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A heterogeneous magnetic copper catalyst was prepared via anchoring of copper sulfate onto multi‐layered poly(2‐dimethylaminoethyl acrylamide)‐coated magnetic nanoparticles and was characterized using various techniques. The catalyst was found to be active, effective and selective for one‐pot three‐component reaction of alkyl halide, sodium azide and alkyne, known as copper‐catalyzed click synthesis of 1,2,3‐triazoles. As little as 0.3 mol% of catalyst was found to be effective under the optimum conditions. The catalyst could also be recycled and reused up to seven times without significant loss of activity. Thermal stability, high loading level of copper on catalyst, broad diversity of alkyl/benzyl/allyl bromide/chloride and alkyl/aryl terminal alkynes without isolation of azide intermediate, and good to excellent yields of products make this procedure highly economical. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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Potentiometric titration of phenols with sodium methoxide in dimethylformamide, with a glass-calomel electrode system, is limited to monohydric phenols substituted with electron-attracting groups and dihydric phenols in which the two -OH groups are substituted in isolated benzene rings. Brilliant Orange has proved to be a suitable indicator in the titration of all types of mono- and dihydric phenols. Titan Yellow is recommended as indicator for the titration of carboxylic acids. Simultaneous visual titration of -OH and -COOH groups is also described. A detailed study with 62 structurally different compounds covering the various groups is reported, and a suitable procedure for the microdetermination of each class of these compounds with an error of +/- 0.2% absolute or less is presented. 相似文献
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Seyyed Javad Sabounchei Hassan Nemattalab Sadegh Salehzadeh Sima Khani Mehdi Bayat Hamid Reza Khavasi 《Polyhedron》2008
Reaction of phosphorus ylide Ph3PCHC(O)C6H4Cl (Y1) with HgX2 (X = Cl, Br and I) and ylide (p-tolyl)3PCHC(O)CH3 (Y2) with HgI2 in equimolar ratios using methanol as solvent leads to binuclear products. The bridge-splitting reaction of binuclear complex [(Y1) · HgCl2]2 by DMSO yields a mononuclear complex containing DMSO as ligand. O-coordination of DMSO is revealed by single crystal X-ray analysis in mononuclear complex of [(Y1) · HgCl2 · DMSO]. C-coordination of ylides is confirmed by X-ray structure of binuclear complex [(Y2) · HgI2]2. Characterization of the obtained compounds was also performed by elemental analysis, IR, 1H, 31P, and 13C NMR. Theoretical studies on mercury(II) complexes of Y1 show that formation of mononuclear complexes in DMSO solution in which DMSO acts as a ligand, energetically is more favorable than that of binuclear complexes. 相似文献
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A capillary electrophoretic method for the separation of the aminoglutethimide (AGT) enantiomers using methylated-β-cyclodextrin (M-β-CD) as chiral selector is described. Several parameters affecting the separation were studied, including the type and concentration of chiral selector, buffer pH, voltage and temperature. Good chiral separation of the racemic mixture was achieved in less than 9 min with resolution factor Rs = 2.1, using a fused-silica capillary and a background electrolyte (BGE) of tris-phosphate buffer solution (50 mmol L−1, pH 3.0) containing 30 mg mL−1 of M-β-CD. The separation was carried out in normal polarity mode at 25 °C, 16 kV and using hydrostatic injection. Acceptable validation criteria for selectivity, linearity, precision, and accuracy/recovery were included. The proposed method was successfully applied to the assay of AGT enantiomers in pharmaceutical formulations. The computational calculations for the inclusion complexes of the R- and S-AGT-M-β-CD rationalized the reasons for the different migration times between the AGT enantiomers. 相似文献
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To elucidate the nature of the transition-state ensemble along the reaction pathway from a nonspecific protein-DNA complex to the specific complex, we have carried out measurements of DNA bending/unbending dynamics on a cognate DNA substrate in complex with integration host factor (IHF), an architectural protein from E. coli that bends its cognate site by approximately 180 degrees . We use a laser temperature jump to perturb the IHF-DNA complex and monitor the relaxation kinetics with time-resolved FRET measurements on DNA substrates end-labeled with a FRET pair. Previously, we showed that spontaneous bending/kinking of DNA, from thermal disruption of base-pairing/-stacking interactions, may be the rate-limiting step in the formation of the specific complex (Kuznetsov, S. V.; Sugimura, S.; Vivas, P.; Crothers, D. M.; Ansari, A. Proc. Natl. Acad. Sci. USA 2006, 103, 18515). Here, we probe the effect of varying [KCl], which affects the stability of the complex, on this rate-limiting step. We find that below approximately 250 mM KCl, the observed relaxation kinetics are from the unimolecular bending/unbending of DNA, and the relaxation rate kr is independent of [KCl]. Above approximately 300 mM KCl, dissociation of the IHF-DNA complex becomes significant, and the observed relaxation process includes contributions from the association/dissociation step, with kr decreasing with increasing [KCl]. The DNA bending step occurs with a positive activation enthalpy, despite the large negative enthalpy change reported for the specific IHF-DNA complex (Holbrook, J. A.; Tsodikov, O. V.; Saecker, R. M.; Record, M. T., Jr. J. Mol. Biol. 2001, 310, 379). Our conclusion from these studies is that in the uphill climb to the transition state, the DNA is kinked, but with no release of ions, as indicated by the salt-independent behavior of k(r) at low [KCl]. Any release of ions in the unimolecular process, together with conformational changes in the protein-DNA complex that facilitate favorable interactions and that contribute to the negative enthalpy change, must occur as the system leaves the transition state, downhill to the final complex. 相似文献