A theoretical study on cytosine tautomers in aqueous media by using continuum models

B3LYP/6-31 + + G** and MP2/6-31 + + G** calculations have been carried out to study six tautomers of the nucleic acid base cytosine in aqueous media. Solvent effects have been analyzed using the self-consistent reaction field theory with two continuum methods. Relative stabilities and optimized geometries have been calculated for the tautomers and compared with experimental data. The present results show the importance of electrostatic solvent effects in determining observable properties of the cytosine tautomers. The amino-oxo form (C1) is the most abundant tautomer in aqueous media while the other amino-oxo form (C4) is the most energetically favored when solvent effects are included. These results can be justified by the larger values of the dipole moments for both C1 and C4 tautomers. Theoretical and experimental results of the harmonic vibrational frequencies and rotational constants show good agreement. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Two-dimensional modeling of material failure in reinforced concrete by means of a continuum strong discontinuity approach

The paper presents a new methodology to model material failure, in two-dimensional reinforced concrete members, using the Continuum Strong Discontinuity Approach (CSDA). The mixture theory is used as the methodological approach to model reinforced concrete as a composite material, constituted by a plain concrete matrix reinforced with two embedded orthogonal long fiber bundles (rebars). Matrix failure is modeled on the basis of a continuum damage model, equipped with strain softening, whereas the rebars effects are modeled by means of phenomenological constitutive models devised to reproduce the axial non-linear behavior, as well as the bondslip and dowel effects. The proposed methodology extends the fundamental ingredients of the standard Strong Discontinuity Approach, and the embedded discontinuity finite element formulations, in homogeneous materials, to matrix/fiber composite materials, as reinforced concrete. The specific aspects of the material failure modeling for those composites are also addressed. A number of available experimental tests are reproduced in order to illustrate the feasibility of the proposed methodology. (c) 2007 Elsevier B.V. All rights reserved.

Mamíferos não voadores do Parque Estadual Carlos Botelho, Continuum florestal do Paranapiacaba

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

Short-time dynamics of percolation observables

We consider the critical short-time evolution of magnetic and droplet-percolation order parameters for the Ising model in two and three dimensions, through Monte Carlo simulations with the (local) heat-bath method. We find qualitatively different dynamic behaviors for the two types of order parameters. More precisely, we find that the percolation order parameter does not have a power-law behavior as encountered for the magnetization, but develops a scale (related to the relaxation time to equilibrium) in the Monte Carlo time. We argue that this difference is due to the difficulty in forming large clusters at the early stages of the evolution. Our results show that, although the descriptions in terms of magnetic and percolation order parameters may be equivalent in the equilibrium regime, greater care must be taken to interpret percolation observables at short times. In particular, this concerns the attempts to describe the dynamics of the deconfinement phase transition in QCD using cluster observables.

Dynamic critical behavior of percolation observables in the 2d Ising model

We present preliminary results of our numerical study of the critical dynamics of percolation observables for the two-dimensional Ising model. We consider the (Monte-Carlo) short-time evolution of the system obtained with a local heat-bath method and with the global Swendsen-Wang algorithm. In both cases, we find qualitatively different dynamic behaviors for the magnetization and Omega, the order parameter of the percolation transition. This may have implications for the recent attempts to describe the dynamics of the QCD phase transition using cluster observables.

Percolation of Monte Carlo clusters

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

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

Um método de correção de interferência espectral e de transporte é proposto, e foi aplicado para minimizar interferências por moléculas de PO produzidas em chama ar-acetileno e de transporte causada pela variação da concentração de ácido fosfórico. Átomos de Pb e moléculas de PO absorvem a 217,0005 nm, então Atotal217,0005 nm = A Pb217,0005 nm + A PO217,0005 nm. Monitorando o comprimento de onda alternativo de PO em 217,0458 nm, é possível calcular a contribuição relativa de PO na absorbância total a 217,0005 nm: A Pb217,0005 nm = Atotal217,0005 nm - A PO217,0005 nm = Atotal217,0005 nm - k (A PO217,0458 nm). O fator de correção k é a razão entre os coeficientes angulares de duas curvas analíticas para P obtidas a 217,0005 e 217,0458 nm (k = b217,0005 nm/b217,0458 nm). Fixando-se a taxa de aspiração da amostra em 5,0 ml min-1, e integrando-se a absorbância no comprimento de onda a 3 pixels, curvas analíticas para Pb (0,1 - 1,0 mg L-1) foram obtidas com coeficientes de correlação típicos > 0,9990. As correlações lineares entre absorbância e concentração de P nos comprimentos de onda 217,0005 e 217,0458 foram > 0,998. O limite de detecção de Pb foi 10 µg L-1. O método de correção proposto forneceu desvios padrão relativos (n=12) de 2,0 a 6,0%, ligeiramente menores que os obtidos sem correção (1,4-4,3%). As recuperações de Pb adicionado às amostras de ácido fosfórico variaram de 97,5 a 100% (com correção pelo método proposto) e de 105 a 230% (sem correção).

Fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines, side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm: 202.585 nm; 202.586 nm: 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min(-1) sample flow-rate, calibration curves in the 0.1-0.5 mg L-1 Cu, 0.5-4.0 mg L-1 Fe, 0.5-4.0 mg L-1 Mn, 0.2-1.0 mg L-1 Zn, 10.0-100.0 mg L-1 Ca, 5.0-40.0 mg L-1 Mg and 50.0-250.0 mg L-1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89-103%, 84-107%, 87-103%, 85-105%, 92-106%, 91-114%, 96-114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L-1 Ca, 0.4 mg L-1 Mg, 0.4 mg L-1 K, 7.7 mu g L-1 Cu, 7.7 mu g L-1 Fe, 1.5 mu g L-1 Mn and 5.9 mu g L-1 Zn. (C) 2009 Elsevier B.V. All rights reserved.

Determination of macro- and micronutrients in plant leaves by high-resolution continuum source flame atomic absorption spectrometry combining instrumental and sample preparation strategies

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

Evaluation of Lubricating Oil Preparation Procedures for the Determination of Al, Ba, Mo, Si and V by High-Resolution Continuum Source FAAS

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

Evaluation of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for direct determination of chromium in medicinal plants

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

Determination of lead in medicinal plants by high-resolution continuum source graphite furnace atomic absorption spectrometry using direct solid sampling

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

Evaluation of alternate lines of Fe for sequential multi-element determination of Cu, Fe, Mn and Zn in soil extracts by high-resolution continuum source flame atomic absorption spectrometry

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

DETERMINATION of SILICON IN LUBRICANT OIL BY HIGH-RESOLUTION CONTINUUM SOURCE FLAME ATOMIC ABSORPTION SPECTROMETRY USING LEAST-SQUARE BACKGROUND CORRECTION and INTERNAL STANDARDIZATION

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

Internal standardization and least-squares background correction in high-resolution continuum source flame atomic absorption spectrometry to eliminate interferences on determination of Pb in phosphoric acid

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