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The additions of various five-membered ring aminoheterocycles to α-cyanocinnamonitriles were studied. Regiochemistry of product formation can in most cases be controlled by choosing the appropriate electrophile. An α-cyanocinnamonitrile with an additional β-leaving group normally provides products arising from initial attack of the ring amino group, while exo attack predominates in the case of the parent α-cyanocinnamonitrile. Aminopyrazole and aminoindazole provide only exo products with either electrophile. Product assignments were made via X-ray and 2D NMR methods; these assignments serve as a benchmark to several literature references and to future investigations of conjugate additions of these nucleophiles.  相似文献   
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Statistical heteroporosity theory is applied to the case of ultrafiltration across a membrane composed of an array of independent channels or pores. The primary question addressed is: For given values of the reflection coefficient σ, and diffusive permeability Ps, measured independently for a membrane of unknown heteroporosity, how accurately can the rejection coefficient R be predicted by using the Spiegler—Kedem expression for rejection, derived without concern for heteroporosity? For the case of applied pressure much greater than back-osmotic pressure, limits are analytically derived which show a maximum 30% relative error in R at σ → 0, and a maximum absolute error of 0.06 at σ ? 0.5. Experimental regions where heteroporosity effects should be largest are given explicitly. It appears that, except for these regions, the Spiegler—Kedem equation can be used to describe accurately rejection across membranes of arbitrary heteroporosity. p]For the case of appreciable solute concentration in the feedstream, a proposed test of heteroporosity consists of measurements of rejection vs. volume flux, at small and large solute concentrations. For a particular model of membrane structure called the two-pipe model it is shown that, in principle, heteroporosity can result in significant changes of rejection with concentration at a given volume flow, but for three real membranes used as examples the effects are predicted to be relatively small.  相似文献   
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Analytical and Bioanalytical Chemistry - In this work we describe a very fast and flexible method for fabrication of plasmon-supporting substrates with micro-patterning capability, which is...  相似文献   
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We describe a multi-purpose platform for the three-dimensional cultivation of tissues. The device is composed of polymer chips featuring a microstructured area of 1-2 cm(2). The chip is constructed either as a grid of micro-containers measuring 120-300 x 300 x 300 microm (h x l x w), or as an array of round recesses (300 microm diameter, 300 microm deep). The micro-containers may be separately equipped with addressable 3D-micro-electrodes, which allow for electrical stimulation of excitable cells and on-site measurements of electrochemically accessible parameters. The system is applicable for the cultivation of high cell densities of up to 8 x 10(6) cells and, because of the rectangular grid layout, allows the automated microscopical analysis of cultivated cells. More than 1000 micro-containers enable the parallel analysis of different parameters under superfusion/perfusion conditions. Using different polymer chips in combination with various types of bioreactors we demonstrated the principal suitability of the chip-based bioreactor for tissue culture applications. Primary and established cell lines have been successfully cultivated and analysed for functional properties. When cells were cultured in non-perfused chips, over time a considerable degree of apoptosis could be observed indicating the need for an active perfusion. The system presented here has also been applied for the differentiation analysis of pluripotent embryonic stem cells and may be suitable for the analysis of the stem cell niche.  相似文献   
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The combination of ZnEt2 and chiral pyridinebisoxazoline (pybox) or pyridinebisimidazoline (pybim) ligands catalyzed the asymmetric hydrosilylation of aryl, alkyl, cyclic, heterocyclic, and aliphatic ketones. Under mild conditions, high yields and good enantioselectivities were achieved. ESI measurements allowed for the characterization of the active catalyst.  相似文献   
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