New insights on the Lewis acidity of diorganolead(IV) compounds: Diphenyllead(IV) complexes with N,O,S-chelating ligands

The reactions of PbPh2(OAC)(2) with alkylglyoxylate thiosemicarbazones (HRGTSC, R = Et, Bu) afforded complexes of the type [PbPh2(GTSC)] center dot H2O, [PbPh2(RGTSC)(2)] and [PbPh2Cl(BUGTSC)]. The structures of HRGTSC (R = Me, Et, Bu), [PbPh2(OAc)(RGTSC)](R = Me, Et, Bu), [PbPh2Cl(BuGTSC)] and [PbPh2(GTSC)] center dot H2O have been studied by X-ray diffraction. [PbPh2(OAc)(RGTSC)] and [PbPh2(GTSC)] center dot H2O have [PbC2NO3S] kernels and the coordination sphere of the metal is pentagonal bipyramidal. [PbPh2Cl(BuGTSC)] has a [PbC2NOSCI] kernel and the coordination geometry around lead is pentagonal bipyramidal with one vacant site. Analysis of the bond distances in [PbPh2(GTSC)] center dot H2O suggests a significant affinity between diphenyllead(IV) and carboxylate donor groups, supporting a borderline acidic character for this organometallic cation. H-1 and C-13 NMR spectra in DMSO-d(6) suggest the partial dissociation of the acetate in [PbPh2(OAc)(RGTSC)] solutions and indicate some differences in the coordination mode of the two RGTSC(-) ligands in [PbPh2(RGTSC)(2)] complexes. (C) 2007 Elsevier Ltd. All rights reserved.

Crystalline structure of mangiferin, a C-glycosyl-substituted 9H-xanthen-9-one isolated from the stem bark of Mangifera indica

The crystalline structure of mangiferin (= 2-beta-D-glucopyranosyl-1,3,6,7-tetrahydroxy-9H-xanthen-9-one; 1), a biologically active xanthenone C-glycoside, isolated from the stem bark of Mangifera indica (Anacardiaceae), was unambiguously determined by single-crystal X-ray diffraction (XRD). The crystal structure is summarized as follows: triclinic, P1, a = 7.6575(5), b = 11.2094(8), c = 11.8749(8) angstrom, alpha = 79.967(5), beta = 87.988(4), gamma = 72.164(4)degrees, V = 955.3(1) angstrom(3), and Z = 2. The structure also shows two molecules in the asymmetric unit cell and five crystallization H2O molecules. The packing is stabilized by several intermolecular H-bonds involving either the two symmetry-independent mangiferin molecules 1a and 1b, or the H2O ones.

New Pd(II) and Pt(II) complexes with N,S-chelated pyrazolonate ligands: Molecular and supramolecular structure and preliminary study of their in vitro antitumoral activity

New Pd(II) and Pt(II) complexes [ML2] (HL = a substituted 2,5-dihydro-5-oxo-1H-pyrazolone-1-carbothioamide) have been synthesized by reacting K2MCl4 (M = Pd, Pt) or Pd(OAc)(2) with beta-ketoester thiosemicarbazones. The structures of seven of these complexes were determined by X-ray diffraction. Although all exhibit a distorted square-planar coordination with trans- or (in one case) cis-[MN2S2] kernels, their supramolecular arrangements vary widely from isolated molecules to 3D-networks. The in vitro antitumoral assays performed with two HL ligands and their metal complexes showed significant cytostatic activity for the latter, with the most active [ML2] derivative (a palladium complex) being about sixteen times more active than cis-DDP against the cis-platinum-resistant cell line A2780cisR. (c) 2007 Elsevier Inc. All rights reserved.

Inhibition of Mycobacterium tuberculosis tyrosine phosphatase PtpA by synthetic chalcones: Kinetics, molecular modeling, toxicity and effect on growth

Tuberculosis (TB) is a major cause of morbidity and mortality throughout the world, and it is estimated that one-third of the world`s population is infected with Mycobacterium tuberculosis. Among a series of tested compounds, we have recently identified five synthetic chalcones which inhibit the activity of M. tuberculosis protein tyrosine phosphatase A (PtpA), an enzyme associated with M. tuberculosis infectivity. Kinetic studies demonstrated that these compounds are reversible competitive inhibitors. In this work we also carried out the analysis of the molecular recognition of these inhibitors on their macromolecular target, PtpA, through molecular modeling. We observed that the predominant determinants responsible for the inhibitory activity of the chalcones are the positions of the two methoxyl groups at the A-ring, that establish hydrogen bonds with the amino acid residues Arg17, His49, and Thr12 in the active site of PtpA, and the substitution of the phenyl ring for a 2-naphthyl group as B-ring, that undergoes p stacking hydrophobic interaction with the Trp48 residue from PtpA. Interestingly, reduction of mycobacterial survival in human macrophages upon inhibitor treatment suggests their potential use as novel therapeutics. The biological activity, synthetic versatility, and low cost are clear advantages of this new class of potential tuberculostatic agents. (C) 2010 Elsevier Ltd. All rights reserved.

Rankamaite from the Urubu pegmatite, Itinga, Minas Gerais, Brazil: Crystal chemistry and Rietveld refinement

A new occurrence of rankamaite is here described at the Urubu pegmatite, Itinga municipality, Minas Gerais, Brazil. The mineral forms cream-white botryoidal aggregates of acicular to fibrous crystals, intimately associated with simpsonite, thoreaulite, cassiterite, quartz, elbaite, albite, and muscovite. The average of six chemical analyses obtained by electron microprobe is (range in parentheses, wt%): Na(2)O 2.08 (1.95-2.13), K(2)O 2.61 (2.52-2.74), Al(2)O(3) 1.96 (1.89-2.00), Fe(2)O(3) 0.01 (0.00-0.03), TiO(2) 0.02 (0.00-0.06), Ta(2)O(5) 81.04 (79.12-85.18), Nb(2)O(5) 9.49 (8.58-9.86), total 97.21 (95.95-101.50). The chemical formula derived from this analysis is (Na(1.55)K(1.28))(Sigma 2.83)(Ta(8.45)Nb(1.64)Al(0.89)Fe(0.01)(3+)Ti(0.01))(Sigma 11.00)[O(25.02)(OH)(5.98)](Sigma 31.00). Rankamaite is an orthorhombic ""tungsten bronze"" (OTB), crystallizing in the space group Cmmm. Its unit-cell parameters refined from X-ray diffraction powder data are: a = 17.224(3), b = 17.687(3), c = 3.9361(7) angstrom, V = 1199.1(3) angstrom(3), Z = 2. Rietveld refinement of the powder data was undertaken using the structure of LaTa(5)O(14) as a starting model for the rankamaite structure. The structural formula obtained with the Rietveld analyses is: (Na(2.21)K(1.26))Sigma(3.37)(Ta(9.12)NB(1.30) Al(0.59))(Sigma 11.00)[O(26.29)(OH)(4.71)](Sigma 31.00). The tantalum atoms are coordinated by six and seven oxygen atoms in the form of distorted TaO(6) octahedra and TaO(2) pentagonal bipyramids, respectively. Every pentagonal bipyramid shares edges with four octahedra, thus forming Ta(5)O(14) units. The potassium atom is in an 11-fold coordination, whereas one sodium atom is in a 10-fold and the other is in a 12-fold coordination. Raman and infrared spectroscopy were used to investigate the room-temperature spectra of rankamaite.

The Sphene-Centered Ocellar Texture: An Effect of Grain-Supported Flow and Melt Migration in a Hyperdense Magma Mush

The sphene-centered ocellar texture consists of leucocratic ocelli with sphene (titanite) crystals at the center, enclosed in a biotite-rich matrix. This texture has been recognized worldwide in hybrid intermediate rocks. On the basis of structural, petrological, and geochronological data from selected outcrops of the Variscan Ribadelago pluton (NW Iberian Massif), we propose that the ocelli were formed by migration and accumulation of a residual melt through a plagioclase- and biotite-dominated crystalline framework. At the late stage of crystallization, the magma acted as a hyperdense suspension and reacted to the pressure gradient caused by the regional stress field, entering the domain of grain-supported flow. Microstructures reveal that aligned crystal domains arose in the crystal framework from the shearing and compaction of the crystal mush and behaved as magmatic microshears. Relative displacement of adjacent crystal clusters along these microshears corresponded to the onset of Reynolds dilatancy that generated an expansion of the crystal mush, involving melt migration and pore aperture. The mineralogy of the ocelli, dominated by andesine and sphene, represents the composition of the migrating melt. The chemistry of this late, Ti-rich melt stems from the incongruent melting of biotite. Magmatic sphene from the ocelli yields a U-Pb age of 317 +/- 1 Ma, which represents the final crystallization of the hybridized magmatic system. Moreover, this texture offers an opportunity to better understand the rheological behavior of highly crystallized magmas.

Menezesite, the first natural heteropolyniobate, from Cajati, Sao Paulo, Brazil: Description and crystal structure

Menezesite, ideally Ba2MgZr4(BaNb12O42)center dot 12H(2)O, occurs as a vug mineral in the contact zone between dolomite carbonatite and ""jacupirangite"" (=a pyroxenite) at the Jacupiranga mine, in Cajati county, Sao Paulo state, Brazil, associated with dolomite, calcite, magnetite, clinohumite, phlogopite, ancylite-(Ce), strontianite, pyrite, and tochilinite. This is also the type locality for quintinite-2H. The mineral forms rhombododecahedra up to I mm, isolated or in aggregates. Menezesite is transparent and displays a vitreous luster; it is reddish brown with a white streak. It is non-fluorescent. Mohs hardness is about 4. Calculated density derived from the empirical formula is 4.181 g/cm(3). It is isotropic, 1.93(1) (white light); n(calc) = 2.034. Menezesite exhibits weak anomalous birefringence. The empirical formula is (Ba1.47K0.53Ca0.3,Ce0.17Nd0.10Na0.06La0.02)(Sigma 2.66)(Mg0.94Mn0.23Fe0.23Al0.03)(Sigma 1.43)(Zr2.75Ti0.96Th0.29)(Sigma 4.00)[(Ba0.72Th0.26U0.02)(Sigma 1.00)(Nb9.23Ti2.29Ta0.36Si0.12)Sigma O-12.00(42)]center dot 12H(2)O. The mineral is cubic, space group 10 (204), a = 13.017(1) angstrom, V = 2206(1) angstrom(3), Z = 2. Menezesite is isostructural with the synthetic compound Mg-7[MgW12O42](OH)(4)center dot 8H(2)O. The mineral was named in honor of Luiz Alberto Dias Menezes Filho (born 1950), mining engineer, mineral collector and merchant. Both the description and the name were approved by the CNMMN-IMA (Nomenclature Proposal 2005-023). Menezesite is the first natural heteropolyniobate. Heteropolyanions have been employed in a range of applications that include virus-binding inorganic drugs (including the AIDs virus), homogeneous and heterogeneous catalysts, electro-optic and electrochromic materials, metal and protein binding, and as building blocks for nanostructuring of materials.

Endividamento público municipal no Brasil pós 1988: o caso da responsabilidade fiscal de São Jose do Rio Preto

Trata da questão do endividamento público dos municípios brasileiros, analisando o caso de São José do Rio Preto dentro de uma amostra de outros quinze municípios do interior paulista. Aponta as condições que permitiram que São José do Rio Preto mantivesse, ao contrário da maioria da amostra estudada, um baixo e estável endividamento no período posterior à promulgação da Constituição de 1988

Prácticas culturales para el manejo de la Sigatoka negra en bananos y plátanos

Black sigatoka (Mycosphaerella fijiensis) control consists in the continuous use of fungicide sprays and cultural practices. Cultural control reduces inoculum sources of the pathogen and favorable environmental conditions for its development, as well as it increases the vigor of the plants. In order to manage the disease it is necessary to know its behavior through the time, its relationship with the weather and the crop management. The most important cultural practice to reduce the inoculum source is the removal of the whole affected leaves or only the diseased portions of the leaves. The removed tissue is placed over the ground and the use of urea is feasible to accelerate its decomposition. An alternative practice is the "mini-composting" that consists in forming small heaps with the dead leaves and harvested plants for its quick degradation, which allows to reduce the pathogen inoculum and to incorporate nutrients and organic matters into the soil. The early pruning of the tips of the Young leaves before they show symptoms of the disease and the quick elimination of harvested plants reduce the inoculum. Also, the agronomic management of the crop helps to reduce the favorable conditions and to increase the vigor of the plants: this management considers plantation density, drainage systems, irrigation methods, control of weeds, chemical-biological fertilization, and nematode control.

Nenneguya garavelli n. sp and Myxobolus peculiaris n. sp (Myxozoa : Myxobolidae) in the gills of Cyphocharax nagelli (Osteichthyes : Curimatidae) from Rio do Peixe Reservoir, Sao Jose do Rio Pardo, São Paulo, Brazil

The present work describes myxozoans found in Cyphocharax nagelli (Characiformes: Curimatinae) commonly called saguiru collected from Rio do Peixe Reservoir, Sao Jose do Rio Pardo, São Paulo, Brazil. From a total of 38 examined fish, 24 were infected with Henneguya garavelli n. sp. (63% prevalence) and two with Myxobolus peculiaris n. sp. (5% prevalence) in the gills. Spores were studied by staining and fresh spores were observed by differential interference contrast optics. Henneguya garavelli n. sp. differs from Henneguya iheringi , Henneguya occulta, Henneguya cesarpintoi, Henneguya santae, Henneguya pisciforme, Henneguya amazonica, Henneguya striolata, Henneguya leporinicola and Henneguya chydadea in spore length and from Henneguya travassosi, Henneguya adherens, Henneguya malabarica, Henneguya piaractus and also Henneguya chydadea in polar capsule length and tail length. Myxobolus peculiaris n. sp. was very different when compared to other species of Myxobolus in its morphology and the biggest size of spore body. The authors present tables with comparative measurements of Brazilian myxozoan parasites. (c) 2006 Elsevier B.V. All rights reserved.

Projeto e controle de um sistema de aquecimento no Laboratório de Avaliação de Medição em Petróleo

The Oil Measurement Evaluation Laboratory (LAMP), located in the Federal University of Rio Grande do Norte (UFRN), has as main goal to evaluate flow and BS&W meters, where the simulation of a bigger number of operation variable in field, guarantees a less uncertain evaluation. The objective of this work is to purpose a heating system design and implementation, which will control the temperature safely and efficiently in order to evaluate and measure it. Temperature is one of the variables which influence the flow and BS&W accurate measurement, directly affecting the fluid viscosity and density in the experiment. To project the heating system it is of great importance to take the laboratory requirements, conditions and current restrictions into consideration. Three alternatives were evaluated: heat exchanger, internal resistance and external resistance. After the analyses are made in order to choose the best alternative for the heating system in the laboratory, control strategies were determined for it, PID control methods in combination with fuzzy logic were used. Results showed a better performance with fuzzy logic than with classic PID

Protein Hydrolysis by Immobilized and Stabilized Trypsin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

Contando o passado, tecendo a saudade: a construção simbólica do engenho açucareiro em Jose Lins do Rego (1919-1943)

In this work I have searched the symbolical sense of a specific place. I have started from the theoretical assumption that places are social relations resulting from material and symbolical conditions developed in a certain time and by certain factors. In this sense, I have analyzed the symbolical aspect of sugar plantation from some literary works created by the writer José Lins do Rego from the state of Paraíba. I intend to analyze the symbolical dimension senses, values and images used by this writer to show the sugar plantation. Giving special attention to the works from the named cycle of sugar plantation , I have searched for the senses and meanings used in José Lins do Rego literary discourse to create a fictional sugar plantation, showing this place in a specific way. Based in cultural history, I have used several sources: literary works, prefaces of books, memory works, journalistic works, letters written by intellectual men and history books. My time of analysis is from 1919 the beginning of José Lins do Rego s intellectual activity - until 1943 publication of Fogo Morto, last literary work that I have analyzed. In symbolical terms, what is sugar plantation, this place that has totally touched José Lins do Regos life and literary work? That was the structural question that has determined the present research