Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.

Comparative molecular field analysis of a series of inhibitors of HIV-1 protease

Several protease inhibitors have reached the world market in the last fifteen years, dramatically improving the quality of life and life expectancy of millions of HIV-infected patients. In spite of the tremendous research efforts in this area, resistant HIV-1 variants are constantly decreasing the ability of the drugs to efficiently inhibit the enzyme. As a consequence, inhibitors with novel frameworks are necessary to circumvent resistance to chemotherapy. In the present work, we have created 3D QSAR models for a series of 82 HIV-1 protease inhibitors employing the comparative molecular field analysis (CoMFA) method. Significant correlation coefficients were obtained (q(2) = 0.82 and r(2) = 0.97), indicating the internal consistency of the best model, which was then used to evaluate an external test set containing 17 compounds. The predicted values were in good agreement with the experimental results, showing the robustness of the model and its substantial predictive power for untested compounds. The final QSAR model and the information gathered from the CoMFA contour maps should be useful for the design of novel anti-HIV agents with improved potency.

Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

A novel Schiff base-copper(II) complex [Cu(2)L(2)(N(3))(2)](ClO(4))(2) 1, where L = (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), containing azide-bridges between adjacent copper ions in a dinuclear arrangement was isolated and characterized both in the solid state and in solution by X-ray crystallography and different spectroscopic techniques. Azide binding constants were estimated from titrations of the precursor [CuL(H(2)O)(2)](2+) solutions with sodium azide, giving rise to the azido-bridged species, [Cu(2)L(2)(N(3))(2)](2+). Raman spectra showed asymmetric stretching band at 2060 cm(-1), indicating the presence of azido ligands with a symmetric mu(1,) (1) binding geometry. EPA spectra, in frozen methanol/water solutions at 77 K, exhibited characteristic features of copper centers in tetragonal pyramidal coordination geometry, exhibiting magnetic interactions between them. Further, in solid state, two different values for magnetic coupling in this species were obtained, J/k = -(5.14 +/- 0.02) cm(-1) attributed to the mu(1, 1) azide-bridge mode, and J`z`/k = -(2.94 +/- 0.11) cm(-1) for the interaction between dinuclear moieties via water/perchorate bridges. Finally, an attempt was made to correlate structure and magnetic data for this dinuclear asymmetric end-on azido bridged-copper(II) 1 complex with those of another correlated dinuclear system, complex [Cu(2)L(2)Cl(2)](ClO(4))(2) 2, containing the same tridentate diimine ligand, but with chloro-bridged groups between the copper centres.

Saturated Ceramides from the Sponge Dysidea robusta

Chemical investigation of the crude extract of a marine sponge Dysidea robusta led to the isolation of an inseparable mixture of saturated ceramides. These were identified from spectroscopic data as well as by hydrolysis followed by LC-MS analysis of the sphingosine moieties.

Chemical variability within the marine sponge Aplysina fulva

Dibromotyrosine-derived metabolites are of common occurrence within marine sponges belonging to the order Verongida. However, previous chemical analysis of crude extracts obtained from samples of the verongid sponge Aplysina fulva collected in Brazil did not provide any dibromotyrosine-derived compounds. In this investigation, five samples of A. fulva from five different locations along the Brazilian coastline and one sample from a temperate reef in the South Atlantic Bight (SAB) (Georgia, USA) were investigated for the presence of bromotyrosine-derived compounds. All six samples collected yielded dibromotyrosine-derived compounds, including a new derivative, named aplysinafulvin, which has been identified by. analysis of spectroscopic data. These results confirm previous assumptions that dibromotyrosine-derived metabolites can be considered as chemotaxonomic markers of verongid sponges. The isolation of aplysinafulvin provides additional support for a biogenetic pathway involving an arene oxide intermediate in the biosynthesis of Verongida metabolites. It cannot yet be established if the chemical variability observed among the six samples of A.fulva collected in Brazil and the SAB is the result of different environmental factors, distinct chemical extraction and isolation protocols, or a consequence of hidden genetic diversity within the postulated morphological plasticity of this species. (C) 2007 Elsevier Ltd. All rights reserved.

Antiparasitic, antineuroinflammatory, and cytotoxic polyketides from the marine sponge Plakortis angulospiculatus collected in Brazil

Investigation of the bioactive crude extract from the sponge Plakortis angulospiculatus from Brazil led to the isolation of plakortenone (1) as a new polyketide, along with five known polyketides (2-6) previously isolated from other Plakortis sponges. The known polyketides were tested in antileishmanial, antitrypanosomal, antineuroinflammatory, and cytotoxicity assays. The results show that plakortide P (3) is a potent antiparasitic compound, against both Leishmania chagasi and Trypanosona cruzi, and exhibited antineuroinflammatory activity. The known polyketides 2-6 were tested for cytotoxicity against four human cancer cell lines, but displayed only moderate cytotoxic activity.

Use of Experimental Design for the Optimization of the Production of New Secondary Metabolites by Two Penicillium Species

A fractional factorial design approach has been used to enhance secondary metabolite production by two Penicillium strains. The method was initially used to improve the production of bioactive extracts as a whole and subsequently to optimize the production of particular bioactive metabolites. Enhancements of over 500% in secondary metabolite production were observed for both P. oxalicum and P. citrinum. Two new alkaloids, citrinalins A (5) and B (6), were isolated and identified from P. citrinum cultures optimized for production of minor metabolites.

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.

Estudo de um solo residual de arenito da rodovia RS 239 : ensaios triaxiais servo-controlados

O estudo das propriedades mecânicas dos solos estruturados necessita de equipamentos de laboratório com características específicas. No caso de ensaios triaxiais, os equipamentos devem incorporar técnicas especiais, tais como: medição local de deformações e controle automático de trajetórias de tensão. Caso o solo seja ensaiado na condição não saturada, o equipamento deve ser capaz de controlar a sucção imposta ao corpo de prova. Esta dissertação apresenta a montagem de um equipamento triaxial automatizado para o estudo de solos estruturados, saturados e não saturados, sendo que para a execução de ensaios com diferentes trajetórias de tensões, pequenas modificações devem ser introduzidas no programa. O equipamento foi montado com peças encontradas no mercado nacional e de fácil aquisição. Este equipamento dispõe de medição local de deformações baseada em sensores de efeito Hall, com uma resolução de deformações axiais e radiais da ordem de 10-4. O equipamento utiliza um sistema de válvulas proporcionais para o controle automático das pressões aplicadas. O equipamento assim construído, foi utilizado para estudar o comportamento mecânico de um solo residual de arenito Botucatu oriundo de uma jazida na rodovia RS 239. Este solo apresenta um índice de vazios médio de 0,62. Envoltórias de resistência ao cisalhamento para valores de pico e para valores de deformações axiais >10%, foram determinadas a partir de resultados de ensaios triaxiais. Os resultados dos ensaios também permitiram identificar uma superfície de fluência. O efeito da cimentação, tanto na superfície de fluência como no módulo de Young, foi constatado através da análise das curvas tensão desvio x deformação axial, que mostram claramente uma mudança de comportamento associada à progressiva desestruturação do material.

Efeitos de abertura comercial sobre a evolução da produtividade industrial no Brasil

Este trabalho avalia a evolução da produtividade industrial brasileira — utilizando um painel de 16 setores da indústria de transformação no período 1985/97 — e o papel da abertura econômica neste processo. Os resultados mostram que a produtividade da indústria brasileira, seja ela medida pelo conceito de produtividade total dos fatores (PTF) ou de produtividade do trabalho, passou por duas fases distintas: de 1985 a 1990, há um processo de estagnação e de 1990 a 1997, a indústria passa a apresentar significativas taxas de crescimento. A abertura comercial, caracterizada por menores tarifas nominais e menores taxas de proteção efetiva, exerce um efeito positivo sobre o aumento da produtividade. Em todas as regressões do modelo — em que se utilizam técnicas de estimação em painéis — não se pode rejeitar a hipótese de que aumentos nas barreiras comerciais implicam menores taxas de crescimento da produtividade do trabalho e da PTF. Este resultado confirma a evidência internacional de que países mais abertos crescem mais rápido e desestimularia a adoção de políticas de restrição comercial como estratégia de desenvolvimento e de proteção à indústria nacional.

Migração e seleção: o caso do Brasil

Este trabalho tem como objetivo verificar se os brasileiros que moram numa unidade federativa diferente da unidade em que nasceram - os migrantes - formam um grupo positivamente selecionado (isto È, um grupo que seja, em mÈdia, mais apto, motivado, empreendedor, agressivo, ambicioso do que outro grupo) da populaÁ„o brasileira. Subsidiados pela literatura existente sobre o assunto e utilizando a Pesquisa Nacional por Amostra de DomicÌlios (PNAD) de 1999, conseguimos mostrar que os migrantes ganham, em mÈdia, mais do que os n„o-migrantes, no Brasil, sendo que esse resultado se mantÈm quando fazemos uma an·lise bivariada (controlando por estado de nascimento, estado de residÍncia, idade ou educaÁ„o) e quando fazemos uma an·lise multivariada, atravÈs de uma regress„o m˙ltipla (que controla conjuntamente uma sÈrie de vari·veis importantes na determinaÁ„o da renda do trabalho). A partir desse resultado, concluimos que, de fato, os migrantes, no Brasil, constituem um grupo positivamente selecionado.

Modelos de ciclos reais de negócios em pequena economia aberta aplicados ao Brasil

O objetivo deste trabalho é testar diversas especificações de modelos de ciclos reais de negócios em pequena economia aberta e avaliar em que medida eles conseguem reproduzir as características dos ciclos econômicos brasileiros. Um problema recorrente nos modelos de pequena economia aberta é que sua dinâmica de equilíbrio depende de condições iniciais e apresenta características não estacionárias. Neste trabalho estão presentes três diferentes especificações de modelos, que diferem na forma como a estacionariedade é induzida, são eles: 1) modelo com taxa de desconto endógena; 2) modelo com prêmio de risco elástico à dívida; 3) modelo com mercados completos. Também é testada a sensibilidade dos modelos a duas especificações de preferências - como em Greenwood et alli(1988) e como em Hansen(1985). Os modelos conseguiram replicar características importantes dos ciclos internacionais - como a correlação negativa entre a balança comercial e o produto, e a característica pró-cíclica das outras variáveis. Apenas o modelo com prêmio de risco conseguiu reproduzir a alta volatilidade do consumo brasileiro, sendo este resultado sensível à especificação de preferências. O choque de juros mostrou-se pouco importante para a dinâmica de todos os modelos e o custo de ajustamento foi essencial para a obtenção dos principais resultados.