Conformational preferences for some 2-substituted N-methoxy-N-methylacetamides through spectroscopic and theoretical studies

The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH(2)C(O)-N(OMe)Me (Y = F1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c(1), c(2)) and (g(1), g(2)) for 2, and (c) and (g(1), g(2)) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c(1) + c(2)) population prevails over the (g(1) + g(2)) one for 2, and the (g(1) + g(2)) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the nu(CO) region, in n-hexane, precludes the estimative of relative populations of the (c, g(1), g(2)) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the nu(CO) band component relative intensities for 1-3. NBO analysis showed that the n(N) -> pi.(CO), orbital interaction is the main factor which stabilizes the gauche (g, g(1), g(2)) conformers for 1-4 into a larger extent relative to the cis (c, c(1), c(2)) ones. The n(y) -> pi(.)(Co,) sigma(C-Y) -> pi.(CO,) pi(CO) -> sigma(C-Y) and 7co orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Y(delta)-(4)center dot center dot center dot O(delta)-(9) and Y(delta)-(4)center dot center dot center dot N(delta)-(7) short contacts in the gauche (g, g(1), g(2)) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g(1), g(2)) and cis (c, c(1), c(2)) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in a first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides. (C) 2010 Elsevier B.V. All rights reserved.

Pharmacogenetics of Warfarin: Development of a Dosing Algorithm for Brazilian Patients

A dosing algorithm including genetic (VKORC1 and CYP2C9 genotypes) and nongenetic factors (age, weight, therapeutic indication, and cotreatment with amiodarone or simvastatin) explained 51% of the variance in stable weekly warfarin doses in 390 patients attending an anticoagulant clinic in a Brazilian public hospital. The VKORC1 3673G>A genotype was the most important predictor of warfarin dose, with a partial R(2) value of 23.9%. Replacing the VKORC1 3673G>A genotype with VKORC1 diplotype did not increase the algorithm`s predictive power. We suggest that three other single-nucleotide polymorphisms (SNPs) (5808T>G, 6853G>C, and 9041G>A) that are in strong linkage disequilibrium (LD) with 3673G>A would be equally good predictors of the warfarin dose requirement. The algorithm`s predictive power was similar across the self-identified ""race/color"" subsets. ""Race/color"" was not associated with stable warfarin dose in the multiple regression model, although the required warfarin dose was significantly lower (P = 0.006) in white (29 +/- 13 mg/week, n = 196) than in black patients (35 +/- 15 mg/week, n = 76).

The effectiveness of proactive telephone support provided to breastfeeding mothers of preterm infants : study protocol for a randomized controlled trial

Background: Although breast milk has numerous benefits for infants' development, with greater effects in those born preterm (at < 37 gestational weeks), mothers of preterm infants have shorter breastfeeding duration than mothers of term infants. One of the explanations proposed is the difficulties in the transition from a Neonatal Intensive Care Unit (NICU) to the home environment. A person-centred proactive telephone support intervention after discharge from NICU is expected to promote mothers' sense of trust in their own capacity and thereby facilitate breastfeeding. Methods/design: A multicentre randomized controlled trial has been designed to evaluate the effectiveness and cost-effectiveness of person-centred proactive telephone support on breastfeeding outcomes for mothers of preterm infants. Participating mothers will be randomized to either an intervention group or control group. In the intervention group person-centred proactive telephone support will be provided, in which the support team phones the mother daily for up to 14 days after hospital discharge. In the control group, mothers are offered a person-centred reactive support where mothers can phone the breastfeeding support team up to day 14 after hospital discharge. The intervention group will also be offered the same reactive telephone support as the control group. A stratified block randomization will be used; group allocation will be by high or low socioeconomic status and by NICU. Recruitment will be performed continuously until 1116 mothers (I: 558 C: 558) have been included. Primary outcome: proportion of mothers exclusively breastfeeding at eight weeks after discharge. Secondary outcomes: proportion of breastfeeding (exclusive, partial, none and method of feeding), mothers satisfaction with breastfeeding, attachment, stress and quality of life in mothers/partners at eight weeks after hospital discharge and at six months postnatal age. Data will be collected by researchers blind to group allocation for the primary outcome. A qualitative evaluation of experiences of receiving/providing the intervention will also be undertaken with mothers and staff. Discussion: This paper presents the rationale, study design and protocol for a RCT providing person-centred proactive telephone support to mothers of preterm infants. Furthermore, with a health economic evaluation, the cost-effectiveness of the intervention will be assessed. Trial registration: NCT01806480

Estudo da influência da variabilidade em genes de apolipoproteínas sobre níveis lipídicos e parâmetros de massa e gordura corporal na população de Porto Alegre

Apolipoproteínas constituem a parte proteica das lipoproteínas e de uma maneira geral desempenham papéis como proporcionar estabilidade estrutural, solubilizar lipídeos altamente hidrofóbicos, servir como ligantes a receptores ou agir como co-fatores para enzimas envolvidas no metabolismo. Diversos estudos têm mostrado que a variabilidade dos genes que codificam estas proteínas podem influenciar os níveis lipídicos em diversas populações. A variabilidade da apo A-IV também foi associada com variáveis antropométricas. Nesta investigação foram analisados 8 RFLPs nos genes das apolipoproteínas C-I (HpaI), C-II (AvaII), C-III (SacI, FokI e MspI) e A-IV (XbaI, HinfI e PvuII). A amostra foi composta por 391 indivíduos caucasóides de Porto Alegre (RS) e dados sobre hábitos de vida, dosagens lipídicas e medidas antropométricas foram obtidas para cada indivíduo. Os fragmentos de interesse de cada gene foram amplificados por PCR e os genótipos foram identificados por eletroforese em géis de agarose ou poliacrilamida corados com brometo de etídio.

O ambiente socio-econômico como fator preditivo nas chances de classificação no vestibular e no êxito acadêmico na universidade: (um estudo da clientela da Fundação CESGRANRIO, Rio de Janeiro - 1975)

o presente trabalho teve como objetivo estudar a influência que o ambiente sócio-econômico poderia exercer sob re as chances do candidato no vestibular e sobre o êxito acadêmico do universitário. Para tanto re alizaram-se duas pesquisas: uma com os candidatos do vestibular unificado da Fundação CESGRANRIO. do Rio de Ja neira, de 1975: outra, com uma amostra de universitários classificados p~ 10 mesmo vest i bular. O pri meiro estudo abrangeu 75.348 candidatos e o segundo 1.608 universitários, de sete instituições e nove carreiras diferentes. Uti lizou-se como instrumentos de pesquisa: um I questionário de informação sócio-cultural. o total de pontos obtidos pelos candidatos no vestibular e a méd ia das notas obtidas no curso superior p~ lo estudante, nos deis primeiros semestres de 1975. A anãlise dos resultados permitiu concluir o se guinte: - Tiveram maior chance de classificação no vest i bular os candidatos que: cursaram o clássico; f reqüentaram tanto escola / particu lar como oficial; cursaram o período diurno, obtiveram concei to "E~ ce lente" no 2? grau; não trabalhavam; possuíam pai com nível de ins trução superior e renda mensal familiar acima de 8.000 cruzei ros. - Exercem influência na classificação do vestibu lar os seguintes indicadores do amb iente sócio-econôm ico: renda mensal fa miliar, nível de instrução e profissão do pai. ativ idade ocupac ional do / candidato e período da escola de 2? grau. Obtiveram bom rendimento na universidade os estudantes que: freqüentaram o período diurno; obtiveram bom rendimento no 2? grau; não exerciam atividade ocupac ional: possuiam pais com profissão / liberal e renda familiar alta. - São os segu intes os indicadores do ambiente sac io-econôm ico do univers i tário que têm valor preditivo no êxito acadêmico: período da escola de 2? grau, at ividade ocupacional. profissão do pai. ren dimento escolar no 2~ grau e renda mensal fami l iar. Vale assinalar que esses resultados se referem aos candidatos do vestibular unificado da Fundação CESGRANRIO.

Estradas de ferro e ensino industrial: um estudo de caso

O objeto deste estudo e o Centro Ferroviário de Ensino e Seleção Profissional de são Paulo , criado em 1934 , conjuntamente pelas ferrovias paulistas e o governo estadual. A criação deste centro em S~ o Paulo deveu-se ao desenvolvimento das ferrovias no estado , por força das necessidades de expansão da economia cafeeira, a exigi r transportes rápidos, baratos , a longa distância. Concorreu igualmente para o surgimento desta instituição , a difusão em são Paulo da doutrina da Organização Racional do Trabalho, que visava, em termos gerais , o aumento da produtividade da força de trabalho . A aplicação desta doutrina na indústria teve grande êxito , evoluindo com a introdução da Seleção Profissional e das Relações Humanas aplicadas ao trabalho industrial, como maneira de melhor aproveitar o "fator humano" . A divulgação desta doutrina no Brasil , deveu-se à atuação do Instituto de Organização Racional do Trabalho de são Paulo (IOORT ), especialmente pela introdução deste s princípio s no ensino ferroviário . Sua utilização na organização e nos métodos de ensino sobressaísse pela elaboração das séries met6dicas de aprendizagem e aplicação de procedimentos psicotécnicos p~ ra seleção de pessoal, e de candidatos aos curso s profissionais. Inicialmente foram empregados pelo Liceu de Artes e Ofícios de São Paulo, e depois, pela Estrada de Ferro Sorocabana. O Centro Ferroviário de Ensino e Seleção Profissional de são Paulo, durante os 11 anos de seu funcionamento, preparou força de "trabalho especializada para os transportes ferroviários paulistas e de outros estados , mediante a aplicação de métodos de aprendizagem e de aperfeiçoamento técnico-profissional . Esta instituição teve importante papel na origem do SENAI, ao qual foi incorporado, em 1945 , como Divisão de Transportes, fornecendo-lhe quadros de pessoa l técnico, métodos de ensino e ideologia em geral.

Harmonised framework for ecological risk assessment of sediments from ports and estuarine zones of North and South Atlantic

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Development of site-specific sediment quality guidelines for North and South Atlantic littoral zones: Comparison against national and international sediment quality benchmarks

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

O medo da morte e os temores infundados: uma investigação acerca da natureza da alma em Lucrécio.

Lucrèce, penseur latin du siècle I, avant J.C., écrire que le peur de la mort imputé par la religion et la superstition, nourrit le souhait à la richesse, l'ambition du pouvoir et les actes insensés, dont les conséquences se reflètent dans les maladies de l'âme. La terreur qui s'installe chez l'homme, à l'être confronté au décès, est aussi un obstacle à la liberté et à la vie équilibrée. Les craintes sans fondement seulement seraient surmonter, avec la compréhension de la nature et du mouvement de l'âme, en percevant leur génération, corporéité et finitude. Pour cela, la compréhension des atomes et du vide, les éléments primordiaux de la nature se basent tout la connaissance de l'âme. L'objectif de ce travail est enquêter la nature de l'âme dans Lucrèce, en présentant une réflexion sur les craintes sans fondement et la peur de la mort, comme une manière de percevoir le mouvement de la vie elle-même, et de que manière sa philosophie affronte à la crainte de la mort.

Artificial neural networks applied in study of atmospheric parameters to high voltage substations concerning lightning

This gaper demonstrates that artificial neural networks can be used effectively for estimation of parameters related to study of atmospheric conditions to high voltage substations design. Specifically, the neural networks are used to compute the variation of electrical field intensity and critical disruptive voltage in substations taking into account several atmospheric factors, such as pressure, temperature, humidity, so on. Examples of simulation of tests are presented to validate the proposed approach. The results that were obtained by experimental evidences and numerical simulations allowed the verification of the influence of the atmospheric conditions on design of substations concerning lightning.

A modified Hopfield model for solving the N-Queens problem

A neural network model for solving the N-Queens problem is presented in this paper. More specifically, a modified Hopfield network is developed and its internal parameters are computed using the valid-subspace technique. These parameters guarantee the convergence of the network to the equilibrium points. The network is shown to be completely stable and globally convergent to the solutions of the N-Queens problem. Simulation results are presented to validate the proposed approach.

Using neural networks for estimation of aquifer dynamical behavior

The systems of water distribution from groundwater wells can be monitored using the changes observed on its dynamical behavior. In this paper, artificial neural networks are used to estimate the depth of the dynamical water level of groundwater wells in relation to water flow, operation time and rest time. Simulation results are presented to demonstrate the validity of the proposed approach. These results have shown that artificial neural networks can be effectively used for the identification and estimation of parameters related to systems of water distribution.

Influence of semen storage and cryoprotectant on post-thaw viability and fertility of stallion spermatozoa

The aim of the current study was to verify that stallion, spermatoza could be cooled for 24 hours and then frozen. In experiment I, one ejaculate from each of 13 stallions was used. Semen was collected and split into two parts; one part immediately frozen using standard cryo-preservation techniques and the other diluted, stored in an Equitainer for 24 hours, and then frozen. In experiment II, one ejaculate from each of 12 stallions was collected, diluted with Botu-Semen, and split into two parts: one cooled in an Equitainer and the other in Max-Semen Express without prior centrifugation. After 24 hours of cooling, the samples were centrifuged to remove seminal plasma and concentrate the sperm, and resuspended in Botu-Crio (R) extender containing on e of three cryoprotectant treatments (1% glycerol + 4% dimethylformamide, 1% glycerol + 4% dimethylacetamide and 1% glycerol + 4% methylformamide), maintained at 5 degrees C for 20 minutes, then frozen in nitrogen vapour. No difference was observed between the two cooling systems. The association of 1% glycerol and 4% methylformamide provided the best post-thaw progressive motility. For experiment III, two stallions were used for a fertility trial. Forty three inseminations were performed using 22 mares. No differences were seen in semen parameters and pregnancy rates when comparing the two freezing protocols (conventional and cooled/frozen). Pregnancy rates for conventional and cooled/frozen semen were, respectively, 72.7% and 82.3% (stallion A), and 40.0% and 50.0% (stallion B). We concluded that cooling equine-semen for 24 hours before freezing while maintaining sperm viability and fertility is possible.