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Alexei Yu. Lukin Sergei V. Shevyakov Alexei V. Laptev Olga I. Davydova Vitali I. Shvets Olga V. Demina Yury P. Strokach Valery A. Barachevsky Michail V. Alfimov Sergei P. Gromov Artem I. Vedernikov Johan Lugtenburg Andrey A. Khodonov 《Journal of inclusion phenomena and macrocyclic chemistry》2004,49(1-2):153-161
An effective synthetic approach to the preparation of a new crown-ether vinylogs involving the Horner–Emmons olefination of carbonyl precursors with the use of C2- and C5-phosphonates was proposed. The effects of the conjugation chain length and the nature of the terminal polar functions in the phosphonate reagent on the yield and process stereoselectivity were discussed. 相似文献
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Kirilyuk IA Bobko AA Khramtsov VV Grigor'ev IA 《Organic & biomolecular chemistry》2005,3(7):1269-1274
A series of 4-dialkylamino-2,5-dihydroimidazole nitroxides with pyridine-4-yl, 4-dimethylaminophenyl or 4-hydroxyphenyl groups in position 2 of the imidazole ring were prepared using the reaction of RMgBr with corresponding 5-dialkylamino-4,4-dimethyl-4H-imidazole 3-oxides. The EPR spectra of the nitroxides were shown to be pH-sensitive due to consecutive protonation of the amidino moiety and the basic group(s) at position 2 of the imidazole ring. The 5,5-dimethyl-4-(dimethylamino)-2-ethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl showed a monotonic increase in the isotropic nitrogen hyperfine (hfi) coupling constant alpha(N) of 1 .4 G over a pH range from 2 to 6.5. Such a broad range of pH-sensitivity could be useful for many biophysical and biomedical applications, including pH-monitoring in the stomach. 相似文献
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A microwave-assisted click chemistry synthesis of 1,4-disubstituted 1,2,3-triazoles via a copper(I)-catalyzed three-component reaction 总被引:4,自引:0,他引:4
A microwave-assisted three-component reaction was used to prepare a series of 1,4-disubstituted-1,2,3-triazoles from corresponding alkyl halides, sodium azide, and alkynes. This procedure eliminates the need to handle organic azides, as they are generated in situ, making this already powerful click process even more user-friendly and safe. 相似文献
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Experimental measurements of Tg for two series of lower homologues of polyethyleneoxide. differing in their end-groups, are discussed in terms of existing theories. Simple free-volume considerations predicting linear dependence of Tg on (molecular weight)?1 are inadequate in systems with end-groups capable of specific interactions (hydrogen bonding). Thermodynamic arguments show that the true Tg of infinitely long PEO chain is 220 ± 5°K. Suitable modification of parameters of the Gibbs-DiMarzio equations to account for the dependence of the free volume fraction on the concentration of end-groups results in good fit of the experimental data for hydroxyl-terminated samples and correctly predicts Tg(∞). Analysis of the data for chlorine-substituted oligomers suggests the existence of specific intermolecular interactions in the latter, involving chlorine atoms. 相似文献
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Immunoassays have traditionally relied on antibodies as diagnostic probes. Their use outside of a laboratory, however, may be problematic because antibodies are often unstable in severe environmental conditions. Environmental monitoring requires thermostable probes, such as landscape phage, that carry thousands of foreign peptides on their surfaces, are superior to antibodies, and can operate in non-controlled conditions. While parent wild-type phage are known to be extremely stable in various media at high temperatures, no work has been done to demonstrate the stability of landscape phage probes. We examined the thermostability of a landscape phage probe and a monoclonal antibody specific for -galactosidase in parallel in an enzyme-linked immunosorbent assay (ELISA) format. They were both stable for greater than six months at room temperature, but at higher temperatures the antibody degraded more rapidly than the phage probe. Phage retained detectable binding ability for more than six weeks at 63 °C, and three days at 76 °C. The activation energy of phage degradation was determined to be 1.34×105 J/mol. These results confirm that phage probes are highly thermostable and can function even after exposure to high temperatures during shipping, storage and operation. 相似文献
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A number of anthranilamide and 2-aminobenzenesulfonamide derivatives with aromatic aldehydes and 1,3-dicarbonyl compounds were synthesized. Substituted benzaldehyde derivatives of neither aminoamides showed tautomerism in solutions. Reaction products of 2-aminobenzenesulfonamide with p-substituted benzoylacetic aldehydes and p-substituted benzoylacetones undergo ring-chain tautomerism with a good linear correlation between the ring-chain equilibrium constants (log K, where K=[ring]/[chain]) and the Hammett-Brown σ+ parameters of the aromatic substituents. The equilibrium constant was measured for the reaction products of 2-aminobenzenesulfonamide with unsubstituted benzoylacetaldehyde at several temperatures which enabled the enthalpy and entropy of this reaction to be evaluated. 相似文献
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Polytriazolylamines were synthesized by the copper(I)-catalyzed ligation of azides and alkynes. The C3-symmetric derivative, TBTA, was shown to be a powerful stabilizing ligand for copper(I), protecting it from oxidation and disproportionation, while enhancing its catalytic activity. 相似文献