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21.
Giovanelli E Leroux S Moisan L Carreyre H Thuéry P Buisson DA Meddour A Coustard JM Thibaudeau S Rousseau B Nicolas M Hellier P Doris E 《Organic letters》2011,13(15):4116-4119
Detailed investigations on one of the key steps of the superacidic fluorination of Vinca alkaloids that is the origin of C20' activation are reported. While two different pathways can be envisioned for the emergence of the transient secondary carbocationic intermediate, isotopic labeling experiments unambiguously revealed the involvement of a 1,2-hydride shift mechanism. 相似文献
22.
Enantioenriched 1-chloro-2-(1,3-dioxolan-2-yl)ethyllithium was generated by PhLi initiated sulfoxide-ligand exchange and deployed in situ for sequential double stereospecific reagent-controlled homologation (StReCH) of B-(2-chloro-pyrid-5-yl) pinacol boronate. This process afforded highly functionalized contiguous stereodiad motifs (typically, % ee ≥ 98%, dr ≥ 85:15) amenable to subsequent annulative transformations as demonstrated by the concise synthesis (5-7 steps) of cyclic adducts related to the analgesic alkaloid epibatidine. 相似文献
23.
Jeffrey P. Emerson Daniel A. Wright Robert A. Fisher Norman E. Phillips 《Czechoslovak Journal of Physics》1996,46(3):1209-1210
The specific heat and magnetic susceptibility of a sample of YBa2Cu3O7?δ (YBCO) was measured for 0≤δ≤0.85, 0.8≤T≤120K, and H=0, 3, 5, 7, 9T. The data show the existence of both S=1/2 and S=2 paramagnetic centers, consistent with EPR results. The δ dependences of their concentrations and of other parameters are reported. 相似文献
24.
Y. H. Zhang R. S. Qin Y. H. Sun R. W. Barber D. R. Emerson 《Journal of statistical physics》2005,121(1-2):257-267
Gas flow in microchannels can often encounter tangential slip motion at the solid surface even under creeping flow conditions.
To simulate low speed gas flows with Knudsen numbers extending into the transition regime, alternative methods to both the
Navier–Stokes and direct simulation Monte Carlo approaches are needed that balance computational efficiency and simulation
accuracy. The lattice Boltzmann method offers an approach that is particularly suitable for mesoscopic simulation where details
of the molecular motion are not required. In this paper, the lattice Boltzmann method has been applied to gas flows with finite
Knudsen number and the tangential momentum accommodation coefficient has been implemented to describe the gas-surface interactions.
For fully-developed channel flows, the results of the present method are in excellent agreement with the analytical slip-flow
solution of the Navier–Stokes equations, which are valid for Knudsen numbers less than 0.1. The present paper demonstrates
that the lattice Boltzmann approach is a promising alternative simulation tool for the design of microfluidic devices. 相似文献
25.
Clarissa O. da Silva André Gustavo H. Barbosa Emerson T. da Silva Edson Luiz L. da Silva Marco Antonio C. Nascimento 《Theoretical chemistry accounts》2004,111(2-6):231-236
In order to better understand the performance of 1,2-dimethyl-5-acetyl barbituric acid (DMB) as an amino protecting group relative to 5,5-dimethylcyclohexane-1,3-dione (DMD), ab initio calculations were performed. pKa calculations using the PCM model indicated that both molecules are more acidic in the enol form. Therefore, the protecting reaction of these molecules should involve the anions formed from the loss of a proton from the enol compounds. Contrary to what would be expected, the larger efficiency exhibited by the DMB molecule cannot be attributed to an extension of the electronic conjugation effect. In the absence of any other noticeable effect that could be responsible for the greater efficiency of the DMB molecule, we are inclined to believe that the difference could be accounted for by the presence of two independent centers of conjugation.This paper is dedicated to Jacopo Tomasi in recognition of his outstanding contribution to the field of computational chemistry in solution. The authors are honored to contribute to this volume; especially so for two of them (COS and MACN) who have the privilege of his friendship.Acknowledgements The authors would like to thank the Brazilian research agencies CNPq, CAPES and FAPERJ for the financial support. C. O. da Silva thanks the Dipartimento di Chimica e Chimica Industriale, University of Pisa, where the MCSCF calculations were performed. 相似文献
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28.
Tatiane M. Arantes Giovanni P. Mambrini Daniel G. Stroppa Edson R. Leite Elson Longo Antonio J. Ramirez Emerson R. Camargo 《Journal of nanoparticle research》2010,12(8):3105-3110
Nanocrystalline zirconium oxide was synthesized by hydrothermal treatment of ZrO(NO3)2 and ZrOCl2 aqueous solutions at different temperatures and time in presence of hydrogen peroxide. Hydrothermal treatment of zirconium salts (0.25 and 0.50 mol L?1) produced nanocrystalline monoclinic ZrO2 powders with narrow size distribution, which were formed by the attachment of the smaller particles with crystallites size of 3.5 nm, estimated by means of the Scherrer’s equation and confirmed by transmission electronic microscopy. Typical monoclinic zirconium oxide X-ray powder diffraction patterns and Raman spectra were obtained for all the crystalline powders. It was observed that the crystallization depends strongly on the temperature, resulting in amorphous material when the synthesis was realized at 100 °C, and crystalline with monoclinic phase when synthesized at 110 °C, independently of the salt used. Zirconium oxide colloidal nanoparticles were formed only at hydrothermal treatments longer than 24 h. The stability of the colloids was successfully characterized of zeta potential, showing an initial value of + 59.2 mV in acid media and isoelectric point at pH = 5.2, in good agreement with previous studies. 相似文献
29.
Monosegmented flow analysis (MSFA) has been used as a flow-batch system to produce a simple, robust, and mechanized titrator
that enables true titrations to be performed without the use of standards. This paper also introduces the use of coulometry
with monosegmented titration by proposing a versatile flow cell. Coulometric generation of the titrand is attractive for titrations
performed in monosegmented systems, because the reagent can be added without increasing the volume of sample injected. Also,
biamperomeric and potentiometric detection of titration end-points can increase the versatility of the monosegmented titrator.
The cell integrates coulometric generation of the titrand with detection of end-point by potentiometry or biamperometry. The
resulting titrator is a flow-batch system in which the liquid monosegment, constrained by the interfaces of the gaseous carrier
stream, plays the role of a sample of known volume to be titrated. The system has been used for determination of ascorbic
acid, by coulometric generation of I2 with biamperometric detection, and for determination of Fe(II), by coulometric generation of Ce(IV) with potentiometric detection
of the end-point, both in feed supplements. 相似文献
30.
We consider a bounded open set with smooth boundary \(\Omega \subset M\) in a Riemannian manifold (M, g), and suppose that there exists a non-trivial function \(u\in C({\overline{\Omega }})\) solving the problem in the distributional sense, with \(V\in L^\infty (\Omega )\), where \(u\equiv 0\) on \(\partial \Omega .\) We prove a sharp inequality involving \(||V||_{L^{\infty }(\Omega )}\) and the first eigenvalue of the Laplacian on geodesic balls in simply connected spaces with constant curvature, which slightly generalises the well-known Faber–Krahn isoperimetric inequality. Moreover, in a Riemannian manifold which is not necessarily simply connected, we obtain a lower bound for \(||V||_{L^{\infty }(\Omega )}\) in terms of its isoperimetric or Cheeger constant. As an application, we show that if \(\Omega \) is a domain on a m-dimensional minimal submanifold of \({\mathbb {R}}^n\) which lies in a ball of radius R, then
相似文献
$$\begin{aligned} -\Delta u=V(x)u, \,\, \text{ in }\,\,\Omega , \end{aligned}$$
$$\begin{aligned} ||V||_{L^{\infty }(\Omega )}\ge \left( \frac{m}{2R}\right) ^{2}. \end{aligned}$$