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We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides. 相似文献
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Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
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D. Sornette 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,3(1):125-137
We propose a formulation of the term structure of interest rates in which the forward curve is seen as the deformation of
a string. We derive the general condition that the partial differential equations governing the motion of such string must
obey in order to account for the condition of absence of arbitrage opportunities. This condition takes a form similar to a
fluctuation-dissipation theorem, albeit on the same quantity (the forward rate), linking the bias to the covariance of variation
fluctuations. We provide the general structure of the models that obey this constraint in the framework of stochastic partial
(possibly non-linear) differential equations. We derive the general solution for the pricing and hedging of interest rate
derivatives within this framework, albeit for the linear case (we also provide in the appendix a simple and intuitive derivation
of the standard European option problem). We also show how the “string” formulation simplifies into a standard N-factor model under a Galerkin approximation.
Received: 30 January 1998 / Revised: 12 February 1998 / Accepted: 16 February 1998 相似文献
117.
A linear three‐dimensional hydrodynamical numerical model, with the application of the Galerkin Method for the vertical dependence, is here presented. The spherical coordinate system is used, in order to allow large‐scale simulations. The equations and mathematical development of the model are shown in detail, together with the boundary and initial conditions, and the sequence of equations' solution. The model is applied to the South Atlantic Ocean, for estimating typical seasonal circulations, and the results are summarized in maps of currents at surface and 1000 m depth, and in transport values of the Brazil Current between 30°S and 40°S. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
118.
James B. Hartle 《International Journal of Theoretical Physics》2006,45(8):1390-1396
Familiar quantum mechanics assumes a fixed spacetime geometry. Quantummechanics must therefore be generalized for quantum gravity where spacetime geometry is not fixed but rather a quantum variable. This extended abstract sketches a fully fourdimensional generalized quantum mechnics of cosmological spacetime geometries that is one such generalization.This contribution to the proceedings of the Glafka Conference is an extended abstract of the author's talk there. More details can be found in the references cited at the end of the abstract expecially (Hartle, 1995). 相似文献
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