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Analytical and Bioanalytical Chemistry -  相似文献   
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The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (Mn) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to Mn = 160,000 g mol?1 for PBA (based on a linear PBA calibration) and up to Mn = 70,000 g mol?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004  相似文献   
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Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   
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Intensity-dependent absorption of 25 ns excimer laser pulses in common UV-window materials was investigated. By employing a calorimetric technique which provides greatly enhanced sensitivity compared to transmissive measurements, two-photon absorption coefficients were determined at intensities of 2–80 MW/cm2 and found to be in good agreement with previous measurements at 10–100 GW/cm2. Also, color-center formation in fused silica was observed. It was possible to quantify transient and cumulative effects as a function of intensity.  相似文献   
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Peroxyoxalate chemiluminescence may be used for sensitive postcolumn detection of phenothiazine analytes separated by high performance liquid chromatography with appropriate optimization of measurement conditions such as solvent, pH and oxalate ester. Detectability of fluorescent analytes by chemical excitation varies greatly, but analytes with low oxidation potentials are generally more readily detected at low levels, as demonstrated for phenothiazines, an important class of fluorescent drugs. Some improvement in detection limits is observed for fluphenazine when chemiluminescence detection is compared to conventional fluorescence detection. Because of the specificity of chemical excitation, fewer interferences from fluorescent impurities in a urine matrix are observed.  相似文献   
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The interaction of triethylgallium (TEG) with the Ga-stabilized GaAs(100) surface in the presence of In and Al has been investigated using AES (Auger electron spectroscopy), HREELS (high resolution electron energy loss spectroscopy) and TDS (thermal desorption spectroscopy) techniques. Al is shown to greatly increase the saturation surface coverage of TEG on the surface and to suppress the desorption of TEG and diethylgallium (DEG). Etching of the surface Al by TEG is observed, resulting in the formation of gas phase Al organic species. Alkyl migration from GA to Al centres occurs, and the presence of Al substantially enhances the irreversible deposition of C. In is found to enhance DEG desorption and to lower the temperature at which absorbed ethyl groups decompose to gas phase ethene. Computer modelling has been carried out to extract kinetic parameters from measured thermal desorption spectra. These parameters are then used to calculate expected partial growth rates of GaAs during the growth of GaxAl1−xAs and GaxIn1−xAs using TEG. The data provide a molecular level understanding of the GaAs pa rtial growth rate variations arising during the deposition of III–V ternary materials.  相似文献   
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