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The effect of 4,6-O-benzylidene acetals, 4,6-O-phenylboronate esters, and 4,6-O-polystyrylboronate esters on the stereoselectivity of couplings to galacto-, gluco-, and mannopyranosyl thioglycosides, otherwise protected with benzyl ethers, has been investigated by the benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride (BSP), diphenyl sulfoxide/trifluoromethanesulfonic anhydride (Ph(2)SO), and N-iodosuccinimide/trimethylsilyl trifluoromethanesulfonate (NIS/TMSOTf) methods. The BSP and Ph(2)SO methods give comparable results in all three systems whereas the NIS method affords significantly different stereoselectivities in both the gluco and manno, but not the galacto series. The benzylidene acetal and boronate esters influence the stereochemistry in a similar manner in the beta-selective manno series and the alpha-selective galacto series but show significant differences with the glucose donors. The differences between the glucose, galactose, and mannose series reflect the established differences in reactivity and, especially for mannose, those in the anomeric effect and are best interpreted in terms of changes in the relative energetics between the alpha- and beta-covalent triflate intermediates and the various contact ion pairs with which they are necessarily in equilibrium. 相似文献
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F.S. Khoo L.P. Teo 《Physics letters. [Part B]》2011,703(2):199-207
We consider the finite temperature Casimir effect of a massive fermionic field confined between two parallel plates, with MIT bag boundary conditions on the plates. The background spacetime is Mp+1×Tq which has q dimensions compactified to a torus. On the compact dimensions, the field is assumed to satisfy periodicity boundary conditions with arbitrary phases. Both the high temperature and the low temperature expansions of the Casimir free energy and the force are derived explicitly. It is found that the Casimir force acting on the plates is always attractive at any temperature regardless of the boundary conditions assumed on the compact torus. The asymptotic limits of the Casimir force in the small plate separation limit are also obtained. 相似文献
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We propose a new scheme for generating radially polarized light by mimicking optical activity using linear birefringence. It involves a birefringent spirally varying retarder sandwiched between two orthogonally oriented quarter-wave plates. Using Poincaré sphere representation, we show that the polarization transformation of such a scheme is equivalent to that of a spirally varying optical activity and is capable of generating radially polarized light. We demonstrate the proof-of-concept using y-cut crystalline quartz. 相似文献
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Silvana Alborés Paola Mora María José Bustamante María Pía Cerdeiras Laura Franco Fraguas 《Applied biochemistry and biotechnology》2014,172(4):2081-2090
A lectin was isolated from fruiting bodies of the mushroom Gymnopilus spectabilis (GSL) by ionic exchange chromatography. The lectin agglutinates mouse red cells exhibiting broad specificity towards several monosaccharides including the N-acetylneuraminic acid. Agglutination was also inhibited by the glycoproteins: fetuin, lactoferrin, and recombinant erythropoietin. GSL is a glycoprotein possessing 16 % of carbohydrates; the SDS-PAGE showed two bands with molecular mass of 52.1 and 64.4 kDa. Isoelectric focusing displayed microheterogeneity, with two bands at pIs 5.1 and 5.3. The lectin was stable between pH 2 and pH 8 while at pH 10, the agglutination decayed to 50 % of initial activity. Incubation at 40 and 80 °C led to 50 and 100 % loss in activity of the lectin, respectively. Synthesized GSL-Sepharose interacts with serum pregnant mare gonadotropin, and at least two subpopulations of this glycoprotein were separated. There was no interaction between transferrin and soluble GSL while a partial recognition was achieved with GSL-Sepharose. The terminal sialic acid seems to play an active role in modifying the interaction with GSL, depending if the lectin is in a soluble or immobilized form. The purified lectin inhibited in vitro the growth of Staphylococcus aureus and Aspergillus niger. 相似文献
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