946 resultados para CHIRAL SYMMETRY-BREAKING


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This paper proposes the hypothesis that the low-frequency variability of the North Atlantic Oscillation (NAO) arises as a result of variations in the occurrence of upper-level Rossby wave–breaking events over the North Atlantic. These events lead to synoptic situations similar to midlatitude blocking that are referred to as high-latitude blocking episodes. A positive NAO is envisaged as being a description of periods in which these episodes are infrequent and can be considered as a basic, unblocked situation. A negative NAO is a description of periods in which episodes occur frequently. A similar, but weaker, relationship exists between wave breaking over the Pacific and the west Pacific pattern. Evidence is given to support this hypothesis by using a two-dimensional potential-vorticity-based index to identify wave breaking at various latitudes. This is applied to Northern Hemisphere winter data from the 40-yr ECMWF Re-Analysis (ERA-40), and the events identified are then related to the NAO. Certain dynamical precursors are identified that appear to increase the likelihood of wave breaking. These suggest mechanisms by which variability in the tropical Pacific, and in the stratosphere, could affect the NAO.

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The field of Molecular Spectroscopy was surveyed in order to determine a set of conventions and symbols which are in common use in the spectroscopic literature. This document, which is Part 2 in a series, establishes the notations and conventions used for the description of symmetry in rigid molecules, using the Schoenflies notation. It deals firstly with the symmetry operators of the molecular point groups (also drawing attention to the difference between symmetry operators and elements). The conventions and notations of the molecular point groups are then established, followed by those of the representations of these groups as used in molecular spectroscopy. Further parts will follow, dealing inter alia with permutation and permutation-inversion symmetry notation, vibration-rotation spectroscopy and electronic spectroscopy.

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The field of Molecular Spectroscopy was surveyed in order to determine a set of conventions and symbols which are in common use in the spectroscopic literature. This document, which is Part 3 in a series, deals with symmetry notation referring to groups that involve nuclear permutations and the inversion operation. Further parts will follow, dealing inter alia with vibration-rotation spectroscopy and electronic spectroscopy.

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Chiral N-heterocyclic carbene–borane complexes have been synthesised, and have been shown to reduce ketones with Lewis acid promotion. Chiral N-heterocyclic carbene–borane and –diorganoborane complexes can reduce ketones with enantioselectivities up to 75% and 85% ee, respectively.

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Conventional seemingly unrelated estimation of the almost ideal demand system is shown to lead to small sample bias and distortions in the size of a Wald test for symmetry and homogeneity when the data are co-integrated. A fully modified estimator is developed in an attempt to remedy these problems. It is shown that this estimator reduces the small sample bias but fails to eliminate the size distortion.. Bootstrapping is shown to be ineffective as a method of removing small sample bias in both the conventional and fully modified estimators. Bootstrapping is effective, however, as a method of removing. size distortion and performs equally well in this respect with both estimators.

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We report herein, the first generation of unsymmetrical ketone-derived chiral stabilized azomethine ylides. Intrairiolecular and intermolecular cycloaddition strategies have been utilized to synthesize both an enantiornerically pure bicyclic proline derivative and an enantionierically pure beta-hydroxy-alpha-amino acid.

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The selective reduction of one of the three carboxyl groups of two chiral citric acid derivatives to the corresponding aldehydes, under Rosenmund conditions, are reported together with the application of these aldehydes to the syntheses of the ester side chains of some potently antileukemic Cephalotaxus alkaloids e.g. anhydroharringtonine.