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61.
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   
62.
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   
63.
64.
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   
65.
A. H. Ahmad  A. K. Arof 《Ionics》2004,10(3-4):200-205
Different amounts of Li3PO4 were mixed to a fixed ratio of LiI:Li2WO4, ground and pelletised before subjected to sintering at 70°C for 7 days. XRD shows that the product formed after sintering process is most likely Li6P4W8O32 due to peaks present at 10.6°, 22.4°, 24.0°, 24.4, 26.2°, 32.4° and 34.0°. Conductivity studies show that the sample with 25 wt.% Li3PO4 exhibits the highest room temperature conductivity of 3.42×10−3 Scm−1. Conductivity is expected to occur through channel-like structures which could have formed due to corner or edge sharing of polyhedra. FTIR studies have shown the existence of WO4 tetrahedra and WO6 octahedral at 850 cm−1 and 952 cm−1, and phosphate tetrahedral at 564 cm−1, 700 cm−1, 890 cm−1 and 1030 cm−1.  相似文献   
66.
The invariance of the geometric mean G with respect to the Lagrangian mean-type mapping (Lf,Lg), i.e. the equation G○(Lf,Lg)=G, is considered. We show that the functions f and g must be of high class regularity. This fact allows to reduce the problem to a differential equation and determine the second derivatives of the generators f and g.  相似文献   
67.
In the paper we indicate an error made in the proof of the main result of the paper [M.A. Darwish, On quadratic integral equation of fractional orders, J. Math. Anal. Appl. 311 (2005) 112-119]. Moreover, we provide correct proof of a slightly modified version of the mentioned result. The main tool used in our proof is the technique associated with the Hausdorff measure of noncompactness.  相似文献   
68.
In this paper we deal with nonlinear second-order boundary value problems with impulses. The impulsive functions depend implicitly on the different considered variables and the boundary value conditions are nonlinear. In both cases functional dependence on the solution is allowed. The existence results follow from the existence of a pair of well-ordered lower and upper solutions.  相似文献   
69.
We study linear dynamical systems with multidimensional time in Banach spaces. Using Taylor functional calculus we prove that under additional assumptions hyperbolic systems have shadowing property.  相似文献   
70.
A Fubini theorem     
Let I0 be the σ-ideal of subsets of a Polish group generated by Borel sets which have perfectly many pairwise disjoint translates. We prove that a Fubini-type theorem holds between I0 and the σ-ideals of Haar measure zero sets and of meager sets. We use this result to give a simple proof of a generalization of a theorem of Balcerzak-Ros?anowski-Shelah stating that I0 on N2 strongly violates the countable chain condition.  相似文献   
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