412 resultados para DIAZO KETONES


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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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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)

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

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Melatonin is an endoleamine that has anti-inflammatory, immunomodulating and antioxidants properties. But there is a contradiction between the antioxidant effects of melatonin and glutathione (GSH). Therefore, the main objective of this work was to study the effect of melatonin on the oxidation of GSH and the effect of GSH on the oxidation of melatonin by peroxyl radicals generated by thermolysis of 2,2 -Azobis(2- amino-propane)-dihydrochloride (AAPH). The influence of the reaction conditions and the identity of the products of oxidation were also studied. The main products obtained during the oxidation of melatonin were its monohydroxylated derivative and N1-acetyl- N2-formyl-5-methoxykynuramine (AFMK), which is the product obtained by oxidative cleavage of the melatonin indole ring. By studying the buffer type, pH and the presence or absence of dissolved oxygen in the reaction system, it was observed that, the yield of AFMK was higher when the pH or the concentration of oxygen was increased. Comparing the reactivity of both molecules GSH and melatonin, it can be seen that intermediates radicals generated during the oxidation of melatonin are able to oxidize GSH itself. We propose that this chemical property could justify the recent reports that demonstrated the inability of melatonin to inhibit the oxidation of GSH in cells

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Most advanced eusocial bees recruit their nestmates to food resources. Recently, studies in Meliponini species showed that the cephalic salivary (labial) glands (CSGs) are responsible for the production of scent-trail pheromones. Studies on CSGs have shown changes in glandular cell morphology since the worker emerges from brood combs (newly emerged) till forager phase, which may be correlated to changes in the composition of secretion produced. However, no study has been made till now regarding to the composition of CSGs secretion of Scaptotrigona postica and the chemical changes that occur in this secretion according to the worker's life phase or tasks performed. In this study, the chemical profile of CSG secretion in S. postica workers was studied. Glands were taken from specimens newly emerged (NE), working in the brood combs area (CA) and forager (FO) and were analyzed by gas chromatography-mass spectrometry. The results showed that glandular secretion consists of oxygenated compounds of middle volatility (acids, alcohols, aldehydes, ketones, esters and ether), and their quantity varies among the different phases of life, increasing as the individual undergoes from intra- to extra-colonial activities. The NE phase contained the smallest variety and quantity of compounds. Due to the variability of compounds, the CA workers were separated into 3 groups according to the chemical constitution of their secretion. Forager workers showed the largest quantity and variety of chemical compounds. The major compounds in forager gland secretion are 7-hexadecen-1-yl acetate and 5-tetradecen-1-yl acetate. Statistical analysis indicates that the chemical composition of glandular secretion is task-related.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Nine marine fungi (Aspergillus sclerotiorum CBMAI 849, Aspergillus sydowii Ce19, Beauveria felina CBMAI 738, Mucor racemosus CBMAI 847, Penicillium citrinum CBMAI 1186, Penicillium miczynskii Ce16, P. miczynskii Gc5, Penicillium oxalicum CBMAI 1185, and Trichoderma sp. Gc1) catalyzed the asymmetric bioconversion of iodoacetophenones 1-3 to corresponding iodophenylethanols 6-8. All the marine fungi produced exclusively (S)-ortho-iodophenylethanol 6 and (S)-meta-iodophenylethanol 7 in accordance to the Prelog rule. B. felina CBMAI 738, P. miczynskii Gc5, P. oxalicum CBMAI 1185, and Trichoderma sp. Gc1 produced (R)-para-iodophenylethanol 8 as product anti-Prelog. The bioconversion of para-iodoacetophenone 3 with whole cells of P. oxalicum CBMAI 1185 showed competitive reduction-oxidation reactions.

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A concise synthesis of the (-)-indolizidine alkaloid 167B and two formal syntheses of (-)-indolizidine 209D and (-)-coniceine are described in just three steps from an alpha,beta-unsaturated diazoketone, via an unusual photochemical Wolff rearrangement. Preparation of the unsaturated diazoketone is straightforward from N-Cbz-prolinal and a 3-diazo-2-oxopropylphosphonate, employing a Horner-Wadsworth-Emmons reaction. The strategy should be feasible and easily adaptable to the synthesis of other indolizidine alkaloids and analogues. (C) 2011 Elsevier Ltd. All rights reserved.