60 resultados para kinetic resolution of activated cyclopropanes

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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Evidence is provided for the inner-sphere mechanism with actual metal coordination of the racemic amine in the crucial hydrogen transfer step promoted by Shvo's catalyst of the chemoenzymatic dynamic kinetic resolution (DKR) of amines. Key intermediates involved in this H-transfer step were intercepted and continuously monitored by electrospray ionization mass spectrometry (ESI-MS) and characterized by their dissociation chemistries via ESI-MS/MS. © 2013 The Royal Society of Chemistry.

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Treatment with phosphatidylinositol-specific phospholipase C of rat osseous plate membranes released up to 90-95% of alkaline phosphatase, but a specific ATPase activity (optimum pH = 7.5) remained bound to the membrane. The hydrolysis of ATP by this ATPase was negligible in the absence of magnesium or calcium ions. However, at millimolar concentrations of magnesium and calcium ions, the membrane-specific ATPase activity increased to about 560-600 U/mg, exhibiting two classes of ATP-hydrolysing sites, and site-site interactions. GTP, UTP, ITP, and CTP were also hydrolyzed by the membrane-specific ATPase. Oligomycin, ouabain, bafilomycin A(1), thapsigargin, omeprazole, ethacrynic acid and EDTA slightly affected membrane-specific ATPase activity while vanadate produced a 18% inhibition. The membrane-specific ATPase activity was insensitive to theophylline, but was inhibited 40% by levamisole. These data suggested that the membrane-specific ATPase activity present in osseous plate membranes, and alkaline phosphatase, were different proteins. (C) 1998 Elsevier B.V. B.V.

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

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

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Post-traumatic complications occasionally lead to tooth loss as well as the need for future implants. However, rehabilitation with endosseous osseointegrated implants does not protect the patient from the risk of suffering a new trauma. Implant fracture and the damage of the hexagon are post-traumatic complications that guide the clinician to preparing a more intricate treatment plan. The authors present a clinical case of a recurrent trauma of maxillary implant fracture. The treatment plan was to remove the implants followed by autogenous bone grafting to correct the defect. Two titanium implants were replaced, followed by connective tissue graft after allowing complete the healing process of the bone graft to occur. In the postoperative period of 6 months, satisfactory results have been shown as regards soft and hard tissues wound healing.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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We investigate and solve in the context of general relativity the apparent paradox which appears when bodies floating in a background fluid are set in relativistic motion. Suppose some macroscopic body, say, a submarine designed to lie just in equilibrium when it rests (totally) immersed in a certain background fluid. The puzzle arises when different observers are asked to describe what is expected to happen when the submarine is given some high velocity parallel to the direction of the fluid surface. on the one hand, according to observers at rest with the fluid, the submarine would contract and, thus, sink as a consequence of the density increase. on the other hand, mariners at rest with the submarine using an analogous reasoning for the fluid elements would reach the opposite conclusion. The general relativistic extension of the Archimedes law for moving bodies shows that the submarine sinks. As an extra bonus, this problem suggests a new gedankenexperiment for the generalized second law of thermodynamics.

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

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Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc. The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn-Wall-Ozawa method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban's samples, but not for leachate's sample. The occurred difference can be attributed to the constituents present in leachate.

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The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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