962 resultados para Geochemical reactions
Resumo:
Petasis and Ugi reactions are used successively without intermediate purification, effectively accomplishing a six-component reaction. The examined reactions are transferred from traditional batch reactors to an automated continuous flow microreactor setup, where optimization and kinetic analyses are performed, proposed mechanisms evaluated, and rate-limiting steps determined.
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The geochemical analysis of soil samples from the Roman town of Calleva Atrebatum (Silchester, Hampshire, UK) has been undertaken in order to enhance our understanding of urban occupation during the late first/early second century AD. Samples taken from a variety of occupation deposits within several, contemporary timber buildings, including associated hearths, have been analysed using laboratory-based x-ray fluorescence for a suite of elements (Cu, Zn, Pb, Sr, P and Ca). The patterns of elemental enrichment seen across the site have allowed us to compare and contrast the buildings that were occupied during this time in an attempt to distinguish different uses, such as between domestic and work-space. Two of the buildings stand out as having high concentrations of elements which suggest that they were dirtier work spaces, whilst other buildings appear to be have lower chemical loadings suggesting they were cleaner.
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Slavic and German colonization of the southern Baltic between the 8th and 15th centuries A.D. is well-documented archaeologically and historically. Despite the large number of pollen profiles from Poland, few palaeoecological studies have examined the ecological impact of a process that was central to the expansion of European, Christian, societies. This study aims to redress this balance through multiproxy analysis of lake sediments from Radzyń Chełminski, Northern Poland, using pollen, element geochemistry (Inductively Coupled-Optical Emission Spectroscopy [ICP-OES]), organic content, and magnetic susceptibility. The close association between lake and medieval settlements presents the ideal opportunity to reconstruct past vegetation and land-use dynamics within a well-documented archaeological, historical, and cultural context. Three broad phases of increasing landscape impact are visible in the pollen and geochemical data dating from the 8th/9th, 10th/11th, and 13th centuries, reflecting successive phases of Slavic and German colonization. This involved the progressive clearance of oak-hornbeam dominated woodland and the development of an increasingly open agricultural landscape. Although the castles and towns of the Teutonic Order remain the most visible signs of medieval colonization, the palynological and geochemical data demonstrate that the major phase of woodland impact occurred during the preceding phase of Slavic expansion; Germans colonists were entering a landscape already significantly altered.
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The combined application of neutron reflectometry (NR) and ellipsometry to determine the oxidation kinetics of organic monolayers at the air–water interface is described for the first time. This advance was possible thanks to a new miniaturised reaction chamber that is compatible with the two techniques and has controlled gas delivery. The rate coefficient for the oxidation of methyl oleate monolayers by gas-phase O3 determined using NR is (5.4 ± 0.6) × 10−10 cm2 per molecule per s, which is consistent with the value reported in the literature but is now better constrained. This highlights the potential for the investigation of faster atmospheric reactions in future studies. The rate coefficient determined using ellipsometry is (5.0 ± 0.9) × 10−10 cm2 per molecule per s, which indicates the potential of this more economical, laboratory-based technique to be employed in parallel with NR. In this case, temporal fluctuations in the optical signal are attributed to the mobility of islands of reaction products. We outline how such information may provide critical missing information in the identification of transient reaction products in a range of atmospheric surface reactions in the future.
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Damage following ischemia and reperfusion (I/R) is common in the intestine and can be caused during abdominal surgery, in several disease states and following intestinal transplantation. Most studies have concentrated on damage to the mucosa, although published evidence also points to effects on neurons. Moreover, alterations of neuronally controlled functions of the intestine persist after I/R. The present study was designed to investigate the time course of damage to neurons and the selectivity of the effect of I/R damage for specific types of enteric neurons. A branch of the superior mesenteric artery supplying the distal ileum of anesthetised guinea pigs was occluded for 1 h and the animals were allowed to recover for 2 h to 4 weeks before tissue was taken for the immunohistochemical localization of markers of specific neuron types in tissues from sham and I/R animals. The dendrites of neurons with nitric oxide synthase (NOS) immunoreactivity, which are inhibitory motor neurons and interneurons, were distorted and swollen by 24 h after I/R and remained enlarged up to 28 days. The total neuron profile areas (cell body plus dendrites) increased by 25%, but the sizes of cell bodies did not change significantly. Neurons of type II morphology (intrinsic primary afferent neurons), revealed by NeuN immunoreactivity, were transiently reduced in cell size, at 24 h and 7 days. These neurons also showed signs of minor cell surface blebbing. Calretinin neurons, many of which are excitatory motor neurons, were unaffected. Thus, this study revealed a selective damage to NOS neurons that was observed at 24 h and persisted up to 4 weeks, without a significant change in the relative numbers of NOS neurons.
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We here report the preparation of supported palladium nanoparticles (NPs) stabilized by pendant phosphine groups by reacting a palladium complex containing the ligand 2-(diphenylphosphino)benzaldehyde with an amino-functionalized silica surface The Pd nanocatalyst is active for Suzuki cross-coupling reaction avoiding any addition of other sources of phosphine ligands The Pd intermediates and Pd NPs were characterized by solid-state nuclear magnetic resonance and transmission electron microscopy techniques The synthetic method was also applied to prepare magnetically recoverable Pd NPs leading to a catalyst that could be reused for up to 10 recycles In summary we gathered the advantages of heterogeneous catalysis magnetic separation and enhanced catalytic activity of palladium promoted by phosphine ligands to synthesize a new catalyst for Suzuki cross-coupling reactions The Pd NP catalyst prepared on the phosphine-functionalized support was more active and selective than a similar Pd NP catalyst prepared on an amino-functionalized support (C) 2010 Elsevier Inc All rights reserved
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We here report the first magnetically recoverable Rh(0) nanoparticle-supported catalyst with extraordinary recovery and recycling properties. Magnetic separation has been suggested as a very promising technique to improve recovery of metal-based catalysts in liquid-phase batch reactions. The separation method is significantly simple, as it does not require filtration, decantation, centrifugation, or any other separation technique thereby, overcoming traditional time- and solvent-consuming procedures. Our new magnetically separable catalytic system, comprised of Rh nanoparticles immobilized on silica-coated magnetite nanoparticles, is highly active and could be reused for up to 20 times for hydrogenation of cyclohexene (180,000 mol/mol(Rh)) and benzene (11,550 mol/mol(Rh) under mild conditions. (c) 2007 Elsevier B. V. All fights reserved.
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We here report the synthesis, characterization and catalytic performance of new supported Ru(III) and Ru(0) catalysts. In contrast to most supported catalysts, these new developed catalysts for oxidation and hydrogenation reactions were prepared using nearly the same synthetic strategy, and are easily recovered by magnetic separation from liquid phase reactions. The catalysts were found to be active in both forms, Ru(III) and Ru(0), for selective oxidation of alcohols and hydrogenation of olefins, respectively. The catalysts operate under mild conditions to activate molecular oxygen or molecular hydrogen to perform clean conversion of selected substrates. Aryl and alkyl alcohols were converted to aldehydes under mild conditions, with negligible metal leaching. If the metal is properly reduced, Ru(0) nanoparticles immobilized on the magnetic support surface are obtained, and the catalyst becomes active for hydrogenation reactions. (c) 2009 Elsevier B.V. All rights reserved.
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We show that halo effects enhance fusion cross sections of weakly bound systems, comparing with the situation when there is no-halo. We introduce dimensionless fusion functions and energy variable quantity to investigate systematical trends in the fusion cross sections of weakly bound nuclei at near-barrier energies. We observe very clearly complete fusion suppression at energies above the barrier due to dynamic effects of the breakup on fusion. We explain this suppression in terms of the repulsive polarization potential produced by the breakup.
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An experimental overview of reactions induced by the stable, but weakly-bound nuclei (6)Li, (7)Li and (9)Be, and by the exotic, halo nuclei (6)He, (8)B, (11)Be and (17)F On medium-mass targets, such as (58)Ni, (59)Co or (64)Zn, is presented. Existing data on elastic scattering, total reaction cross sections, fusion, breakup and transfer channels are discussed in the framework of a CDCC approach taking into account the breakup degree of freedom.
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Using the Sao Paulo potential and the barrier penetration formalism we have calculated the astrophysical factor S(E) for 946 fusion reactions involving stable and neutron-rich isotopes of C, O, Ne, and Mg for center-of-mass energies E varying from 2 to approximate to 18-30 MeV (covering the range below and above the Coulomb barrier). We have parameterized the energy dependence, S(E), by an accurate universal 9-parameter analytic expression and present tables of fit parameters for all the reactions. We also discuss the reduced 3-parameter version of our fit which is highly accurate at energies below the Coulomb barrier, and outline the procedure for calculating the reaction rates. The results can be easily converted to thermonuclear or pycnonuclear reaction rates to simulate various nuclear burning phenomena, in particular, stellar burning at high temperatures and nucleosynthesis in high density environments. (C) 2010 Elsevier Inc. All rights reserved
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The University of Notre Dame, USA (Becchetti et al, Nucl. Instrum. Metho ds Res. A505, 377 (2003)) and later the University of Sao Paulo, Brazil (Lichtenthaler et al, Eur. Phys. J. A25, S-01, 733 (2005)) adopted a system based on superconducting solenoids to produce low-energy radioactive nuclear beams. In these systems the solenoids act as thick lenses to collect, select, and focus the secondary beam into a scattering chamb er. Many experiments with radioactive light particle beams (RNB) such as (6)He, (7)Be, (8)Li, (8)B have been performed at these two facilities. These low-energy RNB have been used to investigate low-energy reactions such as elastic scattering, transfer and breakup, providing useful information on the structure of light nuclei near the drip line and on astrophysics. Total reaction cross-sections, derived from elastic scattering analysis, have also been investigated for light system as a function of energy and the role of breakup of weakly bound or exotic nuclei is discussed.
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Nuclear (p,alpha) reactions destroying the so-called ""light-elements"" lithium, beryllium and boron have been largely studied in the past mainly because their role in understanding some astrophysical phenomena, i.e. mixing-phenomena occurring in young F-G stars [1]. Such mechanisms transport the surface material down to the region close to the nuclear destruction zone, where typical temperatures of the order of similar to 10(6) K are reached. The corresponding Gamow energy E(0)=1.22 (Z(x)(2)Z(X)(2)T(6)(2))(1/3) [2] is about similar to 10 keV if one considers the ""boron-case"" and replaces in the previous formula Z(x) = 1, Z(X) = 5 and T(6) = 5. Direct measurements of the two (11)B(p,alpha(0))(8)Be and (10)B(p,alpha)(7)Be reactions in correspondence of this energy region are difficult to perform mainly because the combined effects of Coulomb barrier penetrability and electron screening [3]. The indirect method of the Trojan Horse (THM) [4-6] allows one to extract the two-body reaction cross section of interest for astrophysics without the extrapolation-procedures. Due to the THM formalism, the extracted indirect data have to be normalized to the available direct ones at higher energies thus implying that the method is a complementary tool in solving some still open questions for both nuclear and astrophysical issues [7-12].
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The traditional reduction methods to represent the fusion cross sections of different systems are flawed when attempting to completely eliminate the geometrical aspects, such as the heights and radii of the barriers, and the static effects associated with the excess neutrons or protons in weakly bound nuclei. We remedy this by introducing a new dimensionless universal function, which allows the separation and disentanglement of the static and dynamic aspects of the breakup coupling effects connected with the excess nucleons. Applying this new reduction procedure to fusion data of several weakly bound systems, we find a systematic suppression of complete fusion above the Coulomb barrier and enhancement below it. Different behaviors are found for the total fusion cross sections. They are appreciably suppressed in collisions of neutron-halo nuclei, while they are practically not affected by the breakup coupling in cases of stable weakly bound nuclei. (C) 2009 Elsevier B.V. All rights reserved.
An imaginary potential with universal normalization for dissipative processes in heavy-ion reactions
Resumo:
In this work we present new coupled channel calculations with the Sao Paulo potential (SPP) as the bare interaction, and an imaginary potential with system and energy independent normalization that has been developed to take into account dissipative processes in heavy-ion reactions. This imaginary potential is based on high-energy nucleon interaction in nuclear medium. Our theoretical predictions for energies up to approximate to 100 MeV/nucleon agree very well with the experimental data for the p, n + nucleus, (16)O + (27)Al, (16)O + (60)Ni, (58)Ni + (124)Sn, and weakly bound projectile (7)Li + (120)Sn systems. (C) 2008 Elsevier B.V. All rights reserved.