mechanism of adsorption of the anionic azo dye Orange G in chitosan, with the isotherms obtained from the variation of the concentration of dye in the continuous phase. The kinetics of the process was analyzed based on models involving the adsorption of molecules of the dye in nonpolar and polar sites. Adsorption experiments were carried out in water and in saline media with different NaCl concentrations, both for the determination of the equilibrium time as isotherms for making kinetic curves in which the amount of dye adsorbed measured indirectly varied with time. The experiments revealed the opening of the biopolymer structure with increasing concentration of Orange G, accompanied by high pH values and change on the type of interaction between the dye and the adsorbent surface, suggesting behavior advocated by the Langmuir equation in a certain range of concentration of the adsorbate and following the Henry's Law at higher concentrations, from the increased number of sites available for adsorption. The studies conducted showed that the saline medium reduces the chitosan s adsorption capacity according to a certain concentration, the occurrence of the cooperative adsorption process steps kinetic mechanism suggested as a new alternative for the interpretation of the phenomenon

Estudo teórico aplicado ao petróleo: estabilidade dos alcenos e recuperação terciária

The present work aims to study the theoretical level of some processes employed in the refining of petroleum fractions and tertiary recovery of this fluid. In the third chapter, we investigate a method of hydrogenation of oil fractions by QTAIM (Quantum Theory of Atoms in Molecules) and thermodynamic parameters. The study of hydrogenation reactions, and the stability of the products formed, is directly related to product improvement in the petrochemical refining. In the fourth chapter, we study the theoretical level of intermolecular interactions that occur in the process of tertiary oil recovery, or competitive interactions involving molecules of non-ionic surfactants, oil and quartz rock where oil is accumulated. Calculations were developed using the semiempirical PM3 method (Parametric Model 3). We studied a set of ten non-ionic surfactants, natural and synthetic origin. The study of rock-surfactant interactions was performed on the surface of the quartz (001) completely hydroxylated. Results were obtained energetic and geometric orientations of various surfactants on quartz. QTAIM was obtained through the analysis of the electron density of interactions, and thus, providing details about the formation of hydrogen bonds and hydrogen-hydrogen systems studied. The results show that the adsorption of ethoxylated surfactants in the rock surface occurs through the hydrogen bonding of the type CH---O, and surfactants derivatives of polyols occurs by OH---O bonds. For structures adsorption studied, the large distance of the surfactant to the surface together with the low values of charge density, indicate that there is a very low interaction, characterizing physical adsorption in all surfactants studied. We demonstrated that surfactants with polar group comprising oxyethylene units, showed the lowest adsorption onto the surface of quartz, unlike the derivatives of polyols

Gastric anti-ulcer activity of leaf fractions obtained of polar extract from Wilbrandia ebracteata in mice

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

Differences in gastroprotective and mutagenic actions between polar and apolar extracts of Ananas ananassoides

Several plants are used in folk medicine to treat gastrointestinal disorders. Ananas ananassoides (Baker) L. B. Smith (Family Bromeliaceae) is a medicinal plant commonly used in the central region of Brazil against gastric pain. We evaluated two extracts (methanol [MeOH] and dichloromethane [DCM]) obtained from the leaves of A. ananassoides for their ability to protect the gastric mucosa against injuries caused by necrotizing agents (0.3 M HCl/60% ethanol, absolute ethanol, non-steroidal anti-inflammatory drugs, and pylorus ligation) in mice and rats. The best results were obtained after pretreatment with the DCM extract, whereas the MeOH extract did not show any significant anti-ulcerogenic activity but presented mutagenic action. The mechanism of action of the DCM extract suggested the effective participation of endogenous sulfhydryl group in the gastroprotective action. The data, taken together with the absence of acute toxicity and mutagenicity, indicate the apolar extract, instead of the polar, extract of A. ananassoides as a safe and potential new anti-ulcerogenic drug.

Tetrachlorocarbonyliridates: Water-Soluble Carbon Monoxide Releasing Molecules Rate-Modulated by the Sixth Ligand

A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR. NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 mu M min(-1) in a 10 mu M solution of myoglobin and 10 mu M of the complexes.

Rhamnolipids and PHAs: Recent reports on Pseudomonas-derived molecules of increasing industrial interest

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

Effect of exogenous galectin-1 on leukocyte migration: modulation of cytokine levels and adhesion molecules

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

Activation of Ca2+-independent membrane-damaging activity in Lys49-phospholipase A(2) promoted by amphiphilic molecules

Association of class-II phospholipase A(2) (PLA(2)) with aggregated phospholipid substrate results in elevated levels of the Ca2+-dependent hydrolytic activity. The Asp49 residue participates in coordination of the Ca2+ ion cofactor, however, in Lys49-PLA(2) homologues (Lys49-PLA(2)S), substitution of the Asp49 by Lys results in loss of Ca2+ binding and lack of detectable phospholipid hydrolysis. Nevertheless, Lys49-PLA2S cause Ca2+-independent damage of liposome membranes. Bothropstoxin-I is a homodimeric Lys49-PLA(2) from the venom of Bothrops jararacussu, and in fluorescent marker release and dynamic light scattering experiments with DPPC liposomes we demonstrate activation of the Ca2+-independent membrane damaging activity by similar to4 molecules of sodium dodecyl sulphate (SDS) per protein monomer. Activation is accomparlied by significant changes in the intrinsic tryptophan fluorescence emission (ITFE) and near UV circular dichroism (UVCD) spectra of the protein. Subsequent binding of 7-10 SDS molecules results in further alterations in the ITFE and far UVCD spectra. Reduction in the rate of N-bromosuccinimide modification of Trp77 at the dimer interface suggests that initial binding of SDS to this region accompanies the activation of the membrane damaging activity. 1-anilinonaphthalene-8-sulphonic acid binding studies indicate that subsequent SDS binding to the active site is concomitant with the second structural transition. These results provide insights in the structural basis of amphiphile/protein coupling in class-II PLA(2)s. (C) 2004 Published by Elsevier B.V.

An ultraviolet photoacoustic spectroscopy study of the interaction between Lys49-phospholipase A(2) and amphiphilic molecules

We have used near ultraviolet photoacoustic spectroscopy (PAS) over the wavelength range 240-320 nm to investigate the complex formed between the homodimeric bothropstoxin-I, a lysine-49-phospholipase A(2) from the venom of Bothrops jararacussu (BthTx-I), with the anionic amphiphile sodium dodecyl sulfate (SDS). At molar ratios > 10, the complex developed a significant light scatter, accompanied by a decrease in the intrinsic tryptophan fluorescence intensity emission (ITFE) of the protein, and an increase in the near UV-PAS signal. Difference PAS spectroscopy at SDS/BthTx-I ratios < 8 were limited to the region 280-290 nm, suggesting initial SDS binding to the tryptophan 77 located at the dimer interface. At SDS/BthTx-I ratios > 10, the intensity between 260 and 320 nm increases demonstrating that the more widespread tyrosine and phenylalanine residues contribute to the SDS/BthTx-I interaction. PAS signal phase changes at wavelengths specific for each aromatic residue suggest that the Trp77 becomes more buried on SDS binding, and that protein structural changes and dehydration may alter the microenvironments of Tyr and Phe residues. These results demonstrate the potential of near UV-PAS for the investigation of membrane proteins/detergent complexes in which light scatter is significant. (c) 2006 Elsevier B.V. All rights reserved.

The effect of sodium chloride on the formation of W/O microemulsions in soy bean oil/surfactant/water systems and the solubilization of small hydrophilic molecules

Partial pseudoternary phase diagrams were constructed for soy bean oil (SBO)/surfactant/NaCl aqueous solution systems, at 25 degrees C, using the anionic sodium bis(2-ethylhexyl) sulfosuccinate (ACT) and zwiterionic phosphatidylcholine (PC) or mixtures of these surfactants. The isotropic single phase of water-in-oil (W/O) microemulsions (MEs) is shown in the phase diagram and their viscosity reported. ME samples containing small amount of surfactant exhibit slightly higher viscosity than pure SBO, and were used in the solubilization of small water soluble molecules. NaCl enhances the area of the ME phase and MEs with different surfactant composition exhibit different induction time as obtained from tests of oxidative stability, and so are the MEs enriched with ascorbic acid, folic acid and FeSO4, with the latter exhibiting lower stability. The so prepared enriched soy bean oil has potential application in food industry since the surfactants are food grade. (C) 2007 Elsevier B.V. All rights reserved.

Selectivity in the mechanism of action of antimicrobial mastoparan peptide Polybia-MP1

Many potent antimicrobial peptides also present hemolytic activity, an undesired collateral effect for the therapeutic application. Unlike other mastoparan peptides, Polybia-MP1 (IDWKKLLDAAKQIL), obtained from the venom of the social wasp Polybia paulista, is highly selective of bacterial cells. The study of its mechanism of action demonstrated that it permeates vesicles at a greater rate of leakage on the anionic over the zwitterionic, impaired by the presence of cholesterol or cardiolipin; its lytic activity is characterized by a threshold peptide to lipid molar ratio that depends on the phospholipid composition of the vesicles. At these particular threshold concentrations, the apparent average pore number is distinctive between anionic and zwitterionic vesicles, suggesting that pores are similarly formed depending on the ionic character of the bilayer. To prospect the molecular reasons for the strengthened selectivity in Polybia-MP1 and its absence in Mastoparan-X, MD simulations were carried out. Both peptides presented amphipathic alpha-helical structures, as previously observed in Circular Dichroism spectra, with important differences in the extension and stability of the helix; their backbone solvation analysis also indicate a different profile, suggesting that the selectivity of Polybia-MP1 is a consequence of the distribution of the charged and polar residues along the peptide helix, and on how the solvent molecules orient themselves according to these electrostatic interactions. We suggest that the lack of hemolytic activity of Polybia-MP1 is due to the presence and position of Asp residues that enable the equilibrium of electrostatic interactions and favor the preference for the more hydrophilic environment.

Hydrothermal syntheses of ETS-10 like vanadosilicates using chiral organic molecules. Part I

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

Quantum description of spin tunneling in magnetic molecules

Starting from a phenomenological Hamiltonian originally written in terms of angular momentum operators we derive a new quantum angle-based Hamiltonian that allows for a discussion on the quantum spin tunneling. The study of the applicability of the present approach, carried out in calculations with a soluble quasi-spin model, shows that we are allowed to use our method in the description of physical systems such as the Mn12-acetate molecule, as well as the octanuclear iron cluster, Fe8, in a reliable way. With the present description the interpretation of the spin tunneling is seen to be direct, the spectra and energy barriers of those systems are obtained, and it is shown that they agree with the experimental ones. (c) 2006 Elsevier B.V. All rights reserved.