77 resultados para (R)-N-(2-(diphenylphosphino)benzylidene)-1-((S)-2-(diphenylphosphino)ferrocenyl)ethylamine


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This article extends results contained in Buzzi et al. (2006) [4], Llibre et al. (2007, 2008) [12,13] concerning the dynamics of non-smooth systems. In those papers a piecewise C-k discontinuous vector field Z on R-n is considered when the discontinuities are concentrated on a codimension one submanifold. In this paper our aim is to study the dynamics of a discontinuous system when its discontinuity set belongs to a general class of algebraic sets. In order to do this we first consider F :U -> R a polynomial function defined on the open subset U subset of R-n. The set F-1 (0) divides U into subdomains U-1, U-2,...,U-k, with border F-1(0). These subdomains provide a Whitney stratification on U. We consider Z(i) :U-i -> R-n smooth vector fields and we get Z = (Z(1),...., Z(k)) a discontinuous vector field with discontinuities in F-1(0). Our approach combines several techniques such as epsilon-regularization process, blowing-up method and singular perturbation theory. Recall that an approximation of a discontinuous vector field Z by a one parameter family of continuous vector fields is called an epsilon-regularization of Z (see Sotomayor and Teixeira, 1996 [18]; Llibre and Teixeira, 1997 [15]). Systems as discussed in this paper turn out to be relevant for problems in control theory (Minorsky, 1969 [16]), in systems with hysteresis (Seidman, 2006 [17]) and in mechanical systems with impacts (di Bernardo et al., 2008 [5]). (C) 2011 Elsevier Masson SAS. All rights reserved.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The understanding of biological membranes may be improved by investigating physical properties of vesicles from natural or synthetic amphiphiles. The application of vesicles as mimetic agents depends on the knowledgment of their structure and properties. Vesicles having different curvature and size may be obtained using different preparation protocols. We have used differential scanning calorimetry (DSC) and steady-state fluorescence to investigate the gel to liquid-crystal phase transition of vesicles prepared by sonication (SUV) and non-sonication (GUV) of the synthetic dioctadecyldimethylammonium bromide (DODAB) in aqueous solution. DSC thermograms for a non-sonicated dispersion show a well-defined pre- and main transition corresponding to two narrow peaks at 36 and 45°C in the first upscan, while in a second upscan, only the main peak was observed. The sharpness of the peaks indicate a cooperative phase behavior for GUV. For a sonicated DODAB dispersion, the first upscan shows a third peak at 40.3°C, whereas for the second upscan the peaks are not well-defined, indicating a less cooperative phase behavior. Alternatively, the fluorescence quantum yield (Φ f) and the anisotropy (r) of trans, trans, trans-1-[4-(3-carboxypropyl)-phenyl]-6-[4-butylphenyl]-1,3,5-hexatriene (4H4A) and the ratio I 1/I 3 of the first to the third vibronic peaks of the pyrene emission spectrum as function of temperature are used as well to describe the phase behavior of DODAB sonicated and non-sonicated dispersions. It is in good agreement with the DSC results that the cooperativity of the thermotropic process is diminished under sonication of the DODAB dispersion, meaning that sonication changes from homogeneous to heterogeneous populations of the amphiphile aggregates. The pre- and main transitions obtained from these techniques are in fairly good accord with results from the literature.

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The Rio da Batateira e Santana formations, the latter with Crato, Ipubi and Romualdo members (Alagoas Stage, Aptian), were studied in four cored and logged wells from the eastern portion of Araripe Basin, Northeastern Brazil. The investigated section is 230 m-thick, and PS-14 well is the most representative, because it is the only one which sampled the evaporites of Ipubi Member. Nine facies cycles were identified, being formed by siliciclastics (estuarine, deltaic and lacustrine), mixed lithologies (lacustrine), carbonates, black shales and marls (lacustrine), and gypsum-anhydrite (lacustrine evaporite). The ordering of facies cycles furnished six depositional sequences. They were formed by siliciclastic, regressive-transgressive R-T cycles (S1 and S4, corresponding to Rio da Batateira Formation and to Santana Formation/Romualdo Member), by siliciclastics and carbonates, R-T cycles (S2, S3.1 and S3.2, corresponding to Crato Member), and by siliciclastic-carbonate, R-T cycles followed by evaporitic cycles (S3.3, referred to Ipubi Member). The last cycles correspond to concentration-dilution, C-D cycles of marine brines, which precipitated gypsum in the restricted lacustrine basin.

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The soluble lipase from Pseudomonas fluorescens (PFL) forms bimolecular aggregates in which the hydrophobic active centers of the enzyme monomers are in close contact. This bimolecular aggregate could be immobilized by multipoint covalent linkages on glyoxyl supports at pH 8.5. The monomer of PFL obtained by incubation of the soluble enzyme in the presence of detergent (0.5% TRITON X-100) could not be immobilized under these conditions. The bimolecular aggregate has two amino terminal residues in the same plane. A further incubation of the immobilized derivative under more alkaline conditions (e.g., pH 10.5) allows a further multipoint attachment of lysine (Lys) residues located in the same plane as the amino terminal residues. Monomeric PFL was immobilized at pH 10.5 in the presence of 0.5% TRITON X-100. The properties of both PFL derivatives were compared. In general, the bimolecular derivatives were more active, more selective and more stable both in water and in organic solvents than the monomolecular ones. The bimolecular derivative showed twice the activity and a much higher selectivity (100 versus 20) for the hydrolysis of R,S-2-hydroxy-4-phenylbutyric acid ethyl ester (HPBEt) in aqueous media at pH 5.0 compared to the monomeric derivative. In experiments measuring thermal inactivation at 75 °C, the bimolecular derivative was 5-fold more stable than the monomeric derivative (and 50-fold more stable than a one-point covalently immobilized PFL derivative), and it had a half-life greater than 4 h. In organic solvents (cyclohexane and tert-amyl alcohol), the bimolecular derivative was much more stable and more active than the monomeric derivative in catalyzing the transesterification of olive oil with benzyl alcohol. © 2012 Elsevier Ltd. All rights reserved.

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Although tannin-rich forages are known to increase protein uptake and to reduce gastrointestinal nematode infections in grazing ruminants, most published research involves forages with condensed tannins (CT), while published literature lacks information on the anthelmintic capacity, nutritional benefits, and antioxidant capacity of alternative forages containing hydrolyzable tannins (HT). We evaluated the anthelmintic activity and the antioxidant capacity of plant extracts containing either mostly CT, mostly HT, or both CT and HT. Extracts were prepared with 70% acetone, lyophilized, redissolved to doses ranging from 1.0mg/mL to 25mg/mL, and tested against adult Caenorhabditis elegans as a test model. The extract concentrations that killed 50% (LC50) or 90% (LC90) of the nematodes in 24h were determined and compared to the veterinary anthelmintic levamisole (8mg/mL). Extracts were quantified for CT by the acid butanol assay, for HT (based on gallic acid and ellagic acid) by high-performance liquid chromatography (HPLC) and total phenolics, and for their antioxidant activity by the oxygen radical absorbance capacity (ORAC) assay. Extracts with mostly CT were Lespedeza cuneata, Salix X sepulcralis, and Robinia pseudoacacia. Extracts rich in HT were Acer rubrum, Rosa multiflora, and Quercus alba, while Rhus typhina had both HT and CT. The extracts with the lowest LC50 and LC90 concentrations, respectively, in the C. elegans assay were Q. alba (0.75 and 1.06mg/mL), R. typhina collected in 2007 (0.65 and 2.74mg/mL), A. rubrum (1.03 and 5.54mg/mL), and R. multiflora (2.14 and 8.70mg/mL). At the doses of 20 and 25mg/mL, HT-rich, or both CT- and HT-rich, extracts were significantly more lethal to adult C. elegans than extracts containing only CT. All extracts were high in antioxidant capacity, with ORAC values ranging from 1800μmoles to 4651μmoles of trolox equivalents/g, but ORAC did not correlate with anthelmintic activity. The total phenolics test had a positive and highly significant (r=0.826, p≤0.01) correlation with total hydrolyzable tannins. Plants used in this research are naturalized to the Appalachian edaphoclimatic conditions, but occur in temperate climate areas worldwide. They represent a rich, renewable, and unexplored source of tannins and antioxidants for grazing ruminants, whereas conventional CT-rich forages, such as L. cuneata, may be hard to establish and adapt to areas with temperate climate. Due to their high in vitro anthelmintic activity, antioxidant capacity, and their adaptability to non-arable lands, Q. alba, R. typhina, A. rubrum, and R. multiflora have a high potential to improve the health of grazing animals and must have their anthelmintic effects confirmed in vivo in both sheep and goats. © 2012.

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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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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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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Pós-graduação em Química - IQ

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