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11.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
12.
M. Dubé C. Daneault V. Vuorinen M. Alava M. Rost 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,56(1):15-26
We investigate the structure and dynamics of the interface between
two immiscible liquids in a three-dimensional disordered porous
medium. We apply a phase-field model that includes explicitly
disorder and discuss both spontaneous and forced imbibition.
The structure of the interface is dominated by a length scale
ξ× which arises from liquid conservation. We further show
that disorder in the capillary and permeability act on different
length scales and give rise to different scalings and
structures of the interface properties. We conclude with a
range of applications. 相似文献
13.
Due to the hot, arid nature of its bordering lands, seawater in the Arabian Gulf can have significant evaporation rates leading to hypersaline conditions. If additional desalination plants were to operate along its coast, then the extraction of desalinated water and returned brine waste stream into the Gulf would increase the salinity. This paper uses a tidally and cross-sectionally averaged mathematical model that reveals multiplicative dependence of the salinity on factors associated with river flow, evaporation rates and each of the desalination plants. Present-day desalinated water production rates are in the linear regime, but hypersalinity has exponential sensitivity to the position and volumetric rate of desalinated water extraction. 相似文献
14.
Anton Deitmar 《数学年刊B辑(英文版)》2007,28(4):463-474
Abstract In this paper, Lefschetz formulae for torus actions on p-adic groups are proven. These are similar to comparable formulae for real Lie groups. Applications lie in the realm of dynamical
zeta functions. 相似文献
15.
We investigate the rate of convergence of the Wong-Zakai approximations for second-order stochastic PDEs of parabolic type
driven by a multi-dimensional Wiener
process W.
The title of this article in the online version was published incorrectly. The correct title appears above. Springer regrets
the error. The online version of the original article can be found at 相似文献
16.
Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends. 相似文献
17.
For any self-adjoint realization S of a singular Sturm-Liouville equation on an interval (a,b) with limit-circle endpoints, we construct a family of self-adjoint realizations S r ,r ∈ (0,∞), of this equation on subintervals (a r ,b r ) of (a,b) such that every eigenvalue of S is the limit of a continuous eigenvalue branch of this family. Of particular interest are the cases when at least one endpoint is oscillatory or the leading coefficient function changes sign. In these cases, we show that the index determining each continuous eigenvalue branch has an infinite number of jump discontinuities and give an explicit characterization of these discontinuities. 相似文献
18.
19.
Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature. 相似文献
20.
Ecaterina Stela Dragan Marcela Mihai Anton Airinei 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):5898-5908
The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, 1H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006 相似文献