Solvatochromic and lonochromic Effects of Iron(II)bis-(1,10-phenanthroline)dicyano: a Theoretical Study

Solvatochromic and ionochromic effects of the iron(II)bis(1,10-phenanthroline)dicyano (Fe(phen)(2)(CN)(2)) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)(2)(CN)(2) in acetonitrile and aqueous solution, as well as including interaction with Mg(2+), were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg(2+), and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro- and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid Fe(II)(d)/cyano N(p) orbital to a phenanthroline pi* orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)(2)(CN)(2) were explained with preferential stabilization of the highest occupied Fe(II)(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg(2+) ions in solution. Such interactions occur through the CN(-) groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylsulfonyl]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenyisulfonyI]propanamides Y-PhSO(2)CH(Me)C(O)N(OMe)Me (Y = OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by HF/6-31G(d,p) calculations of 3,, indicated the existence of two gauche conformers (g(1) and g(2)), the g, conformer being the most stable and the least polar one (in gas phase and in solution). Both conformers are present in solution of the non polar solvent (CCl(4)) for 1-5 and in solution of the more polar solvents (CHCl(3)) for 1. 4, 5 and (CH(2)Cl(2)) for 5, while only the g(1) conformer is present in solution of the most polar solvent (CH(3)CN) for 1-5. The g, and g2 conformers correspond to the enantiomeric pairs of diastereomers (diast(1) and diast(2)) whose relative configurations are [C(3)(R)N(R)]/[C(3)(s)N(s)] and [C(3)(R)N(s)]/[C(3)(s)N(R)], respectively. The computed carbonyl frequencies for g(1) (diast(1)) and g(2) (diast(2)) stereoisomers of3 match well the experimental values. The NBO analysis, for 3 shows the important role of the orbital interactions in conformer stabilization and the overall balance of these interactions corroborates that the g, conformer is more stable than the 92 one. The observed abnormal solvent effect on the relative intensities of the carbonyl doublet components is attributed to the molecular crowding in the g2 conformer which hinders its solvation in comparison to the g, conformer (diast(1)). X-ray single crystal analysis performed for 3 shows the existence Of two 92, and g(1b) conformers of diastereomers (diast2, and diast(1b)) whose absolute configurations are [C(3)(R)N(s)] and [C(3)(R)N(R)], respectively. The larger population and. thus, the larger stabilization of the g(2), conformer over the gib form in the crystals may be associated with a larger energy gain deriving from dipole moment coupling in the former conformer along with a series of C-H center dot center dot center dot O electrostatic and hydrogen bond interactions, (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylthio]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH(2)Cl(2) and CH(3)CN) for 1-5 and in solution of the less polar solvent (CHCl(3)) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C(6)H(14) and CCl(4)) and in solution of CHCl(3) for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LP(O2) -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O([CO])(delta-) center dot center dot center dot H([O-Ph])(delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LP(O22) -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O([OMe])(delta-) center dot center dot center dot H([o`-Ph])(delta+) electrostatic static interaction. As for the 4`-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl(3) solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solution. (C) 2008 Elsevier B.V. All rights reserved.

Conciliação: a solução da lide e a celeridade na prestação jurisdicional

Esta obra tem como tema central a conciliação como método contemporâneo de solução dos conflitos, notadamente nas Varas de Família de Porto Velho/RO. Os métodos alternativos de solução de controvérsias surgem como opção eficaz ao jurisdicionado, em atenção ao clamor da sociedade por uma prestação jurisdicional mais célere. A utilização deste método visa oferecer e assegurar uma melhor e efetiva solução de conflitos à população, fugindo assim dos modelos tradicionais de resoluções de conflitos. O objetivo é procurar demonstrar que, além da jurisdição estatal, existem outros meios de pacificação social, os quais também colocam fim às controvérsias e realizam a justiça. Destaque-se que mecanismos alternativos objetivam não somente oferecer uma prestação jurisdicional mais célere à sociedade, mas também verdadeira pacificação social; além do que, oportunizam também a resolução do conflito antes que seja instaurada qualquer demanda judicial, desafogando assim o Judiciário. Enfatiza-se a importância da conciliação nas matérias concernentes ao direito de família, já que nesta área há preocupação fundamental com a preservação emocional das partes. E dada a carga emocional que circundam as ações dessa natureza, muitas vezes ao juiz é impossível encontrar uma resposta adequada e definitiva para os problemas que lhes são apresentados pelas partes. Os resultados demonstram que a conciliação nas Varas de Família de Porto Velho/RO têm se revelado um mecanismo célere e eficaz, na busca da resolução de conflitos e pacificação social. Os profissionais e operadores do direito têm consciência da importância de sua aplicação.

Sacredness of the constitutional text and interpretative heresy: the Brazilian Supreme Court decision on same-sex civil unions

The paper provides a close lecture of the arguments and methods of legal construction, employed in the extensive individual opinions written by the Justices of the Brazilian Supreme Court in the case which authorized the same sex civil union. After tracing an outline of the legal problem and his possible solutions, we analyze the individual opinions, showing their methodological syncretism, the use of legal methods and arguments in a contradictory way as well the deficiencies in the reasoning. The Justices use legal arguments, but do not meet the requirements of rationality in the decision-making. We have a rhetorical attempt that aims to satisfy the public opinion than to offer a comprehensive and coherent solution according the normative elements of the Brazilian Federal Constitution of 1988.

Human growth, biological maturation, motor performance and contextual factors in Madeira children

The central aims of this study were: (1) to construct age- and gender-specific percentiles for motor coordination (MC), (2) to analyze the change, stability, and prediction of MC, (3) to investigate the relationship between motor performance and body fatness, and (4) to evaluate the relationships between skeletal maturation and fundamental motor skills (FMS) and MC. The data collected was from the ‘Healthy Growth of Madeira Children Study’ and from the ‘Madeira Child Growth Study’. In these studies, MC, FMS, skeletal age, growth characteristics, motor performance, physical activity, socioeconomic status, and geographical area were assessed/measured. Generalized additive models for location, scale and shape, mixed between-within subjects ANOVA, multilevel models, and hierarchical regression (blocks) were some of the statistical procedures used in the analyses. Scores on walking backwards and moving sideways improved with age. It was also found that boys performed better than girls on moving sideways. Normal-weight children outperformed obese peers in almost all gross MC tests. Inter-age correlations were calculated to be between 0.15 and 0.60. Age was associated with a better performance in catching, scramble, speed run, standing long jump, balance, and tennis ball throwing. Body mass index was positively associated with scramble and speed run, and negatively related to the standing long jump. Physical activity was negatively associated with scramble. Semi-urban children displayed better catching skills relative to their urban peers. The standardized residual of skeletal age on chronological age (SAsr) and its interaction with stature and/or body mass accounted for the maximum of 7.0% of variance in FMS and MC over that attributed to body size per se. SAsr alone accounted for a maximum of 9.0% variance in FMS and MC over that attributed to body size per se and interactions between SAsr and body size. This study demonstrates the need to promote FMS, MC, motor performance, and physical activity in children.

A new and improved strategy combining a dispersive-solid phase extraction-based multiclass method with ultra high pressure liquid chromatography for analysis of low molecular weight polyphenols in vegetables

This paper reports on the development and optimization of a modified Quick, Easy, Cheap Effective, Rugged and Safe (QuEChERS) based extraction technique coupled with a clean-up dispersive-solid phase extraction (dSPE) as a new, reliable and powerful strategy to enhance the extraction efficiency of free low molecular-weight polyphenols in selected species of dietary vegetables. The process involves two simple steps. First, the homogenized samples are extracted and partitioned using an organic solvent and salt solution. Then, the supernatant is further extracted and cleaned using a dSPE technique. Final clear extracts of vegetables were concentrated under vacuum to near dryness and taken up into initial mobile phase (0.1% formic acid and 20% methanol). The separation and quantification of free low molecular weight polyphenols from the vegetable extracts was achieved by ultrahigh pressure liquid chromatography (UHPLC) equipped with a phodiode array (PDA) detection system and a Trifunctional High Strength Silica capillary analytical column (HSS T3), specially designed for polar compounds. The performance of the method was assessed by studying the selectivity, linear dynamic range, the limit of detection (LOD) and limit of quantification (LOQ), precision, trueness, and matrix effects. The validation parameters of the method showed satisfactory figures of merit. Good linearity (View the MathML sourceRvalues2>0.954; (+)-catechin in carrot samples) was achieved at the studied concentration range. Reproducibility was better than 3%. Consistent recoveries of polyphenols ranging from 78.4 to 99.9% were observed when all target vegetable samples were spiked at two concentration levels, with relative standard deviations (RSDs, n = 5) lower than 2.9%. The LODs and the LOQs ranged from 0.005 μg mL−1 (trans-resveratrol, carrot) to 0.62 μg mL−1 (syringic acid, garlic) and from 0.016 μg mL−1 (trans-resveratrol, carrot) to 0.87 μg mL−1 ((+)-catechin, carrot) depending on the compound. The method was applied for studying the occurrence of free low molecular weight polyphenols in eight selected dietary vegetables (broccoli, tomato, carrot, garlic, onion, red pepper, green pepper and beetroot), providing a valuable and promising tool for food quality evaluation.

OVARIAN HISTOLOGY and FOLLICULAR SCORE IN FEMALE RATS TREATED WITH NANDROLONE DECANOATE and SUBMITTED TO PHYSICAL EFFORT

The study was conducted to analyze the histology of the ovaries of adults rats treated with steroids, and submitted or not to physical effort. The control group consisted of females submitted to physical effort and sedentary females, both of which received a physiological solution of 0.9% saline. Treated females, sedentary or not, received 6 mg/kg of body weight of nandrolone decanoate. The steroid and physiological solution were administered intraperitoneally, with a single injection per week for 4 consecutive weeks. The applied physical effort was swimming (20 minutes daily, 5 days/week, for the 4 weeks of treatment). Serial sections (5 mu m) of ovaries were prepared for histological evaluation and follicular score. The weight of ovaries and hypophysis, the number of antral and atretic follicles, and the area of corpus luteum were all affected by the steroids. In the ovaries of the control groups, well-developed corpus luteum was observed. In the treated groups, the cortical stroma was occupied by ovarian interstitial tissue. The females treated with steroids presented estral acyclicity. The use of nandrolone decanoate, whether associated with physical effort or not, affected the morphological pattern of the ovaries.

The influence of ripening stage and cultivation system on the total antioxidant activity and total phenolic compounds of yellow passion fruit pulp

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

As práticas exitosas de leitura no ensino fundamental: vozes sociais de professores e de estudantes

The school is the social place which should provide the formation of critical readers. In this context, the role of the teacher is crucial when it comes to teaching reading. Thus, this doctoral research aims to explicit the reading practices evidenced from social voices of teachers and Fundamental School students from state public schools at RN that have successful results, according to IDEB 2009. Moreover, we seek to explicit, through the positions of teachers, the conceptions of reading underlying their reading activities, as well as elucidate the social voices related to teaching of reading that are present in the National Curriculum Guide for 9 years Fundamental School and in the Political-Pedagogical Projects of the educational institutions investigated. In order to accomplish this goal, we carried out observations in the classroom, applied questionnaires with teachers and students in the 9th grade of Fundamental School, in classes of Portuguese Language, and also performed dialogical meetings with the management and pedagogics schools teams. The theoretical foundation that guides the research comes from bakhtinian thinking (2009, 2010), which addresses the dialogical perspective of language and active responsive comprehension. Furthermore, this work is anchored in theoretical reflections of Antunes (2005, 2009) and Geraldi (2003, 2006, 2010) about the reading and writing in the country, which contribute to the resizing of the teaching and learning process of Portuguese Language. This study belongs to the field of Applied Linguistics, which investigates language as social practice in the context of learning mother language or in contexts where relevant questions about the use of language are evidenced. The parameters of qualitative research in a social-historic perspective are adopted seeking to understand the school context by the subjects involved in research. The research corpus is composed of: (i) information constructed through the use of questionnaires with teachers and students; (ii) information constructed from the observed lesson and dialogue with management and pedagogical teams; (iii) a set of selected information, i.e., empiricism built through documentary analysis of the National Curriculum Guide for 9 years Fundamental School (CONSELHO NACIONAL DE EDUCAÇÃO, 2010) and the Political- Pedagogical Projects of the investigated schools. The analysis of the sayings of teachers and students suggest reading practices from various texts, in particular, from the literary sphere, in activities involving discussions, reading and reading comprehension exercises, interviews, songs, seminars organizations, concerts, dramatizations, literary weeks, among other practices. Furthermore, these analyses reveal that teach Portuguese Language requires commitment, responsibility and satisfaction, as well as more grounded theoretical principles, which make teaching practice more efficient. The research also reveals that the success of the teaching-learning process occurs by virtue of the involvement of school s segments in the educational process, creating therefore a network of responsibilities. In this sense, this research may contribute to the production of knowledge that can guide and enrich the teaching and learning of reading, envisioning a pedagogical practice constructed from the relationship with the other, i.e., from the dialogism which provides formation of young people that exercise their citizenship

Adsorption and detection of DNA dendrimers at carbon electrodes

Dendritic nucleic acids are highly branched and ordered molecular structures, possessing numerous single-stranded oligonucleotide arms, which hold great promise for enhancing the sensitivity of DNA biosensors. This article evaluates the interfacial behavior and redox activity of nucleic acid dendrimers at carbon paste electrodes, in comparison to DNA. Factors influencing the adsorption behavior, including the adsorption potential and time, solution conditions, or dendrimer concentration, are explored. The strong adsorption at the anodically pretreated carbon surface is exploited for an effective preconcentration step prior to the chronopotentiometric measurement of the surface species. Coupled with the numerous guanine oxidation sites, such stripping protocol offers remarkably low detection limits (e.g., 3 pM or 2.4 femtomole of the I-layer dendrimer following a 15 min accumulation). The new observations bear important implications upon future biosensing applications of nucleic dendrimers.

Evaluation of hybrid models for static and multistage transmission system planning

Neste trabalho é analisada a aplicação de algoritmos heurísticos para o Modelo Híbrido Linear - Hybrid Linear Model (HLM) - no problema de planejamento da expansão de sistemas de transmissão. O HLM é um modelo relaxado que ainda não foi suficientemente explorado. Assim, é realizada uma análise das características do modelo matemático e das técnicas de solução que podem ser usadas para resolver este tipo de modelo. O trabalho analisa em detalhes um algoritmo heurístico construtivo para o HLM e faz uma extensão da modelagem e da técnica de solução para o planejamento multi-estágio da expansão de sistemas de transmissão. Dentro deste contexto, também é realizada uma avaliação da qualidade das soluções encontradas pelo HLM e as possibilidades de aplicação deste modelo em planejamento de sistemas de transmissão. Finalmente, são apresentados testes com sistemas conhecidos na literatura especializada.

Adequação da metodologia do teste de envelhecimento acelerado em sementes de rúcula

The use of high vigor seed constitutes basic and fundamental. Given the increasing development os the seeds industry and the improvement of vigor tests used to differentiate subtle variations in the quality of seeds of vegetable crops, is needed. The objective was to study variations in conducting the accelerated aging test, to verify their sensitivity for identifying different vigor levels of arugula seed. Were used the cultivars Cultivada and Gigante, using five lots of seeds for each. The seeds were subjected to the determination of water content, germination, first germination, emergence of seedlings and variations in the accelerated aging test, without salt solution ( traditional procedure) and with salt solution in 48, 72 and 96 hours; at 38 degrees C, 41 degrees C and 45 degrees C. The accelerated aging test in traditional procedure is not efficient to evaluation the vigor of arugula seeds. The accelerated aging test with saline solution using the combination 41 degrees C for 72 hours, was sensitive to evaluated of the physiological potential of arugula seeds.

Influence of Pigment and Opacifier on Dimensional Stability and Detail Reproduction of Maxillofacial Silicone Elastomer

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

Silver Distribution and Release from an Antimicrobial Denture Base Resin Containing Silver Colloidal Nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)