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81.
López-Mejías V Knight JL Brooks CL Matzger AJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(12):7575-7579
The phase-selective crystallization of acetaminophen (ACM) using insoluble polymers as heteronuclei was investigated in a combined experimental and computational effort to elucidate the mechanism of polymer-induced heteronucleation (PIHn). ACM heteronucleates from supersaturated aqueous solution in its most thermodynamically stable monoclinic form on poly(n-butyl methacrylate), whereas the metastable orthorhombic form is observed on poly(methyl methacrylate). When ACM crystals were grown through vapor deposition, only the monoclinic polymorph was observed on each polymer. Each crystallization condition leads to a unique powder X-ray diffraction pattern with the major preferred orientation corresponding to the crystallographic faces in which these crystal phases nucleate from surfaces of the polymers. The molecular recognition events leading to these outcomes are elucidated with the aid of computed polymer-crystal binding energies using docking simulations. This investigation illuminates the mechanism by which phase selection occurs during the crystallization of ACM using polymers as heteronuclei, paving the way for the improvement of methods for polymorph selection and discovery based on heterogeneous nucleation promoters. 相似文献
82.
Sankar M Nowicka E Tiruvalam R He Q Taylor SH Kiely CJ Bethell D Knight DW Hutchings GJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(23):6524-6532
In the solvent-free oxidation of benzyl alcohol to benzaldehyde using supported gold-palladium nanoparticles as catalysts, two pathways have been identified as the sources of the principal product, benzaldehyde. One is the direct catalytic oxidation of benzyl alcohol to benzaldehyde by O(2), whereas the second is the disproportionation of two molecules of benzyl alcohol to give equal amounts of benzaldehyde and toluene. Herein we report that by changing the metal oxide used to support the metal-nanoparticles catalyst from titania or niobium oxide to magnesium oxide or zinc oxide, it is possible to switch off the disproportionation reaction and thereby completely stop the toluene formation. It has been observed that the presence of O(2) increases the turnover number of this disproportionation reaction as compared to reactions in a helium atmosphere, implying that there are two catalytic pathways leading to toluene. 相似文献
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Hammond C Lopez-Sanchez JA Ab Rahim MH Dimitratos N Jenkins RL Carley AF He Q Kiely CJ Knight DW Hutchings GJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(15):3927-3937
The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed. 相似文献
85.
Type-I coil planet centrifuge produces a uniformly circulating centrifugal force field to produce vortex motion of two immiscible solvent phases in a cylindrical cavity of the separation column to perform efficient countercurrent chromatography. The partition efficiency obtained from the original vortex column was substantially improved by threading the cylindrical cavity to increase the area of mass transfer between the two phases. Partition efficiency of the threaded column was evaluated by three different two-phase solvent systems with a broad range of hydrophobicity each with a set of suitable test samples. Overall results of the present studies indicated that the threaded cylindrical column substantially improves the partition efficiency in terms of theoretical plate number, peak resolution, and height equivalent of one theoretical plate. The results also indicated that higher peak resolution is produced by eluting either the upper phase in the head to tail direction or the lower phase in the reversed direction. When there is a choice in the mobile phase, a better separation is achieved by using the less viscous phase as the mobile phase. Since the present system gives extremely low column pressure, it may be a potential alternative to the conventional type-J HSCCC system for a large-scale preparative separation. 相似文献
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A computational study is performed to examine the influence of pulsed energy deposition on a cylinder in supersonic flow.
A code is written to solve the compressible Navier–Stokes equations. The energy deposition is modeled as a high temperature,
low density filament introduced at the inflow boundary, and the frequency of energy deposition pulses is varied. It is shown
that the energy deposition reduces both the average drag and the average heat transfer to the front face of the cylinder.
The effectiveness of drag reduction is shown to be inversely proportional to the energy deposition pulsation period. The efficiency
of drag reduction is shown to be approximately 100. The average heat transfer to the face is reduced from the steady state,
with a maximum reduction of 30%. 相似文献
89.
本文结合新经济地理学K关联的思想构造了外部技术创新溢出指数模型,在此基础上运用2006~2014年中国30个省级行政区的面板数据对中国区域间技术创新空间溢出效应进行了实证研究,结果表明:(1)全国技术创新溢出效应主要是东部地区带动的,东部地区的省份对东部、中部和西部地区其他省份存在技术创新溢出效应,而中部和西部并没有对其他地区技术创新产生溢出效应,并且中部地区和西部地区内部各省之间存在竞争效应。(2)无论是全国还是东部、中部和西部地区,R&D经费、R&D人员和知识存量均对技术创新产生正向作用,并且这些地区的技术创新产出均处于规模报酬递减阶段,不同的是,全国、东部和中部地区R&D人员对技术创新的贡献比R&D资本要大,而西部地区R&D资本对技术创新的贡献则要大于R&D人员。 相似文献
90.