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961.
962.
963.
964.
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
965.
Ingrid Persson Folke Tjerneld Bärbel Hähn-Hagerdal 《Applied biochemistry and biotechnology》1991,27(1):9-25
Cellulolytic enzyme production in aqueous two-phase systems withTrichoderma reesei Rutgers C30 has been investigated. The influ ence of different phase systems, as well as addition of media compo nents and substrate on enzyme production have been studied. Extractive enzyme production in fed-batch cultivations was per formed in a phase system composed of PEG 8000 5%-Dextran T500 7% with 1% Solka-Floc BW 200 as substrate. The cellulolytic enzyme system was intermittently withdrawn with the top phase. Addition of media components every 24 h and cellulose every 72 h gave an aver age enzyme activity in the withdrawn top phase of 2.2 FPU/mL dur ing 170 h cultivation. The corresponding productivity was 18 FPU/lh. The productivity was increased to 24 FPU/l.h when media compo nents and cellulose were added every 72 h. The average enzyme con centration was then 1.6 FPU/mL. The results are discussed in relation to methods for cellulolytic enzyme production involving immobiliza tion and cell recycling. 相似文献
966.
S. Chen H. Büttner 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,29(1):15-18
We generalize the Shastry-Sutherland model to three dimensions. By representing the model as a sum of the semidefinite positive
projection operators, we exactly prove that the model has exact dimer ground state. Several schemes for constructing the three-dimensional
Shastry-Sutherland model are proposed.
Received 20 February 2002 / Received in final form 27 May 2002 Published online 17 September 2002 相似文献
967.
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
968.
P Nürnberg I Barth E Fuhrmann C Lenzner T Losanova C Peters H P?che G Thiel 《Electrophoresis》1991,12(2-3):186-192
Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies. 相似文献
969.
970.
P. Y. Zhu 《Il Nuovo Cimento C》1991,14(3):263-283
Summary The effective-medium approximation is applied to investigate scattering from a half-space of randomly and densely distributed
discrete scatterers. Starting from vector wave equations, an approximation, called effective-medium Born approximation, a
particular way, treating Green's functions, and special coordinates, of which the origin is set at the field point, are used
to calculate the bistatic- and back-scatterings. An analytic solution of backscattering with closed form is obtained and it
shows a depolarization effect. The theoretical results are in good agreement with the experimental measurements in the cases
of snow, multi- and first-year sea-ice. The root product ratio of polarization to depolarization in backscattering is equal
to 8; this result constitutes a law about polarized scattering phenomena in the nature. 相似文献