Síntese, caracterização e estudo do comportamento térmico dos oxanatos de lantanídeos(III) e de ítrio(III), no estado sólido

Pós-graduação em Química - IQ

Análise da cintilação ionosférica no Brasil empregando GNSS e técnicas de mineração e visualização de dados

Pós-graduação em Ciências Cartográficas - FCT

Quantum chemical topological analysis of hydrogen bonding in HX…HX and CH3X…HX dimers (X = Br, Cl, F)

We present a systematic investigation of the nature and strength of the hydrogen bonding in HX···HX and CH3X…HX (X = Br, Cl and F) dimers using ab initio MP2/aug-cc-pVTZ calculations in the framework of the quantum theory of atoms in molecules (QTAIM) and electron localisation functions (ELFs) methods. The electron density of the complexes has been characterised, and the hydrogen bonding energy, as well as the QTAIM and ELF parameters, is consistent, providing deep insight into the origin of the hydrogen bonding in these complexes. It was found that in both linear and angular HX…HX and CH3X…HX dimers, F atoms form stronger HB than Br and Cl, but they need short (∼2 Å) X…HX contacts.

Tomografia da ionosfera a partir do GNSS e técnicas algébricas: estudo de caso para a região brasileira

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials

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

Desempenho do RTK em rede sob efeito da cintilação ionosférica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese, caracterização e estudo do comportamento térmico dos glicolatos de lantanídeos e ítrio no estado sólido

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Oral glands in dipsadine ""goo-eater"" snakes: Morphology and histochemistry of the infralabial glands in Atractus reticulatus, Dipsas indica, and Sibynomorphus mikanii

Although snake infralabial glands are generally constituted of mucous cells, among dipsadines, they are much more developed and predominantly serous in nature, possibly due to the peculiar feeding habits of some species of this group, the ""goo-eaters"", which feed on soft and viscous invertebrates. We compared the morphology and histochemistry of the infralabial glands of three goo-eater species of Southeast Brazil, Atractus reticulatus, Dipsas indica and Sibynomorphus mikanii. In A. reticulatus the glands are formed by mixed acini composed of mucous and seromucous cells and in D. indica, they are composed of mucous tubules and seromucous acini. In S. mikanii the glands are organized in seromucous acini; mucous cells are restricted to the gland anterior region and to the duct lining epithelium. Ultrastructurally, secretory granule electron density varies from low to moderate, depending on their mucous or seromucous nature. The results indicate a large morphological and histochemical variation in the infralabial glands, probably reflecting differences in the secretion chemical composition and in feeding specialization among the three species. The protein content in the secretory cells can be related with the presence of toxins that can be used in chemical prey immobilization or detaching of snails from their shells. (c) 2007 Elsevier Ltd. All rights reserved.

A simple criterion to predict the glass forming ability of metallic alloys

A new and simple criterion with which to quantitatively predict the glass forming ability (GFA) of metallic alloys is proposed. It was found that the critical cooling rate for glass formation (R-C) correlates well with a proper combination of two factors, the minimum topological instability (lambda(min)) and the Delta h parameter, which depends on the average work function difference (Delta phi) and the average electron density difference (Delta n(ws)(1/3)) among the constituent elements of the alloy. A correlation coefficient (R-2) of 0.76 was found between R-c and the new criterion for 68 alloys in 30 different metallic systems. The new criterion and the Uhlmann's approach were used to estimate the critical amorphous thickness (Z(C)) of alloys in the Cu-Zr system. The new criterion underestimated R-C in the Cu-Zr system, producing predicted Z(C) values larger than those observed experimentally. However, when considering a scale factor, a remarkable similarity was observed between the predicted and the experimental behavior of the GFA in the binary Cu-Zr. When using the same scale factor and performing the calculation for the ternary Zr-Cu-Al, good agreement was found between the predicted and the actual best GFA region, as well as between the expected and the observed critical amorphous thickness. (C) 2012 American Institute of Physics. [doi:10.1063/1.3676196]

A graphical tool for an analytical approach of scattering photons by the Compton effect

The photons scattered by the Compton effect can be used to characterize the physical properties of a given sample due to the influence that the electron density exerts on the number of scattered photons. However, scattering measurements involve experimental and physical factors that must be carefully analyzed to predict uncertainty in the detection of Compton photons. This paper presents a method for the optimization of the geometrical parameters of an experimental arrangement for Compton scattering analysis, based on its relations with the energy and incident flux of the X-ray photons. In addition, the tool enables the statistical analysis of the information displayed and includes the coefficient of variation (CV) measurement for a comparative evaluation of the physical parameters of the model established for the simulation. (C) 2012 Elsevier B.V. All rights reserved.

Septin C-Terminal Domain Interactions: Implications for Filament Stability and Assembly

Septins form a conserved family of filament forming GTP binding proteins found in a wide range of eukaryotic cells. They share a common structural architecture consisting of an N-terminal domain, a central GTP binding domain and a C-terminal domain, which is often predicted to adopt a coiled-coil conformation, at least in part. The crystal structure of the human SEPT2/SEPT6/SEPT7 heterocomplex has revealed the importance of the GTP binding domain in filament formation, but surprisingly no electron density was observed for the C-terminal domains and their function remains obscure. The dearth of structural information concerning the C-terminal region has motivated the present study in which the putative C-terminal domains of human SEPT2, SEPT6 and SEPT7 were expressed in E. coli and purified to homogeneity. The thermal stability and secondary structure content of the domains were studied by circular dichroism spectroscopy, and homo- and hetero-interactions were investigated by size exclusion chromatography, chemical cross-linking, analytical ultracentrifugation and surface plasmon resonance. Our results show that SEPT6-C and SEPT7-C are able to form both homo- and heterodimers with a high alpha-helical content in solution. The heterodimer is elongated and considerably more stable than the homodimers, with a K (D) of 15.8 nM. On the other hand, the homodimer SEPT2-C has a much lower affinity, with a K (D) of 4 mu M, and a moderate alpha-helical content. Our findings present the first direct experimental evidence toward better understanding the biophysical properties and coiled-coil pairings of such domains and their potential role in filament assembly and stability.

Magnetic field induced charge redistribution in artificially disordered quantum Hall superlattices

The photoluminescence from individual quantum wells of artificially disordered weakly coupled multi-layers embedded in wide AlGaAs parabolic wells was investigated in a strong magnetic field. We show that the response of the individual wells is very different from the average response of the multi-layers studied by transport measurements and that photoluminescence represents a local probe of the quantum Hall state formed in three-dimensional electron system. The observed magnetic field induced variations of the in-layer electron density demonstrate the formation of a new phase in the quasi-three-dimensional electron system. The sudden change in the local electron density found at the Landau filling factor nu = 1 by both the magneto-transport and the magneto-photoluminescence measurements was assigned to the quantum phase transition. Copyright (C) EPLA, 2012

Structural, Spectroscopic (NMR, IR, and Raman), and DFT Investigation of the Self-Assembled Nanostructure of Pravastatin-LDH (Layered Double Hydroxides) Systems

Layered double hydroxide (LDH) nanocontainers, suitable as carriers for anionic drugs, were intercalated with Pravastatin drug using magnesium-aluminum and zinc-aluminum in a M-II/Al molar ratio equal 2 and different Al3+/Pravastatin molar ratios. Postsynthesis treatments were used in order to increase the materials crystallinity. Hybrid materials were characterized by a set of physical chemical techniques: chemical elemental analysis, X-ray diffraction (XRD), mass coupled thermal analyses, vibrational infrared and Raman spectroscopies, and solid-state C-13 nuclear magnetic resonance (NMR). Results were interpreted in light of computational density functional theory (DFT) calculations performed for Sodium Pravastatin in order to assign the data obtained for the LDH intercalated materials. XRD peaks of LDH-Pravastatin material and the one-dimensional (1D) electron density map pointed out to a bilayer arrangement of Pravastatin in the interlayer region, where its associated carboxylate and vicinal hydroxyl groups are close to the positive LDH. The structural organization observed for the stacked assembly containing the unsymmetrical and bulky monoanion Pravastatin and LDH seems to be promoted by a self-assembling process, in which local interactions are maximized and chloride ion cointercalation is required. It is observed a high similarity among vibrational and C-13 NMR spectra of Na-Pravastatin and LDH-Pravastatin materials. Those features indicate that the intercalation preserves the drug structural integrity. Spectroscopic techniques corroborate the nature of the guest species and their arrangement between the inorganic layers. Changes related to carboxylate, alcohol, and olefinic moieties are observed in both vibrational Raman and C-13 NMR spectra after the drug intercalation. Thus, Pravastatin ions are forced to be arranged as head to tail through intermolecular hydrogen bonding between adjacent organic species. The thermal decomposition profile of the hybrid samples is distinct of that one observed for Na-Pravastatin salt, however, with no visible increase in the thermal behavior when the organic anion is sequestrated within LDH gap.

Surface Segregation in Chromium-Doped Nanocrystalline Tin Dioxide Pigments

Surface properties play an important role in understanding and controlling nanocrystalline materials. The accumulation of dopants on the surface, caused by surface segregation, can therefore significantly affect nanomaterials properties at low doping levels, offering a way to intentionally control nanoparticles features. In this work, we studied the distribution of chromium ions in SnO2 nanoparticles prepared by a liquid precursor route at moderate temperatures (500 degrees C). The powders were characterized by infrared spectroscopy, X-ray diffraction, (scanning) transmission electron microscopy, Electron Energy Loss Spectroscopy, and Mossbauer spectroscopy. We showed that this synthesis method induces a limited solid solution of chromium into SnO2 and a segregation of chromium to the surface. The s-electron density and symmetry of Sn located on the surface were significantly affected by the doping, while Sn located in the bulk remained unchanged. Chromium ions located on the surface and in the bulk showed distinct oxidation states, giving rise to the intense violet color of the nanoparticles suitable for pigment application.

Gaussian deconvolution: a useful method for a form-free modeling of scattering data from mono- and multilayered planar systems

A new method for analysis of scattering data from lamellar bilayer systems is presented. The method employs a form-free description of the cross-section structure of the bilayer and the fit is performed directly to the scattering data, introducing also a structure factor when required. The cross-section structure (electron density profile in the case of X-ray scattering) is described by a set of Gaussian functions and the technique is termed Gaussian deconvolution. The coefficients of the Gaussians are optimized using a constrained least-squares routine that induces smoothness of the electron density profile. The optimization is coupled with the point-of-inflection method for determining the optimal weight of the smoothness. With the new approach, it is possible to optimize simultaneously the form factor, structure factor and several other parameters in the model. The applicability of this method is demonstrated by using it in a study of a multilamellar system composed of lecithin bilayers, where the form factor and structure factor are obtained simultaneously, and the obtained results provided new insight into this very well known system.