84 resultados para CHIRAL-SYMMETRY-BREAKING
Resumo:
This paper contributes to a fast growing literature which introduces game theory in the analysis of real option investments in a competitive setting. Specifically, in this paper we focus on the issue of multiple equilibria and on the implications that different equilibrium selections may have for the pricing of real options and for subsequent strategic decisions. We present some theoretical results of the necessary conditions to have multiple equilibria and we show under which conditions different tie-breaking rules result in different economic decisions. We then present a numerical exercise using the in formation set obtained on a real estate development in South London. We find that risk aversion reduces option value and this reduction decreases marginally as negative externalities decrease.
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Both enantiomers of serine adsorb on the intrinsically chiral Cu{531} surface in two different adsorption geometries, depending on the coverage. At saturation, substrate bonds are formed through the two oxygen atoms of the carboxylate group and the amino group (μ3 coordination), whereas at lower coverage, an additional bond is formed through the deprotonated β−OH group (μ4 coordination). The latter adsorption geometry involves substrate bonds through three side groups of the chiral center, respectively, which leads to significantly larger enantiomeric differences in adsorption geometries and energies compared to the μ3 coordination, which involves only two side groups. This relatively simple model system demonstrates, in direct comparison, that attractive interactions of three side groups with the substrate are much more effective in inducing strong enantiomeric differences in heterogeneous chiral catalyst systems than hydrogen bonds or repulsive interactions.
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Using linear theory, it is shown that, in resonant flow over a 2D mountain ridge, such as exists when a layer of uniform wind is topped by an environmental critical level, the conditions for internal gravity-wave breaking are different from those determined in previous studies for non-resonant flows. For Richardson numbers in the shear layer not exceeding 2.25, two zones of flow overturning exist, respectively below and downstream and above and upstream of the expected locations. Flow overturning occurs for values of the dimensionless height of the ridge smaller than those required for a uniform wind profile. These results may have implications for the physical understanding of high-drag states.
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In this article, Northern Hemisphere winter midlatitude blocking is analysed through its wave-breaking characteristics. Rossby wave breaking is identified as a key process in blocking occurrence, as it provides the mechanism for the meridional reversal pattern typical of blocking. Two indices are designed to detect the major properties of wave breaking, i.e. the orientation (cyclonic/anticyclonic–direction of breaking or DB index) and the relative contribution of air masses (warm/cold–relative intensity or RI index). The use of the DB index differentiates between the anticyclonic cases over Europe and Asia and the cyclonic events over the oceanic basins. One of the three regions displaying cyclonic type was found over the Atlantic Ocean, the other two being over the Pacific Ocean. The first of these is located over the western side of the Pacific and is dominated by warm air extrusions, whereas the second is placed northward of the exit region of the jet stream, where the meridional θ gradient is much weaker. Two European blocking types have been detected using the RI index, which separates out the cases dominated by warm and cold air masses. The latter cases in particular exhibited a well-structured dipole, with associated strong anomalies in both temperature and precipitation. Copyright © 2011 Royal Meteorological Society
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A chiral bisurea-based superhydrogelator that is capable of forming supramolecular hydrogels at concentrations as low as 0.2 mm is reported. This soft material has been characterized by thermal studies, rheology, X-ray diffraction analysis, transmission electron microscopy (TEM), and by various spectroscopic techniques (electronic and vibrational circular dichroism and by FTIR and Raman spectroscopy). The expression of chirality on the molecular and supramolecular levels has been studied and a clear amplification of its chirality into the achiral analogue has been observed. Furthermore, thermal analysis showed that the hydroACHTUNGTRENUNGgel- ACHTUNGTRENUNGation of compound 1 has a high response to temperature, which corresponds to an enthalpy-driven self-assembly process. These particular thermal characteristics make these materials easy to handle for soft-application technologies
Resumo:
Climate models consistently predict a strengthened Brewer–Dobson circulation in response to greenhouse gas (GHG)-induced climate change. Although the predicted circulation changes are clearly the result of changes in stratospheric wave drag, the mechanism behind the wave-drag changes remains unclear. Here, simulations from a chemistry–climate model are analyzed to show that the changes in resolved wave drag are largely explainable in terms of a simple and robust dynamical mechanism, namely changes in the location of critical layers within the subtropical lower stratosphere, which are known from observations to control the spatial distribution of Rossby wave breaking. In particular, the strengthening of the upper flanks of the subtropical jets that is robustly expected from GHG-induced tropospheric warming pushes the critical layers (and the associated regions of wave drag) upward, allowing more wave activity to penetrate into the subtropical lower stratosphere. Because the subtropics represent the critical region for wave driving of the Brewer–Dobson circulation, the circulation is thereby strengthened. Transient planetary-scale waves and synoptic-scale waves generated by baroclinic instability are both found to play a crucial role in this process. Changes in stationary planetary wave drag are not so important because they largely occur away from subtropical latitudes.
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This paper generalises and applies recently developed blocking diagnostics in a two- dimensional latitude-longitude context, which takes into consideration both mid- and high-latitude blocking. These diagnostics identify characteristics of the associated wave-breaking as seen in the potential temperature (θ) on the dynamical tropopause, in particular the cyclonic or anticyclonic Direction of wave-Breaking (DB index), and the Relative Intensity (RI index) of the air masses that contribute to blocking formation. The methodology is extended to a 2-D domain and a cluster technique is deployed to classify mid- and high-latitude blocking according to the wave-breaking characteristics. Mid-latitude blocking is observed over Europe and Asia, where the meridional gradient of θ is generally weak, whereas high-latitude blocking is mainly present over the oceans, to the north of the jet-stream, where the meridional gradient of θ is much stronger. They occur respectively on the equatorward and poleward flank of the jet- stream, where the horizontal shear ∂u/∂y is positive in the first case and negative in the second case. A regional analysis is also conducted. It is found that cold-anticyclonic and cyclonic blocking divert the storm-track respectively to the south and to the north over the East Atlantic and western Europe. Furthermore, warm-cyclonic blocking over the Pacific and cold-anticyclonic blocking over Europe are identified as the most persistent types and are associated with large amplitude anomalies in temperature and precipitation. Finally, the high-latitude, cyclonic events seem to correlate well with low- frequency modes of variability over the Pacific and Atlantic Ocean.
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The two-way relationship between Rossby Wave-Breaking (RWB) and intensification of extra tropical cyclones is analysed over the Euro-Atlantic sector. In particular, the timing, intensity and location of cyclone development are related to RWB occurrences. For this purpose, two potential-temperature based indices are used to detect and classify anticyclonic and cyclonic RWB episodes from ERA-40 Re-Analysis data. Results show that explosive cyclogenesis over the North Atlantic (NA) is fostered by enhanced occurrence of RWB on days prior to the cyclone’s maximum intensification. Under such conditions, the eddy-driven jet stream is accelerated over the NA, thus enhancing conditions for cyclogenesis. For explosive cyclogenesis over the eastern NA, enhanced cyclonic RWB over eastern Greenland and anticyclonic RWB over the sub-tropical NA are observed. Typically only one of these is present in any given case, with the RWB over eastern Greenland being more frequent than its southern counterpart. This leads to an intensification of the jet over the eastern NA and enhanced probability of windstorms reaching Western Europe. Explosive cyclones evolving under simultaneous RWB on both sides of the jet feature a higher mean intensity and deepening rates than cyclones preceded by a single RWB event. Explosive developments over the western NA are typically linked to a single area of enhanced cyclonic RWB over western Greenland. Here, the eddy-driven jet is accelerated over the western NA. Enhanced occurrence of cyclonic RWB over southern Greenland and anticyclonic RWB over Europe is also observed after explosive cyclogenesis, potentially leading to the onset of Scandinavian Blocking. However, only very intense developments have a considerable influence on the large-scale atmospheric flow. Non-explosive cyclones depict no sign of enhanced RWB over the whole NA area. We conclude that the links between RWB and cyclogenesis over the Euro-Atlantic sector are sensitive to the cyclone’s maximum intensity, deepening rate and location.
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The reality of the current international order makes it imperative that a just and effective climate regime balance the historical responsibility of developed countries with the increasing absolute emissions from many developing nations. In this short outlook article, key pillars are proposed for a new international climate architecture that envisions replacing the current annex system with two new annexes –Annex α, for countries with high current emissions and historically high emissions, and Annex β, for countries with high current emissions and historically low emissions. Countries in both annexes would implement legally binding targets under this framework. Additionally, this proposal includes tweaks and revisions to funding and technology transfer mechanisms to correct for weaknesses and inequities under the current Kyoto architecture. The proposed framework stems from a belief that a top-down, international approach to climate policy remains the most effective for ensuring environmental integrity. Given the slow rate of institutional learning, reforming and improving the current system is held as a more efficient course of action than abandoning the progress already achieved. It is argued that the proposed framework effectively accommodates key equity, environmental integrity and political feasibility concerns.
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The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which twelve organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally-arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structures derived from the corresponding Pd12 cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl]2 with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3-) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.
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An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.
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We report here a unique chiral hybrid gallium sulfide, [NC2H8]2[Ga10S16(N2C12H12)(NC2H7)2] 1, consisting of helical chains of organically-functionalised supertetrahedral clusters which form quadruple-stranded helical nanotubes of ca. 3 nm diameter. This material therefore consists of discrete metal-organic nanotubes which, to the best of our knowledge, are extremely rare. Whilst solvothermal reactions involving 1,2-di(4-pyridyl)ethylene (DPE) resulted in the formation of such single-walled chiral nanotubes, the use of longer 4,4’-trimethylenedipyridine (TMP) ligands resulted in the synthesis of a two-dimensional hybrid gallium sulfide, [C5H6N]3[Ga10S16(OH)(N2C13H14)] 2 in which, for the first time, inorganic and organic linkages between supertetrahedral clusters coexist.
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The surface structure and morphology of the clean Re(11%21) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show largescale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface.