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61.
P E S?rensen R A McClelland R D Gandour 《Acta chemica Scandinavica (Copenhagen, Denmark : 1989)》1991,45(6):558-566
The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate. 相似文献
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66.
It is known that every conformai embedding of the disk into the extended complex plane possesses a r2-quasiconformal extension across eachr-level line (the r2-property of a domain). We show here that this is a characteristic property of the disk: any simply connected domain which
is not a disk does not admit ther
2-property.
Supported by the RiP-program of the Volkswagen-Stiftung in the Mathematisches Forschungsinstitut Oberwolfach. 相似文献
67.
68.
F. Cannata J. P. Dedonder L. Le?niak 《Zeitschrift für Physik A Hadrons and Nuclei》1992,343(4):451-460
We investigate the origin of the attraction in theK¯K channel around the threshold by introducing an additional channel to theππ andK¯K channels in a separable potential formalism assuming, in general, no direct interaction in theK¯K channel. To reproduce the features of the data, we find that the threshold of the additional channel is much above thef 0(975) meson position. We show that this three-channel problem can be reduced to an effective two-channel problem where thef 0(975) behaves as if it were aK¯K molecule bound by the coupling to the exotic channel. This picture is also supported by the fact that a single pole only, in the complexK¯K momentum plane, is associated to thef 0(975) meson. Various physical observables, like the decay branching ratio and theK¯K scattering length, are then discussed in an effective two-channel framework. 相似文献
69.
Julie Clutterbuck Oliver C. Schnürer Felix Schulze 《Calculus of Variations and Partial Differential Equations》2007,29(3):281-293
We prove stability of rotationally symmetric translating solutions to mean curvature flow. For initial data that converge
spatially at infinity to such a soliton, we obtain convergence for large times to that soliton without imposing any decay
rates.
The authors are members of SFB 647/B3 “Raum – Zeit – Materie: Singularity Structure, Long-time Behaviour and Dynamics of Solutions
of Non-linear Evolution Equations”. 相似文献
70.
W. Brüggemann K. Fischer H. Jahnke 《Journal of Mathematical Modelling and Algorithms》2003,2(2):153-169
In Part I of this study, we suggest to identify an operations research (OR) problem with the equivalence class of models describing the problem and enhance the standard computer-science theory of computational complexity to be applicable to this situation of an often model-based OR context. The Discrete Lot-sizing and Scheduling Problem (DLSP) is analysed here in detail to demonstrate the difficulties which can arise if these aspects are neglected and to illustrate the new theoretical concept. In addition, a new minimal model is introduced for the DLSP which makes this problem eventually amenable to a rigorous analysis of its computational complexity. 相似文献