Analyzing the n→π* Electronic Transition of Formaldehyde in Water. A Sequential Monte Carlo/Time-Dependent Density Functional Theory

The n→π* absorption transition of formaldehyde in water is analyzed using combined and sequential classical Monte Carlo (MC) simulations and quantum mechanics (QM) calculations. MC simulations generate the liquid solute-solvent structures for subsequent QM calculations. Using time-dependent density functional theory in a localized set of gaussian basis functions (TD-DFT/6-311++G(d,p)) calculations are made on statistically relevant configurations to obtain the average solvatochromic shift. All results presented here use the electrostatic embedding of the solvent. The statistically converged average result obtained of 2300 cm-1 is compared to previous theoretical results available. Analysis is made of the effective dipole moment of the hydrogen-bonded shell and how it could be held responsible for the polarization of the solvent molecules in the outer solvation shells.

Ambiente de desenvolvimento e início da vida reprodutiva em mulheres Brasileiras

Modelos teóricos inspirados na teoria da história de vida têm avaliado padrões de reprodução humanos em países desenvolvidos, com resultados ainda não conclusivos. Em vista das condições de vida na população brasileira, foram investigadas relações entre marcos da carreira reprodutiva feminina, condições ambientais e variáveis psicossociais relacionadas às condições de criação. Foram entrevistadas 606 mulheres em seis estados. Os resultados apóiam a teoria da história de vida, mostrando associações entre condições de vida na infância e início da vida sexual e da reprodução, mas não com a idade da menarca. Sugerimos que diferentes marcadores da vida reprodutiva podem estar sob controle de diferentes fenômenos e que a diversidade de condições da população brasileira oferece contextos alternativos para testar hipóteses.

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

Vigilância de Fatores de Risco para Doenças Crônicas por Inquérito Telefônico nas capitais dos 26 estados brasileiros e no Distrito Federal (2006)

OBJETIVO: Descrever métodos e resultados iniciais do Sistema de Vigilância de Fatores de Risco e Proteção para Doenças Crônicas não Transmissíveis por Inquérito Telefônico - VIGITEL implantado no Brasil em 2006. MÉTODOS: O VIGITEL estudou amostras probabilísticas da população com 18 ou mais anos de idade residente em domicílios conectados à rede de telefonia fixa de cada uma das capitais dos 26 Estados brasileiros e do Distrito Federal (54.369 indivíduos no total, sendo pelo menos 2.000 por cidade). A amostragem foi realizada a partir de cadastros eletrônicos completos das linhas residenciais fixas de cada cidade, envolvendo sorteio de linhas (domicílios) e sorteio de um morador por linha para ser entrevistado. O questionário aplicado investigou características demográficas e socioeconômicas, padrão de alimentação e de atividade física, consumo de cigarros e de bebidas alcoólicas, e peso e altura recordados, entre outros quesitos. Estimativas sobre a freqüência de fatores de risco selecionados, estratificadas por sexo e acompanhadas de Intervalo de Confiança de 95%, foram calculadas para a população adulta de cada cidade empregando-se fatores de ponderação que igualam a composição sociodemográfica da amostra em cada cidade àquela observada no Censo Demográfico de 2000. Estimativas para o conjunto das cidades empregam fator de ponderação adicional que leva em conta a população de adultos de cada cidade. RESULTADOS: Os cinco fatores de risco selecionados (tabagismo, consumo abusivo de bebidas alcoólicas, excesso de peso, consumo de carnes com excesso de gordura e sedentarismo) tenderam a ser mais freqüentes em homens do que em mulheres. Dentre os fatores de proteção, o consumo regular de frutas e hortaliças foi mais freqüente em mulheres do que em homens, observando-se situação inversa no caso da atividade física de lazer. Diferenças substanciais na freqüência dos fatores de risco e proteção foram observadas entre as cidades, com padrões de distribuição regional diferenciados por fator. DISCUSSÃO: O desempenho do sistema, avaliado a partir da qualidade dos cadastros telefônicos e de taxas de resposta e de recusas, mostrou-se adequado e, de modo geral, superior ao encontrado em sistemas equivalentes existentes em países desenvolvidos. O custo do sistema de R$ 31,15 por entrevista realizada, foi a metade do custo observado no sistema americano de vigilância de fatores de risco para doenças crônicas por inquérito telefônico e um quinto do custo estimado em inquérito domiciliar tradicional realizado recentemente no Brasil.

Vigilância de fatores de risco para doenças crônicas por inquérito telefônico nas capitais dos 26 estados brasileiros e no Distrito Federal (2006)

Objetivo: Descrever métodos e resultados iniciais do Sistema de Vigilância de Fatores de Risco e Proteção para Doenças Crônicas ão Transmissíveis por Inquérito Telefônico - VIGITEL implantado no Brasil em 2006. Métodos: O VIGITEL estudou amostras probabilísticas da população com 18 ou mais anos de idade residente em domicílios conectados à rede de telefonia fixa de cada uma das capitais dos 26 Estados brasileiros e do Distrito Federal (54.369 indivíduos no total, sendo pelo menos 2.000 por cidade). A amostragem foi realizada a partir de cadastros eletrônicos completos das linhas residenciais fixas de cada cidade, envolvendo sorteio de linhas (domicílios) e sorteio de um morador por linha para ser entrevistado. O questionário aplicado investigou características demográficas e socioeconômicas, padrão de alimentação e de atividade física, consumo de cigarros e de bebidas alcoólicas, e peso e altura recordados, entre outros quesitos. Estimativas sobre a freqüência de fatores de risco selecionados, estratificadas por sexo e acompanhadas de Intervalo de Confiança de 95%, foram calculadas para a população adulta de cada cidade empregando-se fatores de ponderação que igualam a composição sociodemográfica da amostra em cada cidade àquela observada no Censo Demográfico de 2000. Estimativas para o conjunto das cidades empregam fator de ponderação adicional que leva em conta a população de adultos de cada cidade. Resultados: Os cinco fatores de risco selecionados (tabagismo, consumo abusivo de bebidas alcoólicas, excesso de peso, consumo de carnes com excesso de gordura e sedentarismo) tenderam a ser mais freqüentes em homens do que em mulheres. Dentre os fatores de proteção, o consumo regular de frutas e hortaliças foi mais freqüente em mulheres do que em homens, observando-se situação inversa no caso da atividade física de lazer. ) Diferenças substanciais na freqüência dos fatores de risco e proteção foram observadas entre as cidades, com padrões de distribuição regional diferenciados por fator.Discussão: O desempenho do sistema, avaliado a partir da qualidade dos cadastros telefônicos e de taxas de resposta e de recusas, mostrou-se adequado e, de modo geral, superior ao encontrado em sistemas equivalentes existentes em países desenvolvidos. O custo do sistema de R$ 31,15 por entrevista realizada, foi a metade do custo observado no sistema americano de vigilância de fatores de risco para doenças crônicas por inquérito telefônico e um quinto do custo estimado em inquérito domiciliar tradicional realizado recentemente no Brasil

A new constitutive theory extending Hypoplasticity

The purpose of the present theory is to improve Hypoplasticity, especially in relation to reloading processes. This is done by means of two hypoplastic equations (a classical equation along with a new one containing a so-called mnemonic tensor), a cone in stress space and a criterion defining loading, unloading and reloading. (C) 2010 Elsevier Ltd. All rights reserved.

Possible states in the flow around two circular cylinders in tandem with separations in the vicinity of the drag inversion spacing

The possible states in the flow around two identical circular cylinders in tandem arrangements are investigated for configurations in the vicinity of the drag inversion separation. By means of numerical simulations, the hysteresis in the transition between the shedding regimes is studied and the relationship between (three-dimensional) secondary instabilities and shedding regime determination is addressed. The differences observed in the behavior of two- and three-dimensional flows are analyzed, and the regions of bistable flow are delimited. Very good agreement is found between the proposed scenario and results available in the literature. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3420111]

Anomalous thermodynamic properties in ferropericlase throughout its spin crossover transition

The thermodynamics properties of ferropericlase (Mg(1-x)Fe(x)O where x=0.1875) (Fp) throughout its spin crossover were investigated by first principles. Fp was treated as an ideal solid solution of pure high-spin and low-spin states. The Gibbs free energies of the pure states were addressed using the LDA+U method. A vibrational virtual-crystal model was developed to address the vibrational properties of the pure spin cases and used in conjunction with quasiharmonic theory to compute their vibrational free energies. The thermodynamics properties of Fp display significant anomalies that should be typical of spin crossover systems in general. In Fp, in particular, they are fundamental for understanding the state of earth's interior, where the pressure and temperature conditions of the crossover are realized.

Decision theory applied to image quality control in radiology

Background: The present work aims at the application of the decision theory to radiological image quality control ( QC) in diagnostic routine. The main problem addressed in the framework of decision theory is to accept or reject a film lot of a radiology service. The probability of each decision of a determined set of variables was obtained from the selected films. Methods: Based on a radiology service routine a decision probability function was determined for each considered group of combination characteristics. These characteristics were related to the film quality control. These parameters were also framed in a set of 8 possibilities, resulting in 256 possible decision rules. In order to determine a general utility application function to access the decision risk, we have used a simple unique parameter called r. The payoffs chosen were: diagnostic's result (correct/incorrect), cost (high/low), and patient satisfaction (yes/no) resulting in eight possible combinations. Results: Depending on the value of r, more or less risk will occur related to the decision-making. The utility function was evaluated in order to determine the probability of a decision. The decision was made with patients or administrators' opinions from a radiology service center. Conclusion: The model is a formal quantitative approach to make a decision related to the medical imaging quality, providing an instrument to discriminate what is really necessary to accept or reject a film or a film lot. The method presented herein can help to access the risk level of an incorrect radiological diagnosis decision.

Prognostic index expression of cyclin-D1, cerbB-2 and VEGF: metastases vs corresponding primary cancers and metastatic vs non-metastatic adenocarcinomas

The prognostic relevance of different molecular markers in lung cancer is a crucial issue still worth investigating, and the specimens collected and analyzed represent a valuable source of material. Cyclin-D1, c-erbB-2 and vascular endothelial growth factor (VEGF) have shown to be promising as prognosticators in human cancer. In this study, we sought to examine the importance of Cyclin-D1, c-erbB-2 and VEGF, and to study the quantitative relationship among these factors and disease progression in metastases vs corresponding primary cancer, and metastatic vs non metastatic cancers. Material and Methods: We used immunohistochemistry and morphometric analysis to evaluate the amount of tumour staining for Cyclin-D1, c-erbB-2 and VEGF in 52 patients with surgically excised ademocarcinoma of the lung, and the outcome for our study was survival time until death from hematogenic metastases. Results: Metastasis presented lower c-erbB-2 expression than corresponding primary cancers (p=0.02). Cyclin-D1 and VEGF expression were also lower in metastases than in corresponding primary cancers, but this difference did not achieve statistical significance. Non-metastatic cancers also presented significantly lower Cyclin-D1 and c-erbB-2 expression than metastatic cancers (p<0.01 and p<0.01, respectively). Equally significant was the difference between higher c-erbB-2 expression by metastatic cancers compared to non-metastatic cancers (p=0.02). Considering survival in Kaplan-Maier analysis, Cyclin-D1 (p=0.04), c-erbB-2 (p=0.04) and VEGF (p<0.01) were important predictors of survival in metastatic cancers.

Multiple classical limits in relativistic and nonrelativistic quantum mechanics

The existence of a classical limit describing the interacting particles in a second-quantized theory of identical particles with bosonic symmetry is proved. This limit exists in addition to the previously established classical limit with a classical field behavior, showing that the limit h -> 0 of the theory is not unique. An analogous result is valid for a free massive scalar field: two distinct classical limits are proved to exist, describing a system of particles or a classical field. The introduction of local operators in order to represent kinematical properties of interest is shown to break the permutation symmetry under some localizability conditions, allowing the study of individual particle properties.

Dynamics and constraints of the massive graviton dark matter flat cosmologies

We discuss the dynamics of the Universe within the framework of the massive graviton cold dark matter scenario (MGCDM) in which gravitons are geometrically treated as massive particles. In this modified gravity theory, the main effect of the gravitons is to alter the density evolution of the cold dark matter component in such a way that the Universe evolves to an accelerating expanding regime, as presently observed. Tight constraints on the main cosmological parameters of the MGCDM model are derived by performing a joint likelihood analysis involving the recent supernovae type Ia data, the cosmic microwave background shift parameter, and the baryonic acoustic oscillations as traced by the Sloan Digital Sky Survey red luminous galaxies. The linear evolution of small density fluctuations is also analyzed in detail. It is found that the growth factor of the MGCDM model is slightly different (similar to 1-4%) from the one provided by the conventional flat Lambda CDM cosmology. The growth rate of clustering predicted by MGCDM and Lambda CDM models are confronted to the observations and the corresponding best fit values of the growth index (gamma) are also determined. By using the expectations of realistic future x-ray and Sunyaev-Zeldovich cluster surveys we derive the dark matter halo mass function and the corresponding redshift distribution of cluster-size halos for the MGCDM model. Finally, we also show that the Hubble flow differences between the MGCDM and the Lambda CDM models provide a halo redshift distribution departing significantly from the those predicted by other dark energy models. These results suggest that the MGCDM model can observationally be distinguished from Lambda CDM and also from a large number of dark energy models recently proposed in the literature.

Matter-wave two-dimensional solitons in crossed linear and nonlinear optical lattices

The existence of multidimensional matter-wave solitons in a crossed optical lattice (OL) with a linear optical lattice (LOL) in the x direction and a nonlinear optical lattice (NOL) in the y direction, where the NOL can be generated by a periodic spatial modulation of the scattering length using an optically induced Feshbach resonance is demonstrated. In particular, we show that such crossed LOLs and NOLs allow for stabilizing two-dimensional solitons against decay or collapse for both attractive and repulsive interactions. The solutions for the soliton stability are investigated analytically, by using a multi-Gaussian variational approach, with the Vakhitov-Kolokolov necessary criterion for stability; and numerically, by using the relaxation method and direct numerical time integrations of the Gross-Pitaevskii equation. Very good agreement of the results corresponding to both treatments is observed.

Quantum statistical correlations in thermal field theories: Boundary effective theory

We show that the one-loop effective action at finite temperature for a scalar field with quartic interaction has the same renormalized expression as at zero temperature if written in terms of a certain classical field phi(c), and if we trade free propagators at zero temperature for their finite-temperature counterparts. The result follows if we write the partition function as an integral over field eigenstates (boundary fields) of the density matrix element in the functional Schrodinger field representation, and perform a semiclassical expansion in two steps: first, we integrate around the saddle point for fixed boundary fields, which is the classical field phi(c), a functional of the boundary fields; then, we perform a saddle-point integration over the boundary fields, whose correlations characterize the thermal properties of the system. This procedure provides a dimensionally reduced effective theory for the thermal system. We calculate the two-point correlation as an example.

Thermal instability in a gravity-like scalar theory

We study the question of stability of the ground state of a scalar theory which is a generalization of the phi(3) theory and has some similarity to gravity with a cosmological constant. We show that the ground state of the theory at zero temperature becomes unstable above a certain critical temperature, which is evaluated in closed form at high temperature.