276 resultados para C-N coupling

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo (BDPI/USP)


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Colour-magnitude diagrams (CMDs) of the Small Magellanic Cloud (SMC) star cluster NGC 419, derived from Hubble Space Telescope (HST)/Advanced Camera for Surveys (ACS) data, reveal a well-delineated secondary clump located below the classical compact red clump typical of intermediate-age populations. We demonstrate that this feature belongs to the cluster itself, rather than to the underlying SMC field. Then, we use synthetic CMDs to show that it corresponds very well to the secondary clump predicted to appear as a result of He-ignition in stars just massive enough to avoid e(-)-degeneracy settling in their H-exhausted cores. The main red clump instead is made of the slightly less massive stars which passed through e(-) degeneracy and ignited He at the tip of the red giant branch. In other words, NGC 419 is the rare snapshot of a cluster while undergoing the fast transition from classical to degenerate H-exhausted cores. At this particular moment of a cluster`s life, the colour distance between the main-sequence turn-off and the red clump(s) depends sensitively on the amount of convective core overshooting, Lambda(c). By coupling measurements of this colour separation with fits to the red clump morphology, we are able to estimate simultaneously the cluster mean age (1.35(-0.04)(+0.11) Gyr) and overshooting efficiency (Lambda(c) = 0.47(-0.04)(+0.14)). Therefore, clusters like NGC 419 may constitute important marks in the age scale of intermediate-age populations. After eye inspection of other CMDs derived from HST/ACS data, we suggest that the same secondary clump may also be present in the Large Magellanic Cloud clusters NGC 1751, 1783, 1806, 1846, 1852 and 1917.

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Oscillator networks have been developed in order to perform specific tasks related to image processing. Here we analytically investigate the existence of synchronism in a pair of phase oscillators that are short-range dynamically coupled. Then, we use these analytical results to design a network able of detecting border of black-and-white figures. Each unit composing this network is a pair of such phase oscillators and is assigned to a pixel in the image. The couplings among the units forming the network are also dynamical. Border detection emerges from the network activity.

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We investigate the influence of couplings among continuum states in collisions of weakly bound nuclei. For this purpose, we compare cross sections for complete fusion, breakup, and elastic scattering evaluated by continuum discretized coupled channel (CDCC) calculations, including and not including these couplings. In our study, we discuss this influence in terms of the polarization potentials that reproduces the elastic wave function of the coupled channel method in single channel calculations. We find that the inclusion of couplings among continuum states renders the real part of the polarization potential more repulsive, whereas it leads to weaker absorption to the breakup channel. We show that the noninclusion of continuum-continuum couplings in CDCC calculations may lead to qualitative and quantitative wrong conclusions.

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Excitation functions of quasi-elastic scattering at backward angles have been measured for the (6,7)Li + (144)Sm systems at near-barrier energies, and fusion barrier distributions have been extracted from the first derivatives of the experimental cross sections with respect to the bombarding energies. The data have been analyzed in the framework of continuum discretized coupled-channel calculations, and the results have been obtained in terms of the influence exerted by the inclusion of different reaction channels, with emphasis on the role played by the projectile breakup.

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A method to determine the effects of the geometry and lateral ordering on the electronic properties of an array of one-dimensional self-assembled quantum dots is discussed. A model that takes into account the valence-band anisotropic effective masses and strain effects must be used to describe the behavior of the photoluminescence emission, proposed as a clean tool for the characterization of dot anisotropy and/or inter-dot coupling. Under special growth conditions, such as substrate temperature and Arsenic background, 1D chains of In(0.4)Ga(0.6) As quantum dots were grown by molecular beam epitaxy. Grazing-incidence X-ray diffraction measurements directly evidence the strong strain anisotropy due to the formation of quantum dot chains, probed by polarization-resolved low-temperature photoluminescence. The results are in fair good agreement with the proposed model.

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In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

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Crop evapotranspiration (ETc) was measured as evaporative heat flux from an irrigated acid lime orchard (Citrus latifolia Tanaka) using the aerodynamic method. Crop transpiration (T) was determined by a stem heat balance method. The irrigation requirements were determined by comparing the orchard evapotranspiration (ETc) and T with the reference evapotranspiration (ETo) derived from the Penman-Monteith equation, and the irrigation requirements were expressed as ETc/ETo (Kc) and T/ETo (Kcb) ratios. The influence of inter-row vegetation on the ETc was analyzed because the measurements were taken during the summer and winter, which are periods with different regional soil water content. In this study, the average Mc values obtained were 0.65 and 0.24 for the summer and winter, respectively. The strong coupling of citrus trees to the atmosphere and the sensitivity of citrus plants to large vapor pressure deficits and air/leaf temperatures caused variations in the Kcb in relation to the ETo ranges. During the summer, the Kcb value ranged from 0.34 when the ETo exceeded 5 mm d(-1) to 0.46 when the ETo was less than 3 mm d(-1). (C) 2011 Elsevier B.V. All rights reserved.

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A convenient, mild and highly stereoselective method for C-glycosidation (alkynylation) of D-glucal with various potassium alkynyltrifluoroborates, mediated by BF(3)center dot OEt(2) and involving oxonium intermediates, preferentially provides the alpha-acetylene glycoside products with good yields.

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The copper-catalyzed dimerization of alkynyltrifluoroborates proceeds readily with good yields. The homo-coupling reaction can be effected in DMSO, in the open air, using Cu(OAc)(2) as catalyst in the absence of any other additives. A variety of functional groups are tolerated. (C) 2008 Elsevier Ltd. All rights reserved.

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A complete analysis of H-1 and C-13 NMR spectra of the trypanocidal sesquiterpene lactone eremantholide C and two of its analogues is described. These structurally similar sesquiterpene lactones were submitted to H-1 NMR, C-13 (H-1) NMR, gCOSY, gHSQC, gHMBC, J-resolved and DPFGSE-NOE NMR techniques. The detailed analysis of those results, correlated to some computational calculations (molecular mechanics), led to the total and unequivocal assignment of all H-1 and C-13 NMR data. The determination of all H-1/H-1 coupling constants and all signal multiplicities, together with the elimination of previous ambiguities were also achieved. Copyright (C) 2008 John Wiley & Sons, Ltd.

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A simple protocol for the Pd(OAc)(2)-catalyzed cross-coupling reaction of 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones with potassium aryltrifluoroborates was developed. The reaction is performed at 110 degrees C with a ligand-free catalyst. In all cases, complete conversion of the 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones and aryltrifluoroborates into the C-C coupling products was observed within 30-360 min. It is noteworthy that a large variety of groups present in the potassium aryltrifluoroborates (-CF(3), -OMe, -SEt, -CN, -CHO, -Cl, -Cbz, -NCbz, -OH, -CO(2)H) could be tolerated. Hydrogenation of the endocyclic double bonds in the Suzuki-Miyaura products followed by acid hydrolysis afforded highly enantioenriched alpha-aryl-substituted beta-amino acids.

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The (2,3)J(CH) dependence on dihedral angle (theta H-C-C-X) for cyclopentane derivatives was investigated. We observed that the combined use of experimentally obtained (2,3)J(CH) values and the theoretically determined dihedral angles between the corresponding nuclei can be used to infer the relative stereochemistry of the ring substituents in cyclopentane derivatives. There is a good correlation between the magnitude of (3)J(CH) and the dihedral angle between the hydrogen and the coupled carbon (R-2 = 0.88). Copyright (C) 2008 John Wiley & Sons, Ltd.

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Sonogashira cross-coupling reactions involving (E)-iodo vinyl stannanes and terminal acetylenes were carried out in the presence of Pd(PPh(3))(4), Cul and several amines, affording (Z)-tributylstannyl enynes in moderate to good yields (62-91%). Utilizing the catalytic system containing Pd(PPh(3))(4) (5%), Cul (10%), and TBAOH (40% in aqueous media) as activator, better yields (72-91%) and lower reaction times were achieved. (C) 2011 Elsevier Ltd. All rights reserved.

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In this article we present a complete (1)H and (13)C NMR spectral analysis of three 7,7`-dihydroarylnaphthalene lignan lactones using modern NMR techniques such as COSY, HSQC, HMBC and NOE experiments. Complete assignment and homonuclear hydrogen coupling constant measurements were performed. Copyright (C) 2009 John Wiley & Sons, Ltd.

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Chantler PD, Nussbacher A, Gerstenblith G, Schulman SP, Becker LC, Ferrucci L, Fleg JL, Lakatta EG, Najjar SS. Abnormalities in arterial-ventricular coupling in older healthy persons are attenuated by sodium nitroprusside. Am J Physiol Heart Circ Physiol 300: H1914-H1922, 2011. First published March 4, 2011; doi:10.1152/ajpheart.01048.2010.-The coupling between arterial elastance (E(A); net afterload) and lea ventricular elastance (E(LV); pump performance), known as E(A)/E(LV), is a key determinant of cardiovascular performance and shifts during exercise due to a greater increase in E(LV) versus E(A). This normal exercise-induced reduction in E(A)/E(LV) decreases with advancing age. We hypothesized that sodium. nitroprusside (SNP) can acutely ameliorate the age-associated deficits in E(A)/E(LV). At rest and during graded exercise to exhaustion, EA was characterized as end-systolic pressure/stroke volume and E(LV) as end-systolic pressure/end-systolic volume. Resting E(A)/E(LV): did not differ between old (70 +/- 8 yr. n = 15) and young (30 +/- 5 yr. n = 17) subjects because of a tandem increase in E(A) and E(LV) in older subjects. During peak exercise, a blunted increase in E(LV) in old (7.8 +/- 3.1 mmHg/ml) versus young (11.4 +/- 6.5 mmHg/ml) subjects blunted the normal exercise-induced decline in E(A)/E(LV) in old (0.25 +/- 0.11) versus young (0.16 +/- 0.05) subjects. SNP administration to older subjects lowered resting E(A)/E(LV) by 31% via a reduction E(A) (10%) and an increase in E(LV) (47%) and lowered peak exercise E(A)/E(LV) (36%) via an increase in E(LV) (68%) without a change in E(A). Importantly, SNP attenuated the age-associated deficits in E(A)/E(LV) and E(LV) during exercise, and at peak exercise E(A)/E(LV) in older subjects on drug administration did not differ from young subjects without drug administration. In conclusion, some age-associated deficiencies in E(A)/E(LV), E(A), and E(LV), in older subjects can be acutely abolished by SNP infusion. This is relevant to common conditions in older subjects associated with a significant impairment of exercise performance such as frailty or heart failure with preserved ejection fraction.