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991.
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
992.
We report on the integration of the kinematic dynamo problem in a spherical domain forced by velocity fields that are convective
fluid flows resulting from a bifurcation analysis of the spherical Bénard problem. We derive a code based on generalized spherical
harmonics that ensures a divergence-free magnetic field. We determine the growth or decay of a magnetic field in the kinematic
dynamo equation for various physically relevant velocity fields which are stationary as well as time-periodic and chaotic.
Velocity signals that are produced by heteroclinic cycles are used as an input to an energy-saturated kinematic dynamo equation
that limits the growth of the linearly unstable modes. Preliminary calculations indicate the possibility of reversals of the
magnetic field for this case of forcing.
Received 8 October 1996 and accepted 28 April 1997 相似文献
993.
B. Griepink E. A. Maier P. Quevauviller H. Muntau 《Fresenius' Journal of Analytical Chemistry》1991,339(9):599-603
Summary The Community Bureau of Reference (BCR) has undertaken the production of a wide range of certified reference materials (CRMs) for the improvement of accuracy and measurement harmony in various areas of concern at European Community level. This paper provides an overview of the sectors of the BCR-programme in the field of environment i.e. for water systems (water, sediment, biota), soil analysis (soil, fertiliser, waste), plant analysis (aquatic and terrestrial plants), analysis related to animals (e.g. muscle or liver) or man (e.g. industry and food). 相似文献
994.
W. Hoheisel U. Schulte M. Vollmer F. Träger 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):381-383
This paper reports new results on the optical spectra of Na particles and on laser-induced photodissociation of Na atoms from the surface of these particles. In continuation of our earlier studies we have performed experiments to elucidate the mechanism of thenonthermal dissociation process. Furthermore, theoretical calculations have been carried out with the goal to correlate the wavelength dependence of the photodissociation yield with the optical absorption spectra of the metal particles. In addition, manipulation of the size distribution of metal particles on supports is outlined as an application of the effect. This allows for the preparation of very special surfaces with novel physical and chemical properties. 相似文献
995.
996.
Summary Global average temperatures from 1860 to 1989 were analysed with a simple fitting procedure. The temperature records can be
fitted with a rising exponential up to 1946 and with the same exponential minus an increasing cooling action from 1946 to
1989. It is shown that the results are compatible with the hypothesis of an albedo increase caused by SO2 emissions. This hypothesis gives satisfactory explanations of the temperature drop in the years 1940–1970, of the different
warming of the northern and southern hemispheres and of the slower warming observed over North America. The results give an
indication that the greenhouse warming in the next years could be faster than predicted until now.
Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction. 相似文献
997.
Arthur Greenberg Oleg P. Charkin Ralph H. Bartram István Hargittai Gyula Beke 《Structural chemistry》1992,3(3):221-224
Unsigned book reviews are by the Book Review Editor. 相似文献
998.
999.
1000.
In this paper, we consider a real-life vehicle routeing problem that occurs in a major Swiss company producing pet food and flour. In contrast with usual hypothetical problems, a large variety of restrictions has to be considered. The main constraints are relative to the accessibility and the time windows at customers, the carrying capacities of vehicles, the total duration of routes and the drivers' breaks. To find good solutions to this problem, we propose two heuristic methods: a fast straightforward insertion procedure and a method based on tabu search techniques. Next, the produced solutions are compared with the routes actually covered by the company. Our outcomes indicate that the total distance travelled can be reduced significantly when such methods are used. 相似文献