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.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

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.

Desenvolvimento de elastômeros termoplásticos a partir de SBR epoxidada e polipropileno

Os elastômeros termoplásticos vulcanizados (TPVs) na sua maioria constituídos por borrachas apolares (EPDM, NR) e poliolefinas (PP, PE), apresentam a vantagem de serem processáveis como termoplásticos e serem facilmente reciclados. No entanto, apresentam desvantagens no que se refere à sua baixa resistência a óleos, combustíveis e graxas em relação à borracha termofixa. Este trabalho, teve como objetivo estudar a obtenção de TPVs com propriedades mecânicas adequadas e resistência a óleos e solventes orgânicos, a partir da borracha comercial SBR 1502 parcialmente epoxidada. Esta, por ter a estrutura química de sua cadeia principal modificada pela introdução de grupos epóxidos, deve apresentar melhor resistência a óleos e solventes. Os TPVs foram obtidos em misturador fechado acoplado a um reômetro Haake, na temperatura de 1800C e velocidade de rotor de 75 rpm, vulcanizados dinamicamente com o sistema Bismaleimida/peróxido de dicumila. Foram caracterizados quanto às suas propriedades mecânicas por medidas tensão-deformação, medidas mecânicas dinâmicas, inchamento em ciclohexano, THF e óleo IRM 903, dureza. A morfologia foi determinada por microscopia eletrônica de varredura, MEV. Foram analisados os fatores que influenciam as propriedades dos TPVs, tais como composição (relação PP/SBR), teor de BMI, grau de epoxidação da borracha, uso de agente compatibilizante. O TPV na composição PP/SBR 40/60, esta epoxidada em 40 mol % e contendo o agente compatibilizante Vestenamer adicionado na forma de blenda (borracha/agente compatibilizante) apresentou a melhor resposta em termos de tensão-deformação na ruptura. Os TPVs com a SBR epoxidada em 70% apresentaram melhor resistência a óleo e solventes. Os fatores, potencialmente, capazes de influenciar a dureza dos TPVs também foram avaliados. Neste particular, verificou-se que o tipo de poliolefina, bem como o uso de plastificante são os fatores que mais influenciam a dureza dos TPVs.

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

Monte Carlo studies of N-methylformamide-dimethyl sulfoxide mixtures

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

Desenvolvimento de misturas ternárias para remoção de reboco de fluido de perfuração sintético

The construction of wells is one of the most important activities of the oil industry. The drilling process is the set of activities and operations to design, program and perform the opening thereof. During this process, the cuttings are removed by the drilling fluid, or mud, and carted to the surface. This fluid is injected into the drill string and returns to the surface through the annular space between the well walls and the drill string. After the descent of the column casing, the annular space between the casing string and the walls of the borehole is filled with cement so as to secure the spine and prevent any migration of fluids between the various permeable zones traversed by the well behind of the coating. To ensure the good quality of the cementation scrubbers are used mattresses which are pumped ahead of the cement slurry so as to avoid contamination of the drilling fluid paste, or vice versa, and assist in the removal of plaster, formed by drilling fluid of the borehole walls, thus enabling a better cement bond to the well. Within this context, this work aims to evaluate the efficiency of mattresses scrubbers, the basis of ionic and nonionic surfactants, on the removal of nonaqueous drilling fluid, based on n-paraffin in oil wells, and the compatibility between the Mattress relations washer / drilling fluid bed scrubber / cement paste mattress washer / cement slurry / drilling fluid and the drilling fluid / cement slurry using laboratory tests rheology, thickening time and compressive strength. Also technique was performed X-ray diffraction (XRD) for a more detailed analysis of these mixtures with hydrated cement paste. In compatibility tests the conditions of temperature and pressure used in the same laboratory procedure simulating the conditions of oil wells, the well is considered the depth of 800 m. The results showed that the compositions of the mattress washer nonionic, KMS obtained a 100% efficient in removing the non-aqueous drilling fluid, and the best formulation showed good results with respect to compliance testing

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Monitoramento da atenuação natural de pluma de contaminação pelo método de radar de penetração no solo (GPR)

O monitoramento da atenuação natural em áreas contaminadas tem se mostrado uma técnica alternativa e de baixo custo para a remediação de áreas contaminadas. A degradação por microorganismos é um dos processos mais importantes na atenuação natural de contaminantes, especialmente compostos de fase líquida não aquosa (NAPL). em muitos casos, a ação efetiva deste processo resulta na geração de ácidos orgânicos, que sob elevadas concentrações ocasionam a dissolução de minerais presentes em subsuperfície onde se encontra a contaminação, com conseqüente liberação de íons. O aumento na quantidade de íons colabora para o aumento da condutividade elétrica do meio. O princípio físico da técnica de Radar de Penetração no Solo (GPR) é a emissão de ondas eletromagnéticas de alta freqüência. A propagação da onda eletromagnética é condicionada à freqüência de sinal emitido e as propriedades elétricas do meio. O aumento da condutividade elétrica do meio resulta na atenuação do sinal e, por conseqüência, na diminuição da profundidade de penetração da onda eletromagnética. Este fator permite o monitoramento de áreas contaminadas sob atenuação natural a partir de análises temporais com o GPR. Este trabalho apresenta um estudo comparativo entre perfis de GPR adquiridos em 1998 e 2003 em uma área contaminada por compostos de fase líquida leve não aquosa (LNAPL), sob atenuação natural. Os resultados indicam um aumento da condutividade elétrica do meio, a partir da atenuação acentuada do sinal GPR observada nas seções de 2003. Este aumento pode estar associado à liberação de íons por dissolução de minerais, pelo ataque de ácidos orgânicos resultantes do processo de biodegradação.

Aplicação de métodos geofísicos no monitoramento de área contaminada sob atenuação natural

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Erbium and ytterbium co-doped SiO2 : GeO2 planar waveguide prepared by the sol-gel route using an alternative precursor

The sol-gel method combined with a spin-coating technique has been successfully applied for the preparation of rare-earth doped silica:germania films used for the fabrication of erbium-doped waveguide amplifiers (EDWA), presenting several advantages over other methods for the preparation of thin films. As with other methods, the sol-gel route also shows some drawbacks, such as cracks related to the thickness of silica films and high hydrolysis rate of certain precursors such as germanium alkoxides. This article describes the preparation and optical characterization of erbium and ytterbium co-doped SiO2:GeO2 crack-free thick films prepared by the sol-gel route combined with a spin-coating technique using a chemically stable non-aqueous germanium oxide solution as an alternative precursor. The non-crystalline films obtained are planar waveguides exhibiting a single mode at 1,550 nm with an average thickness of 3.9 mu m presenting low percentages of porosity evaluated by the Lorentz-Lorenz Effective Medium Approximation, and low stress, according to the refractive index values measured in both transversal electric and magnetic polarizations. Weakly confining core layers (0.3% < Delta n < 0.75%) were obtained according to the refractive index difference between the core and buffer layers, suggesting that low-loss coupling EDWA may be obtained. The life time of the erbium I-4(13/2) metastable state was measured as a function of erbium concentration in different systems and based on these values it is possible to infer that the hydroxyl group was reduced and the formation of rare-earth clusters was avoided.

Aplicação do método eletromagnético indutivo (EM) no monitoramento de contaminantes em subsuperfície

O uso combinado de poços de amostragem e técnicas geofísicas constitui a maneira mais adequada para identificação e o monitoramento de áreas contaminadas. Este procedimento permite a locação de poços de amostragem e de monitoramento em pontos estratégicos, otimizando resultados e minimizando gastos. O método geofísico Eletromagnético Indutivo (EM) apresenta amplas possibilidades de aplicação em estudos ambientais devido à facilidade na aquisição de dados, versatilidade do equipamento em campo e a possibilidade de varredura de grandes áreas num curto espaço de tempo. Este trabalho realiza uma análise comparativa de dados em obtidos no ano de 1992 e em 2003. O local estudado é uma área industrial que apresenta contaminação do solo e água subterrânea por Benzeno, Tolueno, Xileno, 1,2 dicloroetano, Sódio e Cloreto, produto da infiltração de efluentes químicos diretamente do solo. Os resultados indicam uma acentuada atenuação da pluma contaminante, com provável redução no grau de contaminação. Os compostos de fase leve (LNAPLs) apresentaram maior tendência de migração horizontal, concomitante ao movimento da água subterrânea. Os compostos de fase densa (DNAPLs) apresentaram uma tendência mais acentuada de migração no sentido vertical, possivelmente devido à ausência de superfícies impermeáveis. Os compostos inorgânicos acompanharam o fluxo dos compostos de fase líquida não aquosa (NAPLs), o que por sua vez permitiu a caracterização da pluma de contaminação como um corpo condutivo em relação às áreas adjacentes.

Estudo das propriedades de troca iônica e/ou adsorção da celulose e celuloses modificadas

In this work it was studied the capacity of cellulose and chemically modified celluloses (carboxymethylcellulose, cellulose phosphate and oxicellulose) to adsorb copper(II) cations of aqueous and non aqueous solutions. The influence of the principal physical chemical parameters on the adsorption process was examined using the batch adsorption method and copper(II) perchlorate solutions, the maximum adsorption capacity determined for adsorbents were as follows (mol.g(-1)): cellulose, 0.54 . 10(-5); carboxymethylcellulose, 1.28 . 10(-4); cellulose phosphate, 1.12 . 10(-4); oxicellulose, 0.38 . 10(-4).

Structure of SnO2 alcosols and films prepared by sol-gel dip coating

To obtain SnO2 films to be used for surface protection of fluoride glasses, a non-aqueous sol-gel route for the preparation was developed. An ethanolic SnO2 colloidal suspension was prepared by thermohydrolysis of SnCl4 solution at 70 degreesC. By using this procedure, redispersable powders with nanometer sized particles were obtained. Films were obtained by dip coating on glass and mica substrates. The structures of the ethanolic precursor suspension and films were compared to those of similar samples prepared by the classical aqueous sol-gel route. Comparative analyses performed by photon correlation spectroscopy demonstrated that the powders obtained by freeze-drying are fully redispersable either in aqueous or in alcoholic solutions at pH greater than or equal to 8. As prepared sols and redispersed colloidal suspensions have hydrodynamic radius distribution (2-14 nm) with an average size close to 7 nm. The variations in film structures with firing temperature were investigated by small-angle X-ray scattering and X-ray reflectometry. The experimental results show that the films have a two level porous structure composed of agglomerates of primary colloidal particles. The sintering of the primary particles leads to the densification of agglomerates and to the formation of inter-agglomerate spatially correlated pores. The volume fraction of intra-agglomerate pores is reduced from approximate to 50% to approximate to 30% by the precipitation of precursor salts partially hydrolyzed in ethanolic solution. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Chemical, spectroscopic characterization, and in vitro antibacterial studies of a new gold(I) complex with N-acetyl-L-cysteine

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