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971.
Tris(pentafluorophenyl)gallium ( 3 ) and aluminum ( 7 ) are active coinitiators for the production of medium‐high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Brønsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet ( 5 and 8 , respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron ( 2 ), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2‐C6F4[B(C6F5)2]2, 1 ) or diborole (1,2‐C6F4[9‐BC12F8]2, 6 ). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc ( 4 ). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   
972.
973.
974.
For graphene to achieve its full scientific and commercial potential, reliable mass production of the material on the multi-tonne scale is essential. We have investigated five samples of graphene obtained from commercial sources that state they can supply the product on the tonne scale per annum. From electron microscopy at the micrometre to the nanometre scale, and neutron vibrational spectroscopy, we find that none of the materials examined were 100 % isolated graphene sheets. In all cases, there was a substantial content of graphite-like material. The samples exhibited varying oxygen contents, this could be present as carboxylic acid (although other oxygenates, quinones, phenols may also be present) or water. We emphasise that INS spectroscopy is particularly useful for the investigation of inorganic materials that will be used commercially: it provides atomic scale information from macroscopic (10’s of g) amounts of sample, thus ensuring that the results are truly representative.  相似文献   
975.
The diffusion‐thermo and thermal‐diffusion effects on heat and mass transfer by mixed convection boundary layer flow over a vertical isothermal permeable surface embedded in a porous medium were studied numerically in the presence of chemical reaction with temperature‐dependent viscosity. The governing nonlinear partial differential equations are transformed into a set of coupled ordinary differential equations, which are solved numerically by using Runge–Kutta method with shooting technique. Numerical results are obtained for the velocity, temperature and concentration distributions, and the local skin friction coefficient, local Nusselt number and local Sherwood number for several values of the parameters, namely, the variable viscosity parameter, suction/injection parameter, Darcy number, chemical reaction parameter, and Dufour and Soret numbers. The obtained results are presented graphically and in tabulated form, and the physical aspects of the problem are discussed. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   
976.
977.
A facile strategy has been developed to synthesize double‐shelled Zn(OH)2 nanoflowers (DNFs) at room temperature. The nanoflowers were generated via conversion of Cu2O nanoparticles (NPs) using ZnCl2 and Na2S2O3 by a simple process. Outward diffusion of the Cu2+, produced by an oxidation process on the surface of NPs, and the inward diffusion of Zn2+ by coordination and migration, eventually lead to a hollow cavity in the inner NPs with a double‐shelled 3D hollow flower shapes. The thickness of the inner and outer shells is estimated to be about 20 nm, and the thickness of nanopetals is about 7 nm. The nanoflowers have large surface areas and excellent adsorption properties. As a proof of potential applications, the DNFs exhibited an excellent ability to remove organic molecules from aqueous solutions.  相似文献   
978.
Biooxidation of benzoic acid by Ralstonia eutropha B9 provides an unusual cyclohexadiene carboxy diol that contains a quaternary stereocentre. Tricarbonyliron derivatives of this chiron, on treatment with acid, give two isomeric η5‐cyclohexadienyl complexes as observed by NMR spectroscopy. Both of these can be subjected to the addition of nucleophiles to provide isomeric cyclohexadiene complexes with new substituent patterns, several of which have been characterised crystallographically. De‐metallation of these provides a versatile library of cyclohexadiene building blocks, the utility of which is demonstrated by formal syntheses of oseltamivir. The mechanism of product formation and its stereochemical implications are discussed, as are the procedures undertaken to establish the enantiopurity of a representative cyclohexadiene product.  相似文献   
979.

Accurate computation of the evolution of a (typically curved) detonation front in a complex geometry, and of the state behind it, is a practical problem in the design of devices that use high-energy explosives. Direct numerical simulations are infeasible: accuracy demands high resolution of the smallest scale (the reaction zone), which is typically several orders of magnitude smaller than the device scale. Programmed burn is an engineering alternative that has been shown to produce acceptable results at a fraction of the cost. The underlying algorithm prescribes the trajectory of the detonation front a priori and replaces the actual reaction zone by a mock up that is a few computational cells thick and in which the reaction rate is taken to be a constant. The state of the explosive at the end of the reaction zone is thereby computed at a relatively modest cost, and the bulk of the computational effort is reserved for the region behind the reaction zone wherein the products of detonation perform useful work. The reasons for the remarkable fidelity to which the physical situation is captured by the programmed burn are not well-understood. This investigation, aimed at achieving such an understanding, considers a model problem for a steady, curved detonation propagating down a rate stick. It examines the pseudo-reaction-zone structure of the programmed burn, studies the sensitivity of the state of the reaction products to the choice of the reaction zone length, and compares the results to those for the actual, physical reaction zone. Conclusions are drawn as to the causes behind the success of the programmed-burn algorithm. The analysis is based on the asymptotic limits of small front curvature and small departures from the Chapman–Jouguet speed. Results are presented for ideal as well as nonideal explosives.  相似文献   
980.
The effects of material interface curvature on deflagration of a homogeneous solid energetic material (EM) is studied in a limit when the radius of curvature is much larger than the deflagration front thickness. Under the assumption of quasi-steady burning, a method of matched asymptotics is employed do derive first-order curvature corrections to the mass flux across the gas–solid interface as well as to the interface temperature. As an illustration, a problem of quasi-steady spherical particle deflagration is solved numerically and the simulation results are used to verify those obtained through asymptotic analysis. An algorithm for a fully-coupled unsteady solver suitable for EM deflagration simulation is presented. Numerical solution of the unsteady spherical particle deflagration is used to show that the assumption of quasi-steady deflagration is valid.  相似文献   
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