Chemistry of mixed-ligand methoxy bonded oxidovanadium(V) complexes with a family of hydrazone ligands containing VO3+ core and their substituent controlled methoxy-bridged dimeric forms

[(VO)-O-IV(acac)(2)] reacts with an equimolar amount of benzoyl hydrazones of 2-hydroxyacetophenone (H2L1), 2-hydroxy-5-methylacetophenone (H2L2) and 5-chloro-2-hydroxyacetophenone (H2L4) in methanol to afford the penta-coordinated mixed-ligand methoxy bonded oxidovanadium(V) complexes [(VO)-O-V(L-1)-(OCHA(3))](1). [(VO)-O-V(L-2)(OCH3)](2), and [(VO)-O-V(L-4)(OCH3)](4), respectively, whereas, the similar reaction with the benzoyl hydrazone of 2-hydroxy-5-methoxyacetophenone (H2L3) producing only the hexa-coordinated dimethoxy-bridged dimeric complex [(VO)-O-V(L-3)(OCH3)](2) (3A). Similar type of hexa-coordinated dimeric analogue of 1 i.e., [(VO)-O-V(L-1)(OCH3)](2) (1A) was obtained from the reaction of [(VO)-O-IV(acac)(2)] with the equimolar amount of H2L1 in presence of half equivalent 4,4'-bipyridine in methanol while the decomposition of [(VO)-O-IV(L-2)(bipy)] complex in methanol afforded the dimeric analogue of 2 i.e., [(VO)-O-V(L-2)(OCH3)](2) (2A). All these dimeric complexes 1A-3A react with an excess amount of imidazole in methanol producing the respective monomeric complex. The X-ray structural analysis of 1-3 and their dimeric analogues 1A-3A indicates that the geometry around the vanadium center in the monomeric form is distorted square-pyramidal while that of their respective dimeric forms is distorted octahedral, where the ligands are bonded to vanadium meridionally in their fully deprotonated enol forms. Due to the formation of bridge, the V-O(methoxy) bond in the dimeric complexes is lengthened to such an extent that it becomes equal in length with the V-O(phenolate) bond in 3A and even longer in 1A and 2A, which is unprecedented. The H-1 NMR spectra of the complexes 1A-3A in CDCl3 solution, indicates that these dimeric complexes are converted appreciably into their respective monomeric form. Complexes are electro-active displaying one quasi-reversible reduction peak near +0.25 V versus SCE in CH2Cl2 solution. The E-1/2 values of the complexes show linear relationship with the Hammett parameter (sigma) of the substituents. All these VO3+-complexes are converted to the corresponding complexes with V2O34+ motif simply on refluxing them in acetone and to the complexes with VO2+ motif on reaction with 2 KOH in methanol. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, structure and solution chemistry of a family of dinuclear hydrazonato-vanadium(V) complexes with [OV(mu-O)VO](4+) core

Dinuclear trioxidic [{VOL}(2)mu-O] (1-4) complexes were synthesized from the reaction of [(VO)-O-IV(acac)(2)] with an equimolar amount of H2L [H2L is the general abbreviation of hydrazone ligands (H2L1-4) derived from the condensation of benzoyl hydrazine with either 2-hydroxyacetophenone or its para substituted derivatives] in acetone or CH2Cl2 or acetonitrile. These V2O3L2 complexes were also obtained from the reaction of VOSO4 with H2L in the presence of two equivalents sodium acetate in aqueous-methanolic (50% V/V) medium and also from the decomposition of [(VO)-O-IV(L)(bipy/phen)] complexes in CH2Cl2 Solution. Black monoclinic crystals of 2 and 4 with C2/c space group were obtained from the reaction of [(VO)-O-IV(acac)(2)], respectively, with H2L2 and H2L4 in acetone in which the respective ligands are bonded meridionally to vanadium in their fully deprotonated enol forms. The V-O bond lengths follow the order: V-O(oxo) < V-O(oxo-bridged) < V-O(phenolate) < V-O(enolate). Complexes (1-4) are diamagnetic exhibiting LMCT transition band near 380 nm in CH2Cl2 solution and they are electroactive displaying a quasi-reversible reduction peak in the 0.14-0.30 V versus SCE region. The and the reduction peak potential (E-p(c)) values show linear relationships with the Hammett constant (sigma) of the substituents in the hydrazone ligands. These dinuclear complexes are converted to the corresponding mononuclear cis dioxo complexes K(H2O)(+)[(VO2)-O-V(L)](-) (5-8) and mixed-ligand [(VO)-O-V(L)(hq)] complexes on reaction, respectively, with two equivalents KOH in methanol and two equivalents 8-hydroxyquinoline (Hhq) in CHCl3. Ascorbic acid reduces the dioxovanadium(V) complexes reversibly under aerobic condition. (C) 2008 Elsevier Ltd. All rights reserved.

Religious schools, social values, and economic attitudes: evidence from Bangladesh

This paper uses new data on female graduates of registered secondary secular schools and madrasas from rural Bangladesh and tests whether there exist attitudinal gaps by school type and what teacher-specific factors explain these gaps. Even after controlling for a rich set of individual, family and school traits, we find that madrasa graduates differ on attitudes associated with issues such as working mothers, desired fertility, and higher education for girls, when compared to their secular schooled peers. On the other hand, madrasa education is associated with attitudes that are still conducive to democracy. We also find that exposure to female and younger teacher is associated with more favorable attitudes among graduates.

Patriarchal values : girls are more apt to change

Patriarchal values: girls are more apt to change How has the family value system changed between generations, especially when taking into account the gender dimension? This article presents some results from a study carried outin 2007 in one village of the Gourani tribe where the people are followers of Ahle Hagh in Islamabad Gharb (west of Iran). The differences between generations (those born and raised before and after the Islamic Revolution) in patriarchal values in the family are statistically significant. The older generation opts for the man of the family to make most of the decisions; on children’s education, marriage, naming, the families expenditure, the place for residence, the social network of the family and even the number of children. The younger generation has a different value system and it has moved towards a more egalitarian type of family. With the gender variable included in the findings we see that although the values of the younger male population have evolved toward a less patriarchal decision making structure inthe family, the degree of changes among the young women is much higher. Looking into the preferences for male sex for the first child as well as a larger number of boys in the family, the difference between generations is significant. However data on the differences analyzed with the gender variable proves that the changes concerning the equality of sexes are mainly due to drastic changes in the young women’s value system. That is, the male population, young or old, still prefer to have a boy as their first born and to have more sons in the family. But the young female generation in the rural area sees less difference in having boys or girls in the family. It is concluded that reforms in the old value system is an evolving process of everyday life and that the girls are the main social force for change.

Minimizing inter-genotypic competition effects to predict genetic values and selection in forestry genetic tests

The effect of competition is an important source of variation in breeding experiments. This study aimed to compare the selection of plants of open-pollinated families of Eucalyptus with and without the use of competition covariables. Genetic values were determined for each family and tree and for the traits height, diameter at breast height and timber volume in a randomized block design, resulting in the variance components, genetic parameters, selection gains, effective size and selection coincidence, with and without the use of covariables. Intergenotypic competition is an important factor of environmental variation. The use of competition covariables generally reduces the estimates of variance components and influences genetic gains in the studied traits. Intergenotypic competition biases the selection of open-pollinated eucalypt progenies, and can result in an erroneous choice of superior genotypes; the inclusion of covariables in the model reduces this influence.

Thermal and Rheological Properties of a Family of Botryosphaerans Produced by Botryosphaeria rhodina MAMB-05

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

Phylogenetic relationships within the speciose family Characidae (Teleostei: Ostariophysi: Characiformes) based on multilocus analysis and extensive ingroup sampling

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

A family of stadium-like billiards with parabolic boundaries under scaling analysis

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

Dissipation and its consequences in the scaling exponents for a family of two-dimensional mappings

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Locating invariant tori for a family of two-dimensional Hamiltonian mappings

The location of invariant tori for a two-dimensional Hamiltonian mapping exhibiting mixed phase space is discussed. The phase space of the mapping shows a large chaotic sea surrounding periodic islands and limited by a set of invariant tori. Given the mapping considered is parameterised by an exponent γ in one of the dynamical variables, a connection with the standard mapping near a transition from local to global chaos is used to estimate the position of the invariant tori limiting the size of the chaotic sea for different values of the parameter γ. © 2011 Elsevier B.V. All rights reserved.

Building sustainable values in organizations with the support of human resource management: Evidence from one firm considered as the 'best place to work' in Brazil

Researchers and other professionals unanimously agree that companies should become more sustainable, but this will not happen without the support of human resource management. Paradoxically, there is a lack of information on the support human resource management offers to organizational sustainability applied to real cases. Therefore, this research presents a case study on this topic that was carried out in a leading Brazilian company, which is considered as a model and has been selected as 'the best place to work in the country'. The results provide practical examples of how this family company has been working to guarantee an increasingly sustainable performance with the support of human resources, highlighting the achievements and challenges the company has faced. One of the main results indicates that companies seeking to achieve sustainability need the assistance of the human resource field in order to design a communication system which bridges the gap between practices and sustainable values. © 2012 Management Centre for Human Values.

Scaling invariance of the diffusion coefficient in a family of two-dimensional Hamiltonian mappings

We consider a family of two-dimensional nonlinear area-preserving mappings that generalize the Chirikov standard map and model a variety of periodically forced systems. The action variable diffuses in increments whose phase is controlled by a negative power of the action and hence effectively uncorrelated for small actions, leading to a chaotic sea in phase space. For larger values of the action the phase space is mixed and contains a family of elliptic islands centered on periodic orbits and invariant Kolmogorov-Arnold-Moser (KAM) curves. The transport of particles along the phase space is considered by starting an ensemble of particles with a very low action and letting them evolve in the phase until they reach a certain height h. For chaotic orbits below the periodic islands, the survival probability for the particles to reach h is characterized by an exponential function, well modeled by the solution of the diffusion equation. On the other hand, when h reaches the position of periodic islands, the diffusion slows markedly. We show that the diffusion coefficient is scaling invariant with respect to the control parameter of the mapping when h reaches the position of the lowest KAM island. © 2013 American Physical Society.

Magnetocrystalline interactions and oxidation state determination of Mn(2-x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family

Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2-x)V(1+x)O4 (x=0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2-x)V(1+x)O4 (x=0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution K beta X-ray fluorescence spectra. The ionic models found are Mn22+V4+O4, Mn5/32+V4/33.5+O4 and Mn2+V23+O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques. (c) 2013 Elsevier Inc. All rights reserved.

Prediction of genomic-enabled breeding values and genome-wide association study for feedlot average daily weight gain in Nelore cattle

Pós-graduação em Genética e Melhoramento Animal - FCAV

Self-Organizing Maps of Molecular Descriptors for Sesquiterpene Lactones and Their Application to the Chemotaxonomy of the Asteraceae Family

The Asteraceae, one of the largest families among angiosperms, is chemically characterised by the production of sesquiterpene lactones (SLs). A total of 1,111 SLs, which were extracted from 658 species, 161 genera, 63 subtribes and 15 tribes of Asteraceae, were represented and registered in two dimensions in the SISTEMATX, an in-house software system, and were associated with their botanical sources. The respective 11 block of descriptors: Constitutional, Functional groups, BCUT, Atom-centred, 2D autocorrelations, Topological, Geometrical, RDF, 3D-MoRSE, GETAWAY and WHIM were used as input data to separate the botanical occurrences through self-organising maps. Maps that were generated with each descriptor divided the Asteraceae tribes, with total index values between 66.7% and 83.6%. The analysis of the results shows evident similarities among the Heliantheae, Helenieae and Eupatorieae tribes as well as between the Anthemideae and Inuleae tribes. Those observations are in agreement with systematic classifications that were proposed by Bremer, which use mainly morphological and molecular data, therefore chemical markers partially corroborate with these classifications. The results demonstrate that the atom-centred and RDF descriptors can be used as a tool for taxonomic classification in low hierarchical levels, such as tribes. Descriptors obtained through fragments or by the two-dimensional representation of the SL structures were sufficient to obtain significant results, and better results were not achieved by using descriptors derived from three-dimensional representations of SLs. Such models based on physico-chemical properties can project new design SLs, similar structures from literature or even unreported structures in two-dimensional chemical space. Therefore, the generated SOMs can predict the most probable tribe where a biologically active molecule can be found according Bremer classification.