893 resultados para CATALYTIC MECHANISM
Resumo:
The clean development mechanism (CDM) has been through a long and complex growing process since it was approved as part of the Kyoto Protocol. It was designed within the framework of the UNFCCC and the Kyoto Protocol, and reflected the political and economic realities of that time. To ensure its continued effectiveness in contributing to future global climate action and to reflect on how best to position the CDM to respond to future challenges, a high-level panel (HLP) was formed at the Durban climate change conference in 2011. Following extensive consultations, the panel published its report in September 2012. Through this Special Report, the CEPS Carbon Market Forum offers its reflections on findings and recommendations of the HLP, as well as, by extension, its own views on the future of the CDM. In the context of the latter, it explores the following questions: Is there a need for an instrument such as the CDM in the future? What ‘demand’ can it fill? In the roles identified under the first question, what can be done to adapt it and also continue to increase its efficacy?
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We developed a family of polymer-drug conjugates carrying the combination of the anticancer agent epirubicin (EPI) and nitric oxide (NO). EPI-PEG-(NO)8, carrying the highest content of NO, displayed greater activity in Caco-2 cells while it decreased toxicity against endothelium cells and cardiomyocytes with respect to free EPI. FACS and confocal microscopy confirmed conjugates internalization. Light scattering showed formation of micelle whose size correlated with internalization rate. EPI-PEG-(NO)8 showed increased bioavailability in mice compared to free EPI.
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The Bonin high is a subtropical anticyclone that is predominant near Japan in the summer. This anticyclone is associated with an equivalent-barotropic structure, often extending throughout the entire troposphere. Although the equivalent-barotropic structure of the Bonin high has been known for years among synopticians because of its importance to the summer climate in east Asia, there are few dynamical explanations for such a structure. The present paper attempts to provide a formation mechanism for the deep ridge near Japan. We propose a new hypothesis that this equivalent-barotropic ridge near Japan is formed as a result of the propagation of stationary Rossby waves along the Asian jet in the upper troposphere (‘the Silk Road pattern’). First, the monthly mean climatology is examined in order to demonstrate this hypothesis. It is shown that the enhanced Asian jet in August is favourable for the propagation of stationary Rossby waves and that the regions of descent over the eastern Mediterranean Sea and the Aral Sea act as two major wave sources. Second, a primitive-equation model is used to simulate the climatology of August. The model successfully simulates the Bonin high with an equivalent-barotropic structure. The upper-tropospheric ridge is found to be enhanced by a height anomaly of more than 80 m at 200 hPa, when a wave packet arrives. Sensitivity experiments are conducted to show that the removal of the diabatic cooling over the Asian jet suppresses the Silk Road pattern and formation of an equivalent-barotropic ridge near Japan, while the removal of the diabatic heating in the western Pacific does not. Copyright © 2003 Royal Meteorological Society
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The propagation velocity and propagation mechanism for vortices on a β plane are determined for a reduced-gravity model by integrating the momentum equations over the β plane. Isolated vortices, vortices in a background current, and initial vortex propagation from rest are studied. The propagation mechanism for isolated anticyclones as well as cyclones, which has been lacking up to now, is presented. It is shown that, to first order, the vortex moves to generate a Coriolis force on the mass anomaly of the vortex to compensate for the force on the vortex due to the variation of the Coriolis parameter. Only the mass anomaly of the vortex is of importance, because the Coriolis force due to the motion of the bulk of the layer moving with the vortex is almost fully compensated by the Coriolis force on the motion of the exterior flow. Because the mass anomaly of a cyclone is negative the force and acceleration have opposite sign. The role of dipolar structures in steadily moving vortices is discussed, and it is shown that their overall structure is fixed by the steady westward motion of the mass anomaly. Furthermore, it is shown that reduced-gravity vortices are not advected with a background flow. The reason for this behavior is that the background flow changes the ambient vorticity gradient such that the vortex obtains an extra self-propagation term that exactly cancels the advection by the background flow. Last, it is shown that a vortex initially at rest will accelerate equatorward first, after which a westward motion is generated. This result is independent of the sign of the vortex.
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Examination of conditional instability of the second kind (CISK) and wind-induced surface heat exchange (WISHE), two proposed mechanisms for tropical cyclone and polar low intensification, suggests that the sensitivity of the intensification rate of these disturbances to surface properties, such as surface friction and moisture supply, will be different for the two mechanisms. These sensitivities were examined by perturbing the surface characteristics in a numerical model with explicit convection. The intensification rate was found to have a strong positive dependence on the heat and moisture transfer coefficients, while remaining largely insensitive to the frictional drag coefficient. CISK does not predict the observed dependence of vortex intensification rate on the heat and moisture transfer coefficients, nor the insensitivity to the frictional drag coefficient since it anticipates that intensification rate is controlled by frictional convergence in the boundary layer. Since neither conditional instability nor boundary moisture content showed any significant sensitivity to the transfer coefficients, this is true of CISK using both the convective closures of Ooyama and of Charney and Eliassen. In comparison, the WISHE intensification mechanism does predict the observed increase in intensification rate with heat and moisture transfer coefficients, while not anticipating a direct influence from surface friction.
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Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.
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Anthraquinone immobilised onto the surface of indigo microcrystals enhances the reductive dissolution of indigo to leuco-indigo. Indigo reduction is driven by glucose in aqueous NaOH and a vibrating gold disc electrode is employed to monitor the increasing leuco-indigo concentration with time. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular "wedge effect'' during co-intercalation of Na+ and anthraquinone into the layered indigo crystal structure. The glucose-driven indigo reduction, which is in effective in 0.1 M NaOH at 65 degrees C, becomes facile and goes to completion in the presence of anthraquinone catalyst. Electron microscopy of indigo crystals before and after reductive dissolution confirms a delamination mechanism initiated at the edges of the plate-like indigo crystals. Catalysis occurs when the anthraquinone-indigo mixture reaches a molar ratio of 1:400 (at 65 degrees C; corresponding to 3 mu M anthraquinone) with excess of anthraquinone having virtually no effect. A strong temperature effect ( with a composite E-A approximate to 120 kJ mol(-1)) is observed for the reductive dissolution in the presence of anthraquinone. The molar ratio and temperature effects are both consistent with the heterogeneous nature of the anthraquinone catalysis in the aqueous reaction mixture.
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Shoot dieback is a problem in frequently trimmed Leyland hedges and is increasingly affecting gardeners’ choice of hedge trees, having a negative effect on a conifer nursery industry. Some damage can be attributed to the feeding by aphids, but it is unclear if there are also underlying physiological causes. In this study, we tested the hypothesis that shoot-clipping of conifer trees during adverse growing conditions (i.e. high air temperature and low soil moisture) could be leading to shoot ‘dieback’. Three-year-old Golden Leyland Cypress (x Cupressocyparis leylandii ‘Excalibur Gold’) plants were subjected to either a well-watered or droughted irrigation regime and placed in either a ‘hot’ (average day temperature = 40°C) or a ‘cool’ (average day temperature = 27°C) glasshouse compartment. Half of the plants from each glasshouse were clipped on Day 14 and again on Day 50. Measurements of soil moisture content (SMC), net CO2 assimilation rate (A), stomatal conductance (gs), branchlet xylem water potential (XWP), plant height and foliage colour were made. Within the clipped and unclipped treatments of both glasshouse compartments, plants from the droughted regime had significantly lower values for A, gs and XWP than those from the well-watered regime. However, there was no difference in these parameters between the hot and cool glasshouse compartments. The trends seen for A, gs and XWP of all treatments generally mirrored changes in SMC indicating a direct effect of water supply on these parameters. By the end of the experiment the overall foliage colour of plants from the hot glasshouse was darker than that of plants from the cool glasshouse and the overall foliage colour was also darker following shoot clipping. In general, shoot clipping led to increases in A, gs XWP and SMC. This may be due to the reduction in total leaf area leading to a greater supply of water for the remaining leaves. No shoot ‘dieback’ was observed in any treatment in response to drought stress or shoot-clipping.
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An outdoor experiment was conducted to increase understanding of apical leaf necrosis in the presence of pathogen infection. Holcus lanatus seeds and Puccinia coronata spores were collected from two adjacent and otherwise similar habitats with differing long-term N fertilization levels. After inoculation, disease and necrosis dynamics were observed during the plant growing seasons of 2003 and 2006. In both years high nutrient availability resulted in earlier disease onset, a higher pathogen population growth rate, earlier physiological apical leaf necrosis onset and a reduced time between disease onset and apical leaf necrosis onset. Necrosis rate was shown to be independent of nutrient availability. The results showed that in these nutrient-rich habitats H. lanatus plants adopted necrosis mechanisms which wasted more nutrients. There was some indication that these necrosis mechanisms were subject to local selection pressures, but these results were not conclusive. The findings of this study are consistent with apical leaf necrosis being an evolved defence mechanism.
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Oxidised low density lipoprotein (LDL) may be involved in the pathogenesis of atherosclerosis. We have therefore investigated the mechanisms underlying the antioxidant/pro-oxidant behavior of dehydroascorbate, the oxidation product of ascorbic acid, toward LDL incubated With Cu2+ ions. By monitoring lipid peroxidation through the formation of conjugated dienes and lipid hydroperoxides, we show that the pro-oxidant activity of dehydroascorbate is critically dependent on the presence of lipid hydroperoxides, which accumulate during the early stages of oxidation. Using electron paramagnetic resonance spectroscopy, we show that dehydroascorbate amplifies the generation of alkoxyl radicals during the interaction of copper ions with the model alkyl hydroperoxide, tert-butylhydroperoxide. Under continuous-flow conditions, a prominent doublet signal was detected, which we attribute to both the erythroascorbate and ascorbate free radicals. On this basis, we propose that the pro-oxidant activity of dehydroascorbate toward LDL is due to its known spontaneous interconversion to erythroascorbate and ascorbate, which reduce Cu2+ to Cu+ and thereby promote the decomposition of lipid hydroperoxides. Various mechanisms, including copper chelation and Cu+ oxidation, are suggested to underlie the antioxidant behavior of dehydroascorbate in LDL that is essentially free of lipid hydroperoxides. (C) 2007 Elsevier Inc. All rights reserved.