Nickel(II) complexes of whole set of the simple ethylenediaminetetracarboxylate ligands:DFT study of complexes invoking molecular orbital and configurational analysis

The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.

Molecular analysis of the dengue virus type 1 and 2 in Brazil based on sequences of the genomic envelope-nonstructural protein 1 junction region

The genomic sequences of the Envelope-Non-Structural protein 1 junction region (E/NS1) of 84 DEN-1 and 22 DEN-2 isolates from Brazil were determined. Most of these strains were isolated in the period from 1995 to 2001 in endemic and regions of recent dengue transmission in São Paulo State. Sequence data for DEN-1 and DEN-2 utilized in phylogenetic and split decomposition analyses also include sequences deposited in GenBank from different regions of Brazil and of the world. Phylogenetic analyses were done using both maximum likelihood and Bayesian approaches. Results for both DEN-1 and DEN-2 data are ambiguous, and support for most tree bipartitions are generally poor, suggesting that E/NS1 region does not contain enough information for recovering phylogenetic relationships among DEN-1 and DEN-2 sequences used in this study. The network graph generated in the split decomposition analysis of DEN-1 does not show evidence of grouping sequences according to country, region and clades. While the network for DEN-2 also shows ambiguities among DEN-2 sequences, it suggests that Brazilian sequences may belong to distinct subtypes of genotype III.

Analysis of Forest Effects in Wind Farm Performance

The objective of the thesis is to analyze the behaviour of the wind flow when it is passing beside the forest. To complete this analysis, a parametric study was done based upon generalized situations. Some abacus have been made, which are related to forest and wind characteristics. The abacus were compared with a particular real case, namely Alexandrovo (Bulgaria), where it was concluded that the applicability of the abacus in projects with complex terrain is low and they must be used, from a quantitative point of view, for flat terrain, being hc the most important parameter.

A complete molecular biology assay for hepatitis C virus detection, quantification and genotyping

Introduction Molecular biology procedures to detect, genotype and quantify hepatitis C virus (HCV) RNA in clinical samples have been extensively described. Routine commercial methods for each specific purpose (detection, quantification and genotyping) are also available, all of which are typically based on polymerase chain reaction (PCR) targeting the HCV 5′ untranslated region (5′UTR). This study was performed to develop and validate a complete serial laboratory assay that combines real-time nested reverse transcription-polymerase chain reaction (RT-PCR) and restriction fragment length polymorphism (RFLP) techniques for the complete molecular analysis of HCV (detection, genotyping and viral load) in clinical samples. Methods Published HCV sequences were compared to select specific primers, probe and restriction enzyme sites. An original real-time nested RT-PCR-RFLP assay was then developed and validated to detect, genotype and quantify HCV in plasma samples. Results The real-time nested RT-PCR data were linear and reproducible for HCV analysis in clinical samples. High correlations (> 0.97) were observed between samples with different viral loads and the corresponding read cycle (Ct - Cycle threshold), and this part of the assay had a wide dynamic range of analysis. Additionally, HCV genotypes 1, 2 and 3 were successfully distinguished using the RFLP method. Conclusions A complete serial molecular assay was developed and validated for HCV detection, quantification and genotyping.

Regional income inequalities in Europe: an updated measurement and some decomposition results

In this paper well-known summary inequality indexes are used to explore interregional income inequalities in Europe. In particular, we mainly employ Theils’population-weighted index because of its appealing properties. Two decomposition analysis are applied. First, regional inequalities are decomposed by regional subgroups (countries). Second, intertemporal inequality changes are separated into income and population changes. The main results can be summarized as follows. First, data confirm a reduction in crossregional inequality during 1982-97. Second, this reduction is basically due to real convergence among countries. Third, currently the greater part of European interregional disparities is within-country by nature, which introduce an important challenge for the European policy. Fourth, inequality changes are due mainly to income variations, population changes playing a minor role.

Inequalities in Child Mortality in India: A District-Level Analysis

This paper measures the degree of inequality in child mortality rates across districts in India, using data from the 1981, 1991 and 2001 Indian population censuses. The results show that child mortality is more concentrated in less developed districts in all three census years. Further, between 1981 and 2001, the inequality in child mortality seems to have increased to the advantage of the more developed districts (i.e., there was an increasing concentration of child mortality in less developed districts). However, the inequality in female child mortality rates seems to have declined between 1991 and 2001, even as it increased – albeit at a slower rate than before – for male child mortality rates. In the decomposition analysis, it is found that while a more equitable distribution of medical facilities and safe drinking water across districts did contribute towards reducing inequality in child mortality between 1981 and 1991, different levels of structural change among districts were responsible for a very large part of the inequality in child mortality to the advantage of the more developed districts in all three census years. Other variables which played important roles in increasing inequality included a measure of infrastructure development, female literacy, and a social group status variable. The paper concludes with some brief comments on the policy implications of the findings.

Allowing for heterogeneity in the decomposition of measures of inequality in health

This paper shows how recently developed regression-based methods for the decomposition ofhealth inequality can be extended to incorporate heterogeneity in the responses of health to the explanatory variables. We illustrate our method with an application to the GHQ measure of psychological well-being taken from the British Household Panel Survey. The results suggest that there is an important degree of heterogeneity in the association of health to explanatory variables across birth cohorts and genders which, in turn, accounts for a substantial percentage of the inequality in observed health.

Analysis of matched matrices

We consider the joint visualization of two matrices which have common rowsand columns, for example multivariate data observed at two time pointsor split accord-ing to a dichotomous variable. Methods of interest includeprincipal components analysis for interval-scaled data, or correspondenceanalysis for frequency data or ratio-scaled variables on commensuratescales. A simple result in matrix algebra shows that by setting up thematrices in a particular block format, matrix sum and difference componentscan be visualized. The case when we have more than two matrices is alsodiscussed and the methodology is applied to data from the InternationalSocial Survey Program.

Glycogen phosphorylase inhibitors: a free energy perturbation analysis of glucopyranose spirohydantoin analogues

GP catalyzes the phosphorylation of glycogen to Glc-1-P. Because of its fundamental role in the metabolism of glycogen, GP has been the target for a systematic structure-assisted design of inhibitory compounds, which could be of value in the therapeutic treatment of type 2 diabetes mellitus. The most potent catalytic-site inhibitor of GP identified to date is spirohydantoin of glucopyranose (hydan). In this work, we employ MD free energy simulations to calculate the relative binding affinities for GP of hydan and two spirohydantoin analogues, methyl-hydan and n-hydan, in which a hydrogen atom is replaced by a methyl- or amino group, respectively. The results are compared with the experimental relative affinities of these ligands, estimated by kinetic measurements of the ligand inhibition constants. The calculated binding affinity for methyl-hydan (relative to hydan) is 3.75 +/- 1.4 kcal/mol, in excellent agreement with the experimental value (3.6 +/- 0.2 kcal/mol). For n-hydan, the calculated value is 1.0 +/- 1.1 kcal/mol, somewhat smaller than the experimental result (2.3 +/- 0.1 kcal/mol). A free energy decomposition analysis shows that hydan makes optimum interactions with protein residues and specific water molecules in the catalytic site. In the other two ligands, structural perturbations of the active site by the additional methyl- or amino group reduce the corresponding binding affinities. The computed binding free energies are sensitive to the preference of a specific water molecule for two well-defined positions in the catalytic site. The behavior of this water is analyzed in detail, and the free energy profile for the translocation of the water between the two positions is evaluated. The results provide insights into the role of water molecules in modulating ligand binding affinities. A comparison of the interactions between a set of ligands and their surrounding groups in X-ray structures is often used in the interpretation of binding free energy differences and in guiding the design of new ligands. For the systems in this work, such an approach fails to estimate the order of relative binding strengths, in contrast to the rigorous free energy treatment.

Self-adjoint extensions and spectral analysis in the Calogero problem

In this paper, we present a mathematically rigorous quantum-mechanical treatment of a one-dimensional motion of a particle in the Calogero potential alpha x(-2). Although the problem is quite old and well studied, we believe that our consideration based on a uniform approach to constructing a correct quantum-mechanical description for systems with singular potentials and/or boundaries, proposed in our previous works, adds some new points to its solution. To demonstrate that a consideration of the Calogero problem requires mathematical accuracy, we discuss some `paradoxes` inherent in the `naive` quantum-mechanical treatment. Using a self-adjoint extension method, we construct and study all possible self-adjoint operators (self-adjoint Hamiltonians) associated with a formal differential expression for the Calogero Hamiltonian. In particular, we discuss a spontaneous scale-symmetry breaking associated with self-adjoint extensions. A complete spectral analysis of all self-adjoint Hamiltonians is presented.

UV optical absorption spectra analysis of beryl crystals from Brazil

The spectral decomposition analysis was applied to the optical absorption spectra of green and colorless beryl crystals from the Brazilian Eastern Pegmatitic province in the natural state, Submitted to heat treatment and irradiated with UV light The attributions of the lines were made taking into account highly accurate quantum mechanical calculations The deconvolution of the green beryl spectra revealed four lines, two of them around 12,000 cm(-1) (1 5eV) and two of them around 34,000 cm(-1) (4.2 eV) attributed to Fe(2+) and Fe(3+), respectively The deconvolution of the colorless beryl spectra without any treatment, after heating and for the same heat treatment followed by UV light irradiation revealed five lines The analysis of ratio relations showed that the lines at 36,400 cm(-1) (4.5 eV) and 41,400 cm(-1) (5 1 eV) belongs to a single defect attributed to a silicon dangling bond defect (=Si). Discussions and comparison with reported defects in quartz have supported the allocation of the lines at 61,000 cm(-1) (7.6 eV) and 43,800 cm(-1) (5 4 eV) to diamagnetic oxygen vacancy defect ( Si-Si ) and unrelaxed ( Si Si ) defect, respectively Finally, the line at 39.100 cm(-1) (4.8 eV), quite polarized along the c-axis, was attributed to a (Fe(2+) OH(-)) defect in the structural channels (C) 2009 Elsevier B V All rights reserved

Study of the phenanthroline-Mn-imidazole bonding in Mn(I) triscarbonyl complex: A X-ray and DFT computational analysis

355 nm light irradiation of fac-[Mn(CO)(3)(phen)(imH)](+) (fac-1) produces the mer-1 isomer and a long lived radical which can be efficiently trapped by electron acceptor molecules. EPR experiments shows that when excited, the manganese(I) complex can be readily oxidized by one-electron process to produce Mn(II) and phen(.-). In the present study, DFT calculations have been used to investigated the photochemical isomerization of the parent Mn(I) complex and to characterize the electronic structures of the long lived radical. The theoretical calculations have been performed on both the fac-1 and mer-1 species as well as on their one electron oxidized species fac-1+ and mer-1+ for the lowest spin configurations (S = 1/2) and fac-6 and mer-6 (S = 5/2) for the highest one to characterize these complexes. In particular, we used a charge decomposition analysis (CDA) and a natural bonding orbital (NBO) to have a better understanding of the chemical bonding in terms of the nature of electronic interactions. The observed variations in geometry and bond energies with an increasing oxidation state in the central metal ion are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The X-ray structure of fac-1 is also described. (C) 2011 Elsevier B.V. All rights reserved.

Síntese e Caracterização de Titanatos de Cobalto e Níquel, dopados com Praseodímio, obtidos a partir da decomposição de Nitrilotriacetatos

In recent years, studies about the physicochemical properties of mixed oxides, call attention of the scientific community, properties like as piezoelectricity, photoluminescence, or applications as catalysts, arise in these compounds, when their chemical compositions are modified, in this context some routes are employed in the synthesis of these materials, among which can be cited these methods: ceramic, combustion, co-precipitation, Pechini or polymeric precursor method, hydrothermal, sol-gel; these routes are divided into traditional routes or chemical routes. In this work were synthesized oxides with variable composition, from the thermal decomposition of titanium, cobalt, nickel and praseodymium nitrilotriacetates. The nitrilotriacetates were characterized by IR Spectroscopy (FTIR), Thermogravimetric (TG/ DTG) and Differential Scanning Calorimetry (DSC), while oxides have been characterized by X-ray diffraction (XRD), Spectrofluorimetry and IR Spectroscopy (FTIR). From FTIR data, it was demonstrated that the displacement of the band corresponding to the carboxylate group (νCOOH) at 1712 cm-1, present in nitrilotriacetic acid (H3NTA), for 1680-1545 cm-1, these stretches are characteristics of coordinated nitrilotriacetates, By thermal analysis (TG/DTG /DSC), it was suggested, that in an oxidizing atmosphere (air) oxides are obtained at lower temperatures than in an inert atmosphere N2(g). By results from X-ray Diffraction (XRD), it was determinated that the oxides are crystalline and the predominant phases obtained are summarized titanate phases rutile and ilmenite. By fluorimetry was observed that the intensity of emission bands are directly proportional to the concentration of ions Ni2+, Co2+ and Pr3+, and IR spectroscopy (FTIR) from oxides, demonstrated the disappearance of characteristic bands by nitrilotriacetates, determining the complete decomposition of the nitrilotriacetates in oxides

DECOMPOSITION RATES OF SPENT FUNGAL REFUSE OF ATTA-SEXDENS (HYMENOPTERA, FORMICIDAE) AND IMPLICATIONS FOR ESTIMATING FORAGE INTAKE BY LEAF-CUTTING ANTS

Using simulated ceramic refuse chambers, field decomposition studies were performed on the spent fungal refuse of the lead-cutting ant Atta sexdens rubropilosa. Refuse half life was estimated at 40 days, with complete decomposition at 100 days. These results suggest that the conversion-factor method used to estimate forage input into leaf-cutting ant colonies must be corrected for decomposition, or serious estimation errors will occur.

The use of Gramian matrices for aeroelastic stability analysis

Most of the established procedures for analysis of aeroelastic flutter in the development of aircraft are based on frequency domain methods. Proposing new methodologies in this field is always a challenge, because the new methods need to be validated by many experimental procedures. With the interest for new flight control systems and nonlinear behavior of aeroelastic structures, other strategies may be necessary to complete the analysis of such systems. If the aeroelastic model can be written in time domain, using state-space formulation, for instance, then many of the tools used in stability analysis of dynamic systems may be used to help providing an insight into the aeroelastic phenomenon. In this respect, this paper presents a discussion on the use of Gramian matrices to determine conditions of aeroelastic flutter. The main goal of this work is to introduce how observability gramian matrix can be used to identify the system instability. To explain the approach, the theory is outlined and simulations are carried out on two benchmark problems. Results are compared with classical methods to validate the approach and a reduction of computational time is obtained for the second example. © 2013 Douglas Domingues Bueno et al.