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排序方式: 共有526条查询结果,搜索用时 15 毫秒
1.
2.
Robert WeavingEmmanuel Roulland Claude MonneretJean-Claude Florent 《Tetrahedron letters》2003,44(12):2579-2581
A synthesis of the alkylidene cyclopentenone prostaglandin TEI 9826 has been realized. The synthesis involved the preparation of the chiral 1,5-diene 8 using a stereoselective Claisen rearrangement from the allylic alcohol 6 giving the ester 7 after vinylation. Then a key RCM reaction allowed the preparation of the cyclopentenol 9 which, after oxidation, gave the cyclopentenone 10, precursor of the prostaglandin. 相似文献
3.
The 2,2'-azobis(isobutyronitrile)(AIBN)-induced autoxidation of gamma-terpinene (TH) at 50 degrees C produces p-cymene and hydrogen peroxide in a radical-chain reaction having HOO* as one of the chain-carrying radicals. The kinetics of this reaction in cyclohexane and tert-butyl alcohol show that chain termination involves the formal HOO. + HOO. self-reaction over a wide range of gamma-terpinene, AIBN, and O2 concentrations. However, in acetonitrile this termination process is accompanied by termination via the cross-reaction of the terpinenyl radical, T., with the HOO. radical under conditions of relatively high [TH] (140-1000 mM) and low [O2] (2.0-5.5 mM). This is because the formal HOO. + HOO. reaction is comparatively slow in acetonitrile (2k approximately 8 x 10(7) M(-1) s(-1)), whereas, this reaction is almost diffusion-controlled in tert-butyl alcohol and cyclohexane, 2k approximately 6.5 x 10(8) and 1.3 x 10(9) M(-1) s(-1), respectively. Three mechanisms for the bimolecular self-reaction of HOO. radicals are considered: 1) a head-to-tail hydrogen-atom transfer from one radical to the other, 2) a head-to-head reaction to form an intermediate tetroxide, and 3) an electron-transfer between HOO. and its conjugate base, the superoxide radical anion, O2-.. The rate constant for reaction by mechanism (1) is shown to be dependent on the hydrogen bond (HB) accepting ability of the solvent; that by mechanism (2) is shown to be too slow for this process to be of any importance; and that by mechanism (3) is dependent on the pH of the solvent and its ability to support ionization. Mechanism (3) was found to be the main termination process in tert-butyl alcohol and acetonitrile. In the gas phase, the rate constant for the HOO. + HOO. reaction (mechanism (1)) is about 1.8 x 10(9) M(-1) s(-1) but in water at pH< or =2 where the ionization of HOO. is completely suppressed, this rate constant is only 8.6 x 10(5) M(-1) s(-1). The very large retarding effect of water on this reaction has not previously been explained. We find that it can be quantitatively accounted for by using Abraham's HB acceptor parameter, beta(2)(H), for water of 0.38 and an estimated HB donor parameter, alpha(2)(H), for HOO. of about 0.87. These Abraham parameters allow us to predict a rate constant for the HOO. + HOO. reaction in water at 25 degrees C of 1.2 x 10(6) M(-1) s(-1) in excellent agreement with experiment. 相似文献
4.
An experimental investigation of the frequency response of electrochemical probes to transversal velocity fluctuation is reported. The study has been focused on wall shear stress for a modulated flow due to an oscillating cylinder along its own axes since the wall shear stress has been first numerically determined for this flow. Results indicate that a frequency response correction to probe outputs is required and that this correction depends on the amplitude of fluctuations.List of symbols
A
total area of the electrode
-
A
i
area of the part i of the electrode
-
a
amplitude of oscillation
-
C
concentration
-
c
fluctuation of concentration
-
D
cylinder diameter
-
D
diffusion coefficient
-
h
dimensionless velocity normal to the wall
-
H
transfer function modulus
-
K
i
transfer coefficient
-
l
electrode length
-
n
frequency
-
S
wall shear
-
S
fluctuation of the wall shear
-
U
mean value of the fluid velocity far from the wall
-
u
streamwise component of the fluid velocity
-
spanwise component of the fluid velocity (along the cylinder axis)
-
w
component of the fluid velocity perpendicular to the wall
-
x
direction of the mean flow
-
y
direction parallel to the cylinder axis
-
z
direction perpendicular to the wall
-
v
kinematic viscosity
-
dimensionless distance perpendicular to the wall (z)
-
dimensionless distance (x)
-
phase shift
-
azimuthal angle
-
modulation frequency 相似文献
5.
Florent Renac 《Journal of computational physics》2011,230(14):5739-5752
An algorithm for stabilizing linear iterative schemes is developed in this study. The recursive projection method is applied in order to stabilize divergent numerical algorithms. A criterion for selecting the divergent subspace of the iteration matrix with an approximate eigenvalue problem is introduced. The performance of the present algorithm is investigated in terms of storage requirements and CPU costs and is compared to the original Krylov criterion. Theoretical results on the divergent subspace selection accuracy are established. The method is then applied to the resolution of the linear advection–diffusion equation and to a sensitivity analysis for a turbulent transonic flow in the context of aerodynamic shape optimization. Numerical experiments demonstrate better robustness and faster convergence properties of the stabilization algorithm with the new criterion based on the approximate eigenvalue problem. This criterion requires only slight additional operations and memory which vanish in the limit of large linear systems. 相似文献
6.
B. Lott J. L. Charvet E. Crema G. Duchêne H. Doubre J. Fréhaut J. Galin B. Gatty D. Guerreau G. Ingold D. Jacquet U. Jahnke D. X. Jiang C. Magnago M. Morjean Y. Patin E. Piasecki J. Pouthas Y. Pranal F. Saint-Laurent E. Schwinn A. Sokolov J. L. Uzureau X. M. Wang 《Zeitschrift für Physik A Hadrons and Nuclei》1993,346(3):201-208
Inclusive neutron multiplicity distributions were measured by means of 4π liquid-scintillator detectors for Ar and Kr-induced reactions at 44 MeV/nucleon and 32 MeV/nucleon, respectively. For all the systems studied, the observed distributions exhibit a bump structure at large multiplicity, corresponding to highly dissipative collisions. For Ar-induced reactions, the excitation energies necessary to explain the most probable neutron multiplicity associated with these dissipative collisions are estimated, the correspondence between excitation energy and neutron multiplicity being calculated in the framework of the statistical model. The so-obtained values of excitation energies, which are systematically lower than those predicted using the massive-transfer picture, are discussed. 相似文献
7.
B. Sitamtze Youmbi Serge Zékeng Samuel Domngang Florent Calvayrac Alain Bulou 《Ionics》2012,18(4):371-377
To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO3 oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO)
Li3x La( 2 \mathord