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Guy Bayada 《Journal of Mathematical Analysis and Applications》2003,282(1):212-231
The asymptotic behaviour of a Stokes flow with Tresca free boundary friction conditions when one dimension of the fluid domain tends to zero is studied. A specific Reynolds equation associated with variational inequalities is obtained and uniqueness is proved. 相似文献
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Guy Schmitz 《国际化学动力学杂志》2007,39(1):17-21
At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate–bromide reaction that becomes ?d[BrO3?]/dt = [BrO3?][H+]2(k1[Br?] + k2[Br?]2). In perchloric solutions at 25°C, k1 = 2.18 dm3 mol?3 s?1 and k2 = 0.65 dm4 mol?4 s?1 at 1 M ionic strength and k1 = 2.60 dm3 mol3 s?1and k2 = 1.05 dm4 mol?4 s?1 at 2 M ionic strength. A mechanism explaining this rate law, with Br2O2 as key intermediate species, is proposed. Errors that may occur when using the Guggenheim method are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 17–21, 2007 相似文献
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Girard V Farrenq R Sorokin E Sorokina IT Guelachvili G Picqué N 《Chemical physics letters》2006,419(4-6):584-588
The spectral dynamics of a mid-infrared multimode Cr(2+):ZnSe laser located in a vacuum sealed chamber containing acetylene at low pressure is analyzed by a stepping-mode high-resolution time-resolved Fourier transform interferometer. Doppler-limited absorption spectra of C(2)H(2) in natural isotopic abundance are recorded around 4000 cm(-1) with kilometric absorption path lengths and sensitivities better than 3 10(-8) cm(-1). Two cold bands are newly identified and assigned to the ν(1)+ν(4) (1) and ν(3)+ν(5) (1) transitions of (12)C(13)CH(2). The ν(1)+ν(5) (1) band of (12)C(2)HD and fourteen (12)C(2)H(2) bands are observed, among which for the first time ν(2)+2ν(4) (2)+ν(5) (-1). 相似文献
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This study provides a stability theory for the nonlinear least-squares formulation of estimating the diffusion coefficient in a two-point boundary-value problem from an error-corrupted observation of the state variable. It is based on analysing the projection of the observation on the nonconvex attainable set.This research was started while G. Chavent visited the Technical University of Graz. Support through the Steiermaerkische Landesregierung is gratefully acknowledged. 相似文献
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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
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Serge Palacin Christophe Bureau Julienne Charlier Guy Deniau Brigitte Mouanda Pascal Viel 《Chemphyschem》2004,5(10):1468-1481
Electrografting is a powerful and versatile technique for modifying and decorating conducting surfaces with organic matter. Mainly based on the electro-induced polymerization of dissolved electro-active monomers on metallic or semiconducting surfaces, it finds applications in various fields including biocompatibility, protection against corrosion, lubrication, soldering, functionalization, adhesion, and template chemistry. Starting from experimental observations, this Review highlights the mechanism of the formation of covalent metal-carbon bonds by electro-induced processes, together with major applications such as derivatization of conducting surfaces with biomolecules that can be used in biosensing, lubrication of low-level electrical contacts, reversible trapping of ionic waste on reactive electrografted surfaces as an alternative to ion-exchange resins, and localized modification of conducting surfaces, a one-step process providing submicrometer grafted areas and which is used in microelectronics. 相似文献
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A phenanthridinium salt was prepared in four steps, including an intramolecular CH-arylation and a hydride abstraction reaction. Treatment with sterically demanding bases does not lead to the corresponding carbene, but rather to addition products: the planar-constrained geometry significantly enhances the electrophilicity over the acidity of C-aryl iminium salts. 相似文献