Interactions of Diorganolead(IV) with 3-(2-Thienyl)-2-sulfanylpropenoic Acid and/or Thiamine: Chemical and in Vitro and in Vivo Toxicological Results

The reactions of PbR(2)(OAc)(2) (R=Me, Ph) with 3-(2-thienyl)-2-sulfanylpropenoic acid (H(2)tSpa) in methanol or ethanol afforded complexes [PbR(2)(tspa)] that electrospray ionization-mass spectrometry (ESI-MS) and IR data suggest are polymeric. X-ray studies showed that [PbPh(2)(tspa)(dmso)] center dot dmso, crystallized from a solution of [PbPh(2)(tspa)] in dmso, is dimeric, and that [HQ](2)[PbPh(2)(tspa)(2)] (Q=diisopropylamine), obtained after removal of [PbPh(2)(tspa)] from a reaction including Q, contains the monomeric anion [PbPh(2)(tSpa)(2)](2-). In the solid state the lead atoms are O,S-chelated by the tspa ligands in all these products, and in the latter two have distorted octahedral coordination environments. NMR data suggest that tspa(2-) remains coordinated to PbR(2)(2+) in solution in dmso. Neither thiamine nor thiamine diphosphate reacted with PbMe(2)(NO(3))(2) in D(2)O. Prior addition of H(2)tSpa protected LLC center dot PK1 renal proximal tubule cells against PbMe(2)(NO(3))(2); thiamine had no statistically significant effect by itself, but greatly potentiated the action of H(2)tSpa. Administration of either H(2)tspa or thiamine to male albino Sprague-Dawley rats dosed 30 min previously with PbMe(2)(NO(3))(2) was associated with reduced inhibition of delta-ALAD by the organolead compound, and with lower lead levels in kidney and brain, but joint administration of both H(2)tspa and thiamine only lowered lead concentration in the kidney.

Evidence of redox interactions between polypyrrole and Fe(3)O(4) in polypyrrole-Fe(3)O(4) composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe(3)O(4) incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation. (C) 2009 Elsevier Ltd. All rights reserved.

Excited Electronic States, Transition Probabilities, and Radiative Lifetimes of CAs: A Theoretical Contribution and Challenge to Experimentalists

High-level CASSCF/MRCI calculations with a quintuple-zeta quality basis set are reported by characterizing for the first time a manifold of electronic states of the CAs radical yet to be investigated experimentally. Along with the potential energy curves and the associated spectroscopic constants, the dipole moment functions for selected electronic states as well as the transition dipole moment functions for the most relevant electronic transitions are also presented. Estimates of radiative transition probabilities and lifetimes complement this investigation, which also assesses the effect of spin-orbit interaction on the A (2)Pi state. Whenever pertinent, comparisons of similarities and differences with the isovalent CN and CP radicals are made.

Spectroscopic investigation of the interactions between emeraldine base polyaniline and Eu(III) ions

The interactions of emeraldine base form of polyaniline (EB-PANI) and Eu(III) ions in 1-methyl-2-pyrrolidinone (NMP) solution and in films have been investigated by UV-vis-NIR, resonance Raman. luminescence and electron paramagnetic resonance (EPR) spectroscopies. These spectroscopic techniques allowed to characterize quinone and semiquinone segments in the polymeric chains. and the oxidation state of europium ions in Eu-PANI samples. For high values of Eu(III)/N molar ratio (24/1) the presence of a weak polaronic absorption band at 980 nm in UV-vis-NIR spectrum and the observation of bands at 1330 and 1378 (nu(center dot)(C-N+)) cm(-1) due to emeraldine salt in the Raman spectrum at 1064 nm indicate a low doping degree. Oxidation of EB-PANI to pernigraniline base (PB-PANI) occurs in diluted solutions. The experimental data showed that the solvent plays an important role on the nature of formed species. The narrow EPR signal at g = 2.006 (line width 8G) confirms the presence of PANI radical cations in Eu-PANI film. The absence of broad signal characteristic of Eu(II) in EPR spectrum suggested that europium ions are primarily at Eu(III) oxidation state. The luminescence spectra of Eu-PANI film presented emission bands at 405 and 418 nm assigned to PANI moieties and bands at 594,615 and 701 nm assigned to (5)D(0) -> (7)F(J) (J = 1, 2 and 4, respectively) transitions of Eu(III). EPR and photoluminescence data confirm that europium ions are mainly in Eu(III) oxidation state in Eu(III)/PANI films. (C) 2008 Elsevier B.V. All rights reserved.

Isoelectric Point Determination for Glossoscolex paulistus Extracellular Hemoglobin: Oligomeric Stability in Acidic pH and Relevance to Protein-Surfactant Interactions

The extracellular hemoglobin from Glossoscolex paulistus (HbGp) has a molecular mass of 3.6 M Da, It has a high oligomeric stability at pH 7.0 and low autoxidation rates, as compared to vertebrate hemoglobins. In this work, fluorescence and light scattering experiments were performed with the three oxidation forms of HbGp exposed to acidic pH. Our focus is on the HbGp stability at acidic pH and also on the determination of the isoelectric point (pI) of the protein. Our results show that the protein in the cyanomet form is more stable than in the other two forms, in the whole range. Our zeta-potential data are consistent with light scattering results. Average values apt obtained by different techniques were 5.6 +/- 0.5, 5.4 +/- 0.2 and 5.2 +/- 0.5 for the oxy, met, and cyanomet forms. Dynamic light scattering (DLS) experiments have shown that, at pH 6.0, the aggregation (oligomeric) state of oxy-, met- and cyanomet-HbGp remains the same as that at 7.0. The interaction between the oxy-HbGp and ionic surfactants at pH 5.0 and 6.0 was also monitored in the present study. At pH 5,0, below the protein pI, the effects of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium chloride (CTAC) are inverted when compared to pH 7.0. For CTAC, in acid pH 5.0, no precipitation is observed, while for SDS an intense light scattering appears due to a precipitation process. HbGp interacts strongly with the cationic surfactant at pH 7.0 and with the anionic one at pH 5.0. This effect is due to the predominance, in the protein surface, of residues presenting opposite charges to the surfactant headgroups. This information can be relevant for the development of extracellular hemoglobin-based artificial blood substitutes.

Dynamic whole system testing of combined renewable heating systems : the current state of the art

Objective: For the evaluation of the energetic performance of combined renewable heating systems that supply space heat and domestic hot water for single family houses, dynamic behaviour, component interactions, and control of the system play a crucial role and should be included in test methods. Methods: New dynamic whole system test methods were developed based on “hardware in the loop” concepts. Three similar approaches are described and their differences are discussed. The methods were applied for testing solar thermal systems in combination with fossil fuel boilers (heating oil and natural gas), biomass boilers, and/or heat pumps. Results: All three methods were able to show the performance of combined heating systems under transient operating conditions. The methods often detected unexpected behaviour of the tested system that cannot be detected based on steady state performance tests that are usually applied to single components. Conclusion: Further work will be needed to harmonize the different test methods in order to reach comparable results between the different laboratories. Practice implications: A harmonized approach for whole system tests may lead to new test standards and improve the accuracy of performance prediction as well as reduce the need for field tests.

Interactions of Electrons and Rydberg Atoms in Ultra-Cold Plasmas

This thesis discusses an experimental technique for investigating electron temperature control by Rydberg atoms in ultra-cold plasmas. The objective we set ourselves was twofold. Firstly, we sought to gain an insight into the processes whereby the creation of Rydberg atoms within the plasma lengthens the lifetime of the plasma. To this end, we created the plasma using a Littman dye laser and subsequently, at a variable time delay, we excited neutral atoms in the plasma to specific Rydberg states using a narrow bandwidth pulsed dye laser. Secondly, we employed radio-frequency (rf) electric fields to excite electron oscillations within the plasma in order to infer such information as plasma density and electron temperature. Although we found that the introduction of high angular momentum Rydberg states did lengthen the plasma lifetime we were not able to differentiate between the temperature moderation effect due to the Rydberg atoms cooling the plasma, and the binding effect due to an increased positive space charge within the plasma.

Quasi-experimental estimates of fiscal spillovers and spatial interactions among Brazilian cities

Nós usamos a metodologia de Regressões em Descontinuidade (RDD) para estimar o efeito causal do Fundo de Participação dos Municípios (FPM) recebido por um município sobre características dos municípios vizinhos, considerando uma variedade de temas: finanças públicas, educação, saúde e resultados eleitorais. Nós exploramos a regra que gera uma variação exógena da transferência em munícipios próximos às descontinuidades no repasse do fundo de acordo com faixas de população. Nossa principal contribuição é estimar separadamente e em conjunto o efeito spillover e o efeito direto do FPM, considerando ambos municípios vizinhos ou apenas um deles próximos às mudanças de faixa. Dessa forma, conseguimos entender melhor a interação entre municípios vizinhos quando há uma correlação na probabilidade de receber uma transferência federal. Nós mostramos que a estimativa do efeito direto do FPM sobre os gastos locais diminui em cerca de 20% quando controlamos pelo spillover do vizinho, que em geral é positivo, com exceção dos gastos em saúde e saneamento. Nós estimamos um efeito positivo da transferência sobre notas na prova Brasil e taxas de aprovação escolares em municípios vizinhos e na rede estadual do ensino fundamental. Por outro lado, o recebimento de FPM por municípios vizinhos de pequena população reduz o provimento de bens e serviços de saúde em cidades próximas e maiores, o que pode ocorrer devido à redução da demanda por serviços de saúde. A piora de alguns indicadores globais de saúde é um indício, no entanto, de que podem existir problemas de coordenação para os prefeitos reterem seus gastos em saúde. De fato, quando controlamos pela margem de vitória nas eleições municipais e consideramos apenas cidades vizinhas com prefeitos de partido diferentes, o efeito spillover é maior em magnitude, o que indica que incentivos políticos são importantes para explicar a subprovisão de serviços em saúde, por um lado, e o aumento da provisão de bens em educação, por outro. Nós também constatamos um efeito positivo do FPM sobre votos para o partido do governo federal nas eleições municipais e nacionais, e grande parte desse efeito é explicado pelo spillover do FPM de cidades vizinhas, mostrando que cidades com dependência econômica do governo federal se tornam a base de sustentação e apoio político desse governo. Por fim, nós encontramos um efeito ambíguo do aumento de receita devido ao FPM sobre a competição eleitoral nas eleições municipais, com uma queda da margem de vitória do primeiro colocado e uma redução do número de candidatos, o que pode ser explicado pelo aumento do custo fixo das campanhas locais.

Bee communities (Hymenoptera: Anthophila) of the Cerrado ecosystem in São Paulo State, Brazil

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

DNA barcodes identify marine fishes of São Paulo State, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spatial and temporal population interactions between the parasitoids Cotesia flavipes and Tachinidae flies: considerations on the adverse effects of biological control practice

Biological control of Diatraea saccharalis is regarded as one of the best examples of successful classical biological control in Brazil. Since the introduction of the exotic parasitoid Cotesia flavipes, the decrease of D. saccharalis infestation in sugarcane fields has been attributed to the effectiveness of this agent. Recently, the native tachinid fly parasitoids (Lydella minense and Paratheresia claripalpis) have also been implicated in the success. Here, we investigated the spatial and temporal population interactions between C. flavipes and the tachinid flies, and provide a critical analysis of the biological control practice, focusing on the undesirable effects of introductions of exotic natural enemies. To investigate these questions, a large data set comprising information from two sugarcane mills located in the state of São Paulo, Brazil (Barra and Sao Joao Mills), was analysed. Analysis of the correlation between C. flavipes and tachinid fly population densities through time revealed that such populations were inversely correlated in the Sao Joao Mill and not correlated in the Barra Mill. Logistic regressions were computed to investigate the proportion of sites occupied by the parasitoid species at both mills as a function of time. An increasing trend in the proportion of sites occupied by C. flavipes was observed, with a concomitant decrease of the sites occupied by tachinid flies. This effect was more intense in the Sao Joao Mill. Thus, there is a convincing possibility that constant releases of C. flavipes decreased the tachinid fly populations, resulting in an undesirable effect of biological control practice.

Social interactions in Hypsiboas albomarginatus (Anura : Hylidae) and the significance of acoustic and visual signals

Social behavior of Hypsiboas albomarginatus was studied in the Atlantic rain forest, Municipality of Ubatuba, in the north coast of the State of São Paulo, southeastern Brazil. Vocalizations of H. albomarginatus are described, including contexts in which they were emitted and temporal and spectral parameters differentiating advertisement from aggressive calls. Dominant call frequency was inversely correlated with male length and body mass but not with environmental temperature. Number of pulses per note was not correlated with any variable, and advertisement call amplitude was influenced by temperature and time. During chorus aggregation, males interacted acoustically by emitting advertisement calls in antiphony, or by emitting aggressive calls. Some disputes among males culminated in physical combat; males performed kicks and slaps on rivals' heads, in an apparent attempt to dislodge rivals from perches. Visual signals were also displayed during conflicts between males, contributing to an escalation of aggressive behavior. Visual signals were not recorded during courtship between males and females but may help in the accurate localization of the signaling male during aggressive interactions.

Dominance and Subordination Interactions Among Nestmates in Pre and Post-Emergence Phases of the Basal Eusocial Wasp Mischocyttarus (Monogynoecus) montei (Hymenoptera, Vespidae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The Origin of Nonmonotonic Complex Behavior and the Effects of Nonnative Interactions on the Diffusive Properties of Protein Folding

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

Atomic Bose-Einstein condensation with three-body interactions and collective excitations

The stability of a Bose-Einstein condensed state of trapped ultra-cold atoms is investigated under the assumption of an attractive two-body and a repulsive three-body interaction. The Ginzburg-Pitaevskii-Gross (GPG) nonlinear Schrodinger equation is extended to include an effective potential dependent on the square of the density and solved numerically for the s-wave. The lowest collective mode excitations are determined and their dependences on the number of atoms and on the strength of the three-body force are studied. The addition of three-body dynamics can allow the number of condensed atoms to increase considerably, even when the strength of the three-body force is very small compared with the strength of the two-body force. We study in detail the first-order liquid-gas phase transition for the condensed state, which can happen in a critical range of the effective three-body force parameter.