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31.
    
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction.  相似文献   
32.
Considering the importance of the X-ray production cross sections for the determination of the element concentrations in a given material, we have measured them experimentally for Al Si, Sc, Ti, V, Fe, Co, Ni and Cu bombarded by protons with energies ranging from 40 to 180 keV. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   
33.
Unsteady motion in single-line flow-injection systems consisting of n tubular elements with valve or hydrodynamic injection is studied theoretically. A formula for the duration of the initial period of unsteady flow is derived. This initial period is much shorter than the mean residence time of the analyte in practical systems. It can therefore be neglected in mathematical modelling of such systems. Experimental data obtained with single-line systems with valve and hydrodynamic injection confirmed the validity of the theoretical equations.  相似文献   
34.
Summary The adsorption of gaseous molecular iodine on clean silver surfaces proceeds in the first stage by dissociative chemisorption. After the formation of half a monolayer of chemisorbed iodine atoms the formation of silver iodide begins, which forms a very regular overlayer on top of the substrate. Both iodine species can be distinguished due to a difference in chemical shift of the M4N4, 5N4, 5-Auger transitions. After completion of this overlayer further iodine uptake is slowed down significantly. Above an overlayer thickness of about 10 nm a further progress of the reaction cannot be followed anymore due to the limited information depth of XPS.  相似文献   
35.
We consider the plane-strain buckling of a cylindrical shellof arbitrary thickness which is made of a Varga material andis subjected to an external hydrostatic pressure on its outersurface. The WKB method is used to solve the eigenvalue problemthat results from the linear bifurcation analysis. We show thatthe circular cross-section buckles into a non-circular shapeat a value of µ1 which depends on A1/A2 and a mode number,where A1 and A2 are the undeformed inner and outer radii, andµ1 is the ratio of the deformed inner radius to A1. Inthe large mode number limit, we find that the dependence ofµ1 on A1/A2 has a boundary layer structure: it is constantover almost the entire region of 0 < A1/A2 < 1 and decreasessharply from this constant value to unity as A1/A2 tends tounity. Our asymptotic results for A1 – 1 = O(1) and A1– 1 = O(1/n) are shown to agree with the numerical resultsobtained by using the compound matrix method.  相似文献   
36.
37.
We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules are observed to attain the perpendicular orientation at monolayer coverage. Dedicated to Professor C N R Rao on his 70th birthday  相似文献   
38.
A one-dimensional bulk reaction model for the oxidation of nickeltitanium is formulated, with preferential oxidation of titaniumbeing included. The modelling is directed at the better understandingof the dominant mechanisms involved in the oxidation processand their significance for the biocompatibility of the alloy.Two different regimes for the relative diffusivities of oxygenand the metals are investigated. By assuming fast bulk reactions,different asymptotic structures emerge in different parameterregimes and the resulting models take the form of moving boundaryproblems. Different profiles of nickel concentration are obtained:in particular a nickel-rich layer (observed in practice) ispresent below the oxide/metal interface for the case when oxygenand the metals diffuse at comparable rates.  相似文献   
39.
In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003  相似文献   
40.
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