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.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Stereochemical and electronic interaction studies of some N-methoxy-N-methyl-2-[(4 `-substituted)phenylsulfinyl]propanamides

The (1)H NMR spectra of N-methoxy-N-methyl-2-[(4`-substituted)phenylsulfinyl]-propanamides [Y-Ph-S(O)CH(Me)C(O)N(OMe)Me; Y = OMe 1, Me 2, H 3. Cl 4, NO(2) 5] along with the X-ray diffraction analysis of the nitro-derivative (5). have shown the existence of two pairs of diastereomers (racemic mixture) [C(R)S(S)/C(S)S(R) (diast(1)) and C(R)S(R)/C(S)S(S) (diast(2))] in the ratio of ca. 7:3. respectively. The v(CO) IR analysis of the title compounds supported by HF and B3LYP/6-31G** calculations of 3 and of the parent N-methoxy-N-methyl-propanamide (6) by HF, have shown that diast(1) exists in an equilibrium between the two more polar and more stable quasi-cis (q-c(1) and q-c(2)) conformers and the gauche(g) conformer. The population of the g conformer in the equilibrium increases with the increase in the solvent polarity, which is attributed to a larger solvation effect on the carbonyl and sulfinyl groups. Diast(2) of compound 3 occurs in the gas phase as an equilibrium between the most stable quasi-gauche (q-g) conformer and the quasi-cis (q-c) conformer, both presenting very similar dipole moments. The former is stabilized by electrostatic and charge transfer interactions, which results in a less solvated spatial arrangement. Moreover, all conformers of both diastereomers are stabilized by several intramolecular hydrogen bonds. X-ray single crystal analysis performed for diast(1) and for diast(2) of 5 indicates that both stereoisomers assume, in the solid state, the anti-clinal (gauche) conformation. For the crystal packing, diast(1) of 5 is made up of three molecules joined through two centro-symmetric H center dot center dot center dot O hydrogen bonds. (C) 2008 Elsevier B.V. All rights reserved.

Effect Of Different Hydrological Model Structures On The Assimilation Of Distributed Uncertain Observations

The reliable evaluation of the flood forecasting is a crucial problem for assessing flood risk and consequent damages. Different hydrological models (distributed, semi-distributed or lumped) have been proposed in order to deal with this issue. The choice of the proper model structure has been investigated by many authors and it is one of the main sources of uncertainty for a correct evaluation of the outflow hydrograph. In addition, the recent increasing of data availability makes possible to update hydrological models as response of real-time observations. For these reasons, the aim of this work it is to evaluate the effect of different structure of a semi-distributed hydrological model in the assimilation of distributed uncertain discharge observations. The study was applied to the Bacchiglione catchment, located in Italy. The first methodological step was to divide the basin in different sub-basins according to topographic characteristics. Secondly, two different structures of the semi-distributed hydrological model were implemented in order to estimate the outflow hydrograph. Then, synthetic observations of uncertain value of discharge were generated, as a function of the observed and simulated value of flow at the basin outlet, and assimilated in the semi-distributed models using a Kalman Filter. Finally, different spatial patterns of sensors location were assumed to update the model state as response of the uncertain discharge observations. The results of this work pointed out that, overall, the assimilation of uncertain observations can improve the hydrologic model performance. In particular, it was found that the model structure is an important factor, of difficult characterization, since can induce different forecasts in terms of outflow discharge. This study is partly supported by the FP7 EU Project WeSenseIt.

O problema da liberdade no primeiro livro dos discorsi de Maquiavel

A pesquisa pretende analisar e contextualizar o problema da liberdade cívica no Primeiro Livro dos Discorsi de Maquiavel. A análise será histórico-político-filosófica do ideário da liberdade, construída pelos humanistas cívicos florentinos, entre os séculos XIV e XV, e criticado e realizado teoricamente por Maquiavel pelo viés do republicanismo. O que está em questão é a herança do conceito de libertà e sua confluência contemporâmea na obra do pensador florentino.

Eficiência em serviço de IT terceirizados : o caso CPR/IBM

Alegando razões de eficiência, muitas firmas vêm crescentemente adotando a terceirização de TI como um meio de conseguir economia de custos, maior foco em suas operações e alinhamento estratégico. Não obstante as razões verbalmente alegadas pelas empresas para terceirizar serviços de TI todas elas buscam a prestação de serviço em TI como uma forma de transferir a eficiência da prestadora de serviços para a empresa cliente. Com a competitividade cada vez maior entre as prestadoras de serviço e por mais que as empresas prestadoras de serviço tentem diferenciar-se entre si, o fato é que não existem muitas diferenças que possam saltar a vista entre os grandes prestadores de serviço de terceirização de TI atuais, pois fornecem de forma quase que indiferente custo, qualidade, expertise técnica, métodos e processos, experiência comprovada, boa saúde financeira, presença global. Mas porque alguns provedores de serviço de TI conseguem ser mais eficiente que seus clientes? Porque os departamentos de TI, das empresas clientes, têm dificuldade de copiar o modelo destes fornecedores e operar com os mesmos patamares de eficiência? Quais as dificuldades e barreiras que existem? Quais as melhores práticas adotadas pela provedora de serviço e pelo cliente para realizar uma terceirização de serviços de TI com sucesso? Este trabalho analisa em caráter exploratório, através de um estudo de caso, a terceirização de TI feita pela CPR (Canadian Pacific Railroad) em 2003 junto à IBM Canadá, aonde seu custo contratual teve uma redução de cerca de 20% do custo original de operação da CPR , buscando identificar porque que algumas empresas prestadoras de serviço de TI conseguem ser mais eficiente que seus clientes, porque não se optou em realizar a transformação internamente e quais as melhores práticas adotadas pela provedora de serviço para realizar uma terceirização de serviços de TI com sucesso. Para isto, o trabalho parte da literatura para indicar possíveis fatores motivadores para a terceirização assim como as melhores práticas de gestão utilizadas atualmente pelas prestadoras de serviço e empresas clientes para uma terceirização de serviços de TI. Posteriormente segue para uma etapa de campo, em busca de elementos que permitam a análise de sua relevância. Os fundamentos teóricos para a terceirização se basearam na: Teoria de Custos de Transação (TCT -Transaction Cost Theory) e na Teoria Baseada em Recursos (RBT-Resource Base Theory). Na etapa de campo explorou-se um projeto de terceirização de infra-estrutura de TI entre a IBM e CPR (Canadian Pacific Railroad), aonde foram feitas entrevistas estruturadas com os gestores do cliente CPR, gestores da prestadora de serviços IBM, assim como analisados materiais produzidos pelo projeto, com o objetivo de identificar porque algumas empresas prestadoras de serviço de TI conseguem ser mais eficiente que seus clientes. Os resultados encontrados apontam que a CPR possuía uma menor eficiência do que a IBM por razões: de foco, de processo e de escala. Tais características são em si não facilmente imitáveis pela empresa cliente tornando a parceria estratégica a melhor solução para o aumento de eficiência operacional na empresa cliente.

Estudo in silico da interação da albumina de soro humano com o ibuprofeno

Currently, computational methods have been increasingly used to aid in the characterization of molecular biological systems, especially when they relevant to human health. Ibuprofen is a nonsteroidal antiinflammatory or broadband use in the clinic. Once in the bloodstream, most of ibuprofen is linked to human serum albumin, the major protein of blood plasma, decreasing its bioavailability and requiring larger doses to produce its antiinflamatory action. This study aimes to characterize, through the interaction energy, how is the binding of ibuprofen to albumin and to establish what are the main amino acids and molecular interactions involved in the process. For this purpouse, it was conducted an in silico study, by using quantum mechanical calculations based on Density Functional Theory (DFT), with Generalized Gradient approximation (GGA) to describe the effects of exchange and correlation. The interaction energy of each amino acid belonging to the binding site to the ligand was calculated the using the method of molecular fragmentation with conjugated caps (MFCC). Besides energy, we calculated the distances, types of molecular interactions and atomic groups involved. The theoretical models used were satisfactory and show a more accurate description when the dielectric constant ε = 40 was used. The findings corroborate the literature in which the Sudlow site I (I-FA3) is the primary binding site and the site I-FA6 as secondary site. However, it differs in identifying the most important amino acids, which by interaction energy, in order of decreasing energy, are: Arg410, Lys414, Ser 489, Leu453 and Tyr411 to the I-Site FA3 and Leu481, Ser480, Lys351, Val482 and Arg209 to the site I-FA6. The quantification of interaction energy and description of the most important amino acids opens new avenues for studies aiming at manipulating the structure of ibuprofen, in order to decrease its interaction with albumin, and consequently increase its distribution

Propriedades críticas de sistemas fora do equilíbrio via simulação Monte Carlo

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Macromolecular properties of cepacian in water and in dimethylsulfoxide

Cepacian is the exopolysaccharide produced by the majority of the so far investigated clinical strains of the Burkholderia cepacia complex. This is a group of nine closely related bacterial species that might cause serious lung infections in cystic fibrosis patients, in some cases leading to death. In this paper the aggregation ability and the conformational properties of cepacian chain were investigated to understand its role in biofilm formation. Viscosity and atomic force microscopy studies in water and in mixed (dimethylsulfoxide/water) solvent indicated the formation of double stranded molecular structures in aqueous solutions. Inter-residue short distances along cepacian chain were investigated by NOE NMR, which showed that two side chains of cepacian were not conformation ally free due to strong interactions with the polymer backbone. These interactions were attributed to hydrogen bonding and contributed to structure rigidity. (c) 2007 Elsevier Ltd. All rights reserved.

A preparação de material terminológico em língua inglesa por meio de ferramentas linguístico-computacionais

O objetivo desse estudo é demonstrar, por meio de análise quantitativa e qualitativa, a eficácia de ferramentas linguístico-computacionais na seleção de terminologia para a produção de material terminológico. Serão apresentadas duas ferramentas linguístico-computacionais (WordSmith Tools e VocabProfile) e, também, sugestões para que o ensino de termos ofereça resultados práticos. A fundamentação teórico-metodológica recorreu a Barros (2004); Berber Sardinha (2000; 2005); Biderman (2001); Cabré (2007); Cobb (2007); Nation, (2003) e Sinclair (2004). O corpus da pesquisa foi constituído exclusivamente de material escrito na língua inglesa em diversas áreas de especialidade. Os procedimentos de preparação de material terminológico são exemplificados a partir de uma das áreas de especialidades utilizadas nos corpora de pesquisa, as Redes Neurais Artificiais. Os resultados obtidos indicam que a utilização do Wordsmith Tools juntamente com o VocabProfile pode fornecer dados importantes para a pesquisa linguistica.

Discrete squeezed states for finite-dimensional spaces

We show how discrete squeezed states in an N-2-dimensional phase space can be properly constructed out of the finite-dimensional context. Such discrete extensions are then applied to the framework of quantum tomography and quantum information theory with the aim of establishing an initial study on the interference effects between discrete variables in a finite phase space. Moreover, the interpretation of the squeezing effects is seen to be direct in the present approach, and has some potential applications in different branches of physics.

Erbium-activated silica-zirconia planar waveguides prepared by sol-gel route

Er(3+) doped (100-x)SiO(2)-xZrO(2) planar waveguides were prepared by the sol-gel route, with x ranging from 10 up to 30 mol%. Multilayer films doped with 0.3 mol% Er(3+) ions were deposited on fused quartz substrates by the dip-coating technique. The thickness and refractive index were measured by m-line spectroscopy at different wavelengths. The fabrication protocol was optimized in order to confine one propagating mode at 1.5 mu m. Photoluminescence in the near and visible region indicated a crystalline local environment for the Er(3+) ion. (c) 2007 Elsevier B.V. All rights reserved.

Público e privado na formação social brasileira: velhas, novas e novíssimas tensões

O artigo procura traçar um quadro panorâmico de alguns momentos da história brasileira para tentar encontrar as determinações que fizeram com que a intersubjetividade e a 'eticidade' mergulhassem num padrão deletério e nele ficassem amarradas. Busca assim explicar a dificuldade quase crônica que a elite política brasileira tem de governar de modo republicano, ou seja, fazendo com que o interesse público prevaleça democraticamente sobre os interesses privados, sejam esses interesses os do dinheiro, do voto ou das corporações. Sem virtude pública constituída e sedimentada na sociedade e na cultura política, o Brasil cresceu com dificuldades para se aprumar em termos democráticos e republicanos. Mas é uma comunidade que se reconhece como tal, que compartilha uma cultura rica e expressiva, que bem ou mal tem um sistema político e de governo.

Erbium-activated HfO2-based waveguides for photonics

Silica-based sol-gel waveguides activated by Er3+ ions are attractive materials for integrated optic devices. 70SiO(2)-30HfO(2) planar waveguides, doped with Er3+ concentrations ranging from 0.01 to 4 mol%, were prepared by sol-get route. The films were deposited on v-SiO2 and silica-on-silicon substrates, using dip-coating technique. The waveguides show a homogeneous surface morphology, high densification degree and uniform refractive index across the thickness. Emission in the C-telecommunication band was observed at room temperature for ill the samples upon excitation at 980 nm. The shape is found to be almost independent on erbium content, with a FWHM between 44 and 48 nm. The I-4(13/2) level decay curves presented a single-exponential profile, with a lifetime ranging between 1.1 and 6.7 ms, depending on the erbium concentration. The waveguide deposited on silica-on-silicon substrate supports one single propagation mode at 1.5 mum with a confinement coefficient of 0.85, and a losses of about 0.8 dB/cm at 632.8 nm. (C) 2003 Elsevier B.V. All rights reserved.