Electronic spectroscopy of biomolecules in solution: fluorescein dianion in water

A combined and sequential Monte Carlo-quantum mechanics methodology is used to describe the electronic absorption spectrum of the fluorescein dianion in water. Different sets of 100 statistically relevant configurations composed of the solute and several solvent molecules are sampled from the Monte Carlo simulation for a posteriori quantum mechanical calculations of the spectra. In the largest case the configurations are composed of fluorescein and 90 explicit water molecules embedded in the electrostatic field of all remaining water molecules within a distance of 11.3 angstrom. These configurations include 305 atoms and 842 valence electrons, justifying the use of a semi-empirical approach. The electronic spectrum is then calculated using the INDO/CIS method. The solvatochromic shift of fluorescein in water, compared with in isolation, is calculated using the discrete and explicit solvent models. The use of electrostatically embedded explicit water molecules, in INDO/CIS calculations, gives a good description of the spectral shift of the fluorescein dianion in aqueous environment. The results are verified to converge both statistically and with respect to the number of explicit solvent molecules used.

OSCILLATOR STRENGTHS AND LIFETIMES FOR THE P XII

Semi-empirical weighted oscillator strengths (gf) and lifetimes presented in this work for all experimentally known electric dipole P XII spectral lines and energy levels were computed within a multiconfiguration Hartree-Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure in order to improve the adjustment to experimental energy levels. The method produces lifetime and gf values that are in agreement with intensity observations used for the interpretation of spectrograms of solar and laboratory plasmas.

Adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface: A spectroscopic study

The adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface at 30 degrees C in the dark was investigated. The color reduction was monitored by spectrophotometry at 503 run. The FTIR and Raman spectra of the Direct Red 23 adsorption as a function of ZnO concentration were registered. From the PM3 semi-empirical calculations of the atomic charge density and dipole moment of the Direct Red 23 molecule, it was demonstrated that the azo, dye molecule may be adsorbed onto the ZnO Surface through molecule geometry modifications, enhancing the interfacial area causing a variation in the bonding frequencies. (C) 2009 Elsevier B.V. All rights reserved.

Estudo do comportamento de fundações superficiais assentes em solos tratados

Este trabalho é parte integrante de uma linha de pesquisa destinada ao estudo de viabilidade técnica de melhoramento artificial de camadas de solo. Objetiva-se com este trabalho contribuir para a viabilização de uso de solos melhorados para suporte de fundações superficiais. O estudo baseou-se em resultados experimentais de provas de carga em placas circulares de 0,30m e 0,60m de diâmetro sobre camadas de solo melhorado com cimento (teor de 5%) de 0,15m, 0,30111 e 0,60m de espessura. Os diâmetros das placas (D) e as espessuras das camadas de solo melhorado com cimento (H) foram fixados de forma a obter-se três valores distintos da relação H/D, correspondendo a 0,5, 1 e 2. Os resultados, representados adimensionalmente através de relações entre a tensão normalizada e o recalque relativo, demonstram a influência da espessura da camada de solo melhorado no comportamento de fbndações superficiais submetidas a carregamento vertical. Uma correlação de natureza semiempirica é desenvolvida de forma a permitir a previsão da magnitude de recalques e tensões de ruptura de sapatas a partir de resultados de ensaios de placa. Foram também avaliados a aplicabiidade de modelos analíticos para fundações superficiais assentes em perfis de solos não homegêneos com características coesivo-fnccionais. Neste sentido, apresenta-se urna comparação quantitativa e qualitativa entre os diversos métodos de previsão da capacidade de suporte e recalques, bem como uma validação das proposições através de comparações entre resultados calculados e medidos experimentalmente em campo. Os principais resultados obtidos na pesquisa são: [a] melhora de desempenho das fundações quando apoiadas em solos tratados, [b] dificuldade de previsão das cargas de ruptura e níveis de recalques em fundações apoiadas em solos estratifcados através de métodos analíticos, refletindo a complexidade deste problema de interação solo-estrutura e [c] desenvolvimento de uma metodologia semi-empírica para estimativa do comportamento de fùndações superíiciais com base em resultados de ensaios de placa.

Laminados compósitos de PRFV: efeitos da descontinuidade geométrica e do envelhecimento ambiental acelerado

The growing demand in the use of composite materials necessitates a better understanding of its behavior related to many conditions of loading and service, as well as under several ways of connections involved in mechanisms of structural projects. Within these project conditions are highlighted the presence of geometrical discontinuities in the area of cross and longitudinal sections of structural elements and environmental conditions of work like UV radiation, moisture, heat, leading to a decrease in final mechanical response of the material. In this sense, this thesis aims to develop studies detailed (experimental and semi-empirical models) the effects caused by the presence of geometric discontinuity, more specifically, a central hole in the longitudinal section (with reduced cross section) and the influence of accelerated environmental aging on the mechanical properties and fracture mechanism of FGRP composite laminates under the action of uniaxial tensile loads. Studies on morphological behavior and structural degradation of composite laminates are performed by macroscopic and microscopic analysis of affected surfaces, in addition to evaluation by the Measurement technique for mass variation (TMVM). The accelerated environmental aging conditions are simulated by aging chamber. To study the simultaneous influence of aging/geometric discontinuity in the mechanical properties of composite laminates, a semiempirical model is proposed and called IE/FCPM Model. For the stress concentration due to the central hole, an analisys by failures criteria were performed by Average-Stress Criterion (ASC) and Point-Stress Criterion (PSC). Two polymeric composite laminates, manufactured industrially were studied: the first is only reinforced by short mats of fiberglass-E (LM) and the second where the reinforced by glass fiber/E comes in the form of bidirectional fabric (LT). In the conception configurations of laminates the anisotropy is crucial to the final mechanical response of the same. Finally, a comparative study of all parameters was performed for a better understanding of the results. How conclusive study, the characteristics of the final fracture of the laminate under all conditions that they were subjected, were analyzed. These analyzes were made at the macroscopic level (scanner) microscope (optical and scanning electron). At the end of the analyzes, it was observed that the degradation process occurs similarly for each composite researched, however, the LM composite compared to composite LT (configurations LT 0/90º and LT ±45º) proved to be more susceptible to loss of mechanical properties in both regarding with the central hole as well to accelerated environmental aging

Análise da indução de fluxo de ar por convecção livre em chaminé solar

Experiments were performed to study the effect of surface properties of a vertical channel heated by a source of thermal radiation to induce air flow through convection. Two channels (solar chimney prototype) were built with glass plates, forming a structure of truncated pyramidal geometry. We considered two surface finishes: transparent and opaque. Each stack was mounted on a base of thermal energy absorber with a central opening for passage of air, and subjected to heating by a radiant source comprises a bank of incandescent bulbs and were performed field tests. Thermocouples were fixed on the bases and on the walls of chimneys and then connected to a data acquisition system in computer. The air flow within the chimney, the speed and temperature were measured using a hot wire anemometer. Five experiments were performed for each stack in which convective flows were recorded with values ranging from 17 m³ / h and 22 m³ / h and air flow velocities ranging from 0.38 m / s and 0.56 m / s for the laboratory tests and air velocities between 0.6 m/s and 1.1m/s and convective airflows between 650 m³/h and 1150 m³/h for the field tests. The test data were compared to those obtained by semi-empirical equations, which are valid for air flow induced into channels and simulated data from 1st Thermodynamics equation. It was found that the chimney with transparent walls induced more intense convective flows than the chimney with matte finish. Based on the results obtained can be proposed for the implementation of prototype to exhaust fumes, mists, gases, vapors, mists and dusts in industrial environments, to help promote ventilation and air renewal in built environments and for drying materials, fruits and seeds

Topliss method in the optimization of salicylic acid derivatives as potential antimycobacterial agents

The Topliss method was used to guide a synthetic path in support of drug discovery efforts toward the identification of potent antimycobacterial agents. Salicylic acid and its derivatives, p-chloro, p-methoxy, and m-chlorosalicylic acid, exemplify a series of synthetic compounds whose minimum inhibitory concentrations for a strain of Mycobacterium were determined and compared to those of the reference drug, p-aminosalicylic acid. Several physicochemical descriptors (including Hammett's sigma constant, ionization constant, dipole moment, Hansch constant, calculated partition coefficient, Sterimol-L and -B-4 and molecular volume) were considered to elucidate structure-activity relationships. Molecular electrostatic potential and molecular dipole moment maps were also calculated using the AM1 semi-empirical method. Among the new derivatives, m-chlorosalicylic acid showed the lowest minimum inhibitory concentration. The overall results suggest that both physicochemical properties and electronic features may influence the biological activity of this series of antimycobacterial agents and thus should be considered in designing new p-aminosalicylic acid analogs.

Cruzain inhibition by hydroxymethylnitrofurazone and nitrofurazone: investigation of a new target in Trypanosoma cruzi

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

Molecular Modeling Suggests Cruzain Specificity for Peptide Primaquine Prodrugs

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

Ultrasonic assessment of fresh cheese composition

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise teórica da interação de CO, CO2 e NH3 com ZnO

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

Febrifugine derivative antimalarial activity: quantum mechanical predictors

O desenvolvimento de linhagens resistentes de Plasmodium falciparum tem encorajado a busca por novas drogas antimalariais. A febrifugina é uma substância natural com alta atividade contra o P. falciparum que apresenta propriedade emética e toxicidade para o fígado tal que não permitem o seu uso clínico. A busca por análogos que possam ter uma performance clínica melhor é um tema de pesquisa atual. Nosso objetivo é investigar a estrutura eletrônica teórica de uma família de derivados da febrifugina empregando cálculos semi-empíricos de orbitais moleculares, procurando por índices eletrônicos que possam ajudar a modelar novos derivados mais eficientes. Os resultados teóricos mostram que para as moléculas mais seletivas existe um agrupamento dos valores de determinados índices em intervalos bem definidos. O modelo proposto para se obter alta seletividade foi testado com sucesso.

Synthesis of a functionalized europium complex and deposition of luminescent Langmuir-Blodgett (LB) films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multiple minima hypersurfaces procedures for biomimetic ligands screening

In this work the interaction of the pesticide carbaryl with two groups of biomimetic ligands, peptides and MIPs was screened by multiple minima hypersurfaces (MMH) procedures, through the AM1 semiempirical method. Data related to the properties of the molecular association of the complex biomimetic ligand-pesticide were obtained and compared with another molecular modeling algorithm named Leapfrog, as included in the Sybyl software package, and experimental results from the literature, remarking good correlation between them. All important MMH program parameters (cells number, box size, conformers) were studied and optimized with the aim of getting the minimum computation time without losing the correlation with experimental data. The data demonstrated that MMH approach can be used as a fast biomimetic ligand screening tool for MIPs. In the case of peptides the computation time was not comparable with the molecular dynamics methods conventionally used for this approach. © 2011 Springer Science+Business Media B.V.

Estudo conformacional do peptídeo IAN e seus fragmentos pelo método de análise sistemática reduzida

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)