989 resultados para cubane 4-iodo-1-vinylcubane 1-iodocubane-4-carboxaldehyde Stetter reaction cross metathesis
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This work evaluates some collateral effects caused by the application of the Fenton process to 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) and diesel degradation in soil. While about 80% of the diesel and 75% of the DDT present in the soil were degraded in a slurry system, the dissolved organic carbon (DOC) in the slurry filtrate increased from 80 to 880 mg l(-1) after 64 h of reaction and the DDT concentration increased from 12 to 50 mu g l(-1). Experiments of diesel degradation conducted on silica evidenced that soluble compounds were also formed during diesel oxidation. Furthermore, significant increase in metal concentrations was also observed in the slurry filtrate after the Fenton treatment when compared to the control experiment leading to excessive concentrations of Cr, Ni, Cu and Mn according to the limits imposed for water. Moreover, 80% of the organic matter naturally present in the soil was degraded and a drastic volatilization of DDT and 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene was observed. Despite the high percentages of diesel and DDT degradation in soil, the potential overall benefits of its application must be evaluated beforehand taking into account the metal and target compounds dissolution and the volatilization of contaminants when the process is applied. (c) 2007 Elsevier Ltd. All rights reserved.
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The neutral hydrolysis reaction of post-consumer poly(ethylene terephthalate) in solid state was studied through the reaction of the polymer with water at the molar ratio 1:91 with autogenous pressure. Two sizes of post-consumer PET flakes and temperatures of 135 °C, 170°C and 205°C with pressures of 4.0 atm, 7.5 atm and 13.5 atm, respectively, were considered. With reaction time equal to 6h, the method reached 99% depolymerization at 205°C, 8.2% at 170 °C and 1.7% at 135°C. The reaction extension was measured by separating the terephthalic acid formed in the process and calculating by gravimetry how much material could still be reacted. Through the viscosimetry of diluted, solutions and the counting of carboxylic end groups in the remaining material from the gravimetric assay, it was possible to suggest that the reaction occurs randomly and in the whole volume of the polymeric particle and not solely on the surface. The terephthalic acid obtained and then purified was characterized by elemental analysis, magnetic nuclear resonance, size and panicle size distribution and spectrophotometry in the visible spectrum, and it was similar to the petrochemical equivalent, with purity recorded in carbon base equal to 99.9%.
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Melasma is a common acquired symmetrical hypermelanosis characterized by irregular light- to dark-brown macules on sun-exposed skin areas. The literature shows few studies on its physiopathogeny. However, changes in α-melanocyte stimulating hormone (α-MSH) secretion and melanocortin-1 receptor (MC1-R) expression may play a role to trigger this condition. Biopsies were taken from both melasma skin and adjacent perilesional normal skin of 44 patients. The biopsies were submitted for hematoxylin and eosin and Fontana-Masson staining and immunohistochemistry with Melan-A, α-MSH, and MC1-R, and processed for transmission electron microscopy. In some cases, they were submitted to MC1-R gene expression analysis by real-time polymerase chain reaction. Increased lymphohistiocytic infiltrate and solar elastosis, higher epidermal melanin were observed in melasma skin. Electron microscopy revealed a greater number of mature melanosomes in keratinocytes and melanocytes, and more prominent cytoplasmic organelles in melasma skin. There was no difference in melanocyte number between areas. However, melanocytes were larger and more dendritic in melasma skin. Immunohistochemistry with α-MSH and MC1-R showed significant labeling in melasmic epidermis but MC1-R messenger ribonucleic acid (RNAm) did not show significant quantitative difference between melasma and normal skin. © 2010 by Lippincott Williams & Wilkins.
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Introduction: The analysis of body composition through direct and indirect methods allows the study of the various components of the human body, becoming the central hub for assessing nutritional status. Objective: The objective of the study was to develop equations for predicting body fat% from circumferential body arm, waist and calf and propose percentiles to diagnose the nutritional status of school children of both sexes aged 4-10 years. Methods: We selected intentionally (non-probabilistic) 515 children, 261 children and 254 being girls belonging to Program interaction and development of children and adolescents from the State University of Campinas (Sao Paulo, Brazil). Anthropometric variables were evaluated for weight, height, triceps and subscapular skinfolds and body circumferences of arm, waist and calf, and the% fat determined by the equation proposed by Boileau, Lohman and Slaughter (1985). Through regression method 2 were generated equations to predict the percentage of fat from the body circumferences, the equations 1 and 2 were validated by cross validation method. Results: The equations showed high predictive values ranging with a R2 = 64-69%. In cross validation between the criterion and the regression equation proposed no significant difference (p > 0.05) and there was a high level of agreement to a 95% CI. Conclusion: It is concluded that the proposals are validated and shown as an alternative to assess the percentage of fat in school children of both sexes aged 4-10 years in the region of Campinas, SP (Brazil).
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Pós-graduação em Bases Gerais da Cirurgia - FMB
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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A Alfa-galactosidase A (α-Gal A) humana é uma enzima lisossômica que quando deficiente causa a doença de Fabry. A doença de Fabry é uma esfingolipidose cuja principal causa de morbi-mortalidade é a insuficiência renal crônica (IRC). O objetivo deste estudo foi a implantação de um protocolo laboratorial que permita o diagnóstico da doença de Fabry em plasma e leucócitos, além da análise das características cinéticas da enzima α-Gal A em plasma e busca ativa da doença em 25 indivíduos com IRC de causa desconhecida. Também foram avaliadas a reprodutibilidade e a estabilidade do método enzimático. A padronização dos ensaios foi realizada com o substrato fluorescente 4-metilumbeliferil-α-Dgalactopiranosídeo. A reprodutibilidade foi avaliada utilizando amostras de plasma aliquotadas a 4ºC, -20ºC e -70ºC, analisadas uma vez ao mês por 6 meses e a estabilidade da fluorescência por até 24 horas após o término do ensaio enzimático. A padronização permitiu a implantação de valores de referência da α-Gal A para o estado do Pará, de 4 a 28 nmoles/h/mL (plasma) e de 20 a 96 nmoles/h/mg proteína (leucócitos). A enzima α-Gal A se mostrou termolábil, visto que com apenas 1 minuto de pré-incubação das amostras a 60ºC, sua atividade decaiu 71,09%. Com relação ao tempo de incubação, a atividade enzimática apresentou uma disposição linear crescente entre 15 a 180 minutos de incubação. A α-Gal A apresentou maior atividade no pH 4,8, o Km encontrado para a α-Gal A foi de 1,007 mM e a Vmáx foi 30,9 nmoles/h/mL. A melhor temperatura de armazenamento de plasma até o ensaio enzimático é -20ºC, onde foi observada menor variação em um período máximo de 6 meses. O método enzimático utilizado é estável, mesmo após 24 horas do término do ensaio, em temperatura ambiente. Com relação aos pacientes com IRC de causa desconhecida, todos apresentaram valor de atividade da α-Gal A dentro dos parâmetros de referência e, portanto, nenhum foi diagnosticado com doença de Fabry. O entendimento da cinética da α-Gal A e do seu comportamento in vitro possibilita um melhor diagnóstico laboratorial da doença de Fabry gerando dados para futuras comparações com indivíduos afetados por mutações nesta enzima
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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A measurement of differential cross sections for the production of a pair of isolated photons in proton-proton collisions at root s = 7 TeV is presented. The data sample corresponds to an integrated luminosity of 5.0 fb(-1) collected with the CMS detector. A data-driven isolation template method is used to extract the prompt diphoton yield. The measured cross section for two isolated photons, with transverse energy above 40 and 25 GeV respectively, in the pseudorapidity range vertical bar eta vertical bar < 2.5, vertical bar eta vertical bar (sic) [1.44, 1.57] and with an angular separation Delta R > 0.45, is 17.2 +/-0.2 (stat) +/-1.9 (syst) +/- 0.4 (lumi) pb. Differential cross sections are measured as a function of the diphoton invariant mass, the diphoton transverse momentum, the azimuthal angle difference between the two photons, and the cosine of the polar angle in the Collins-Soper reference frame of the diphoton system. The results are compared to theoretical predictions at leading, next-to-leading, and next-to-next-to-leading order in quantum chromodynamics.
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The objective of the present research was to quantify the seminiferous epithelium cells, spermatogenesis efficiency and characterize the ultrastrucure of Sertoli cells in goats. Eighteen goats were used and divided into three groups: Group I - goats without bipartition of the scrotum; Group II - animals with bipartition of the scrotum in up to 50% of the testicular length; Group III - goats with bipartition of the scrotum in more than 50% of the testicular length. The goat testes in Group III had a greater number of primary spermatocytes (25.37 +/- 4.55 cells per cross sections), spermatids (112 +/- 15.12 cells per cross sections), and Sertoli cells (9.46 +/- 1.74 cells per cross sections) than the animals in Groups land (P <0.05). The spermatogenic mitotic, meiotic, and general efficiency were greater in animals in Group III (1.25 +/- 0.28; 5.12 +/- 1.63; 6.44 +/- 1.96) when compared to those in Groups I and II. Sheet-like processes originated from the Sertoli cell body as simple and smooth structures which involved almost all the surface of germ cells. Slender cord-like processes originated from Sertoli cells and also from the sheet-like processes. The relative frequency of the cycle stages showed differences among the groups of goats studied, and the highest frequency was in Stage 3 (20.68% for goats in Group I, 21.15% for those in Group II, and 16.89% for the animals in Group III). In conclusion, goats with bipartition of the scrotum have a greater number of germ and Sertoli cells per cross section of seminiferous tubule, that indicated a greater sperm production when compared to the other groups, and the ultrastructure of the Sertoli cell process did not present any relationship with bipartition of the scrotum. (C) 2012 Elsevier B.V. All rights reserved.
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In this conference we report cross sections for elastic collisions of low-energy electrons with the HCOOH…(H2O)n complexes, with n = 1, 2 and 3. The scattering cross sections were computed with the Schwinger multichannel method [K. Takatsuka and V. McKoy, Phys. Rev. A 24 , 2473 (1981); Phys. Rev. A 30 , 1734 (1984)] with pseudopotentials [M. H. F. Bettega, L. G. Ferreira, and M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)] in the static-exchange and static-exchange plus polarization approximations, for energies from 0.5 eV to 6 eV. We considered some diÆerent hydrogen-bonded structures for the complexes that were generated with classical Monte Carlo simulations [K. Coutinho and S. Canuto, J. Chem. Phys. 113, 9132, (2000)]. The aim of this work is to investigate the effect of the surrounding water molecules on the π* shape resonance of the solute. Previous theoretical and experimental studies carried out in the gas phase reported a π* state for HCOOH at around 1.9 eV. For the n = 1 case and for all complexes, the stabilization of the resonance was observed (it appears at lower energy compared to the value obtained in the gas phase), as reported previously for the CH2O…H2O complexes [T. C. Freitas, M. A. P. Lima, S. Canuto, and M. H. F. Bettega, Phys. Rev. A 80, 062710 (2009)]. This result indicates that the presence of the solvent may affect the processes related to the π* state, such as the molecular dissociation by electron impact. For the n = 2 case we have observed both stabilization and destabilization of the π* resonance, that is associated with the hydrogen bond donor or acceptor role of the water molecules in the complexes. For the n = 3 case, preliminary static-exchange results show the stabilization of the π* state. We propose an explanation of the stabilization/destabilization of the π* state in terms of the polarization of the solute due to the surrounding water molecules and the net charge in the solute.
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Heterocyclic compounds represent almost two-thirds of all the known organic compounds: they are widely distributed in nature and play a key role in a huge number of biologically important molecules including some of the most significant for human beings. A powerful tool for the synthesis of such compounds is the hetero Diels-Alder reaction (HDA), that involve a [4+2] cycloaddition reaction between heterodienes and suitable dienophiles. Among heterodienes to be used in such six-membered heterocyclic construction strategy, 3-trialkylsilyloxy-2-aza-1,3-dienes (Fig 1) has been demonstrated particularly attractive. In this thesis work, HDA reactions between 2-azadienes and carbonylic and/or olefinic dienophiles, are described. Moreover, substitution of conventional heating by the corresponding dielectric heating as been explored in the frame of Microwave-Assisted-Organic-Synthesis (MAOS) which constitutes an up-to-grade research field of great interest both from an academic and industrial point of view. Reaction of the azadiene 1 (Fig 1) will be described using as dienophiles carbonyl compounds as aldehyde and ketones. The six-membered adducts thus obtained (Scheme 1) have been elaborated to biologically active compounds like 1,3-aminols which constitutes the scaffold for a wide range of drugs (Prozac®, Duloxetine, Venlafaxine) with large applications in the treatment of severe diseases of nervous central system (NCS). Scheme 1 The reaction provides the formation of three new stereogenic centres (C-2; C-5; C-6). The diastereoselective outcome of these reactions has been deeply investigated by the use of various combination of achiral and chiral azadienes and aliphatic, aromatic or heteroaromatic aldehydes. The same approach, basically, has been used in the synthesis of piperidin-2-one scaffold substituting the carbonyl dienophile with an electron poor olefin. Scheme 2 As a matter of fact, this scaffold is present in a very large number of natural substances and, more interesting, is a required scaffold for an huge variety of biologically active compounds. Activated olefins bearing one or two sulfone groups, were choose as dienophiles both for the intrinsic characteristic flexibility of the “sulfone group” which may be easily removed or elaborated to more complex decorations of the heterocyclic ring, and for the electron poor property of this dienophiles which makes the resulting HDA reaction of the type “normal electron demand”. Synthesis of natural compounds like racemic (±)-Anabasine (alkaloid of Tobacco’s leaves) and (R)- and (S)-Conhydrine (alkaloid of Conium Maculatum’s seeds and leaves) and its congeners, are described (Fig 2).