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991.
992.
The nonlinear rheological version of our barrier hopping theory for particle-polymer suspensions and gels has been employed to study the effect of steady shear and constant stress on the alpha relaxation time, yielding process, viscosity, and non-Newtonian flow curves. The role of particle volume fraction, polymer-particle size asymmetry ratio, and polymer concentration have been systematically explored. The dynamic yield stress decreases in a polymer-concentration- and volume-fraction-dependent manner that can be described as apparent power laws with effective exponents that monotonically increase with observation time. Stress- or shear-induced thinning of the viscosity becomes more abrupt with increasing magnitude of the quiescent viscosity. Flow curves show an intermediate shear rate dependence of an effective power-law form, becoming more solidlike with increasing depletion attraction. The influence of polymer concentration, particle volume fraction, and polymer-particle size asymmetry ratio on all properties is controlled to a first approximation by how far the system is from the gelation boundary of ideal mode-coupling theory (MCT). This emphasizes the importance of the MCT nonergodicity transition despite its ultimate destruction by activated barrier hopping processes. Comparison of the theoretical results with limited experimental studies is encouraging. 相似文献
993.
We report the first biocatalytic route to sulfinamides (R-S(O)-NH2), whose sulfur stereocenter makes them important chiral auxiliaries for the asymmetric synthesis of amines. Subtilisin E did not catalyze hydrolysis of N-acetyl or N-butanoyl arylsulfinamides, but did catalyze a highly enantioselective (E > 150 favoring the (R)-enantiomer) hydrolysis of N-chloroacetyl and N-dihydrocinnamoyl arylsulfinamides. Gram-scale resolutions using subtilisin E overexpressed in Bacillus subtilis yielded, after recrystallization, three synthetically useful auxiliaries: (R)-p-toluenesulfinamide (42% yield, 95% ee), (R)-p-chlorobenzenesulfinamide (30% yield, 97% ee), and (R)-2,4,6-trimethylbenzenesulfinamide (30% yield, 99% ee). Molecular modeling suggests that the N-chloroacetyl and N-dihydrocinnamoyl groups mimic a phenylalanine moiety and thus bind the sulfinamide to the active site. Molecular modeling further suggests that enantioselectivity stems from a favorable hydrophobic interaction between the aryl group of the fast-reacting (R)-arylsulfinamide and the S1' leaving group pocket in subtilisin E. 相似文献
994.
Raja R Golovko VB Thomas JM Berenguer-Murcia A Zhou W Xie S Johnson BF 《Chemical communications (Cambridge, England)》2005,(15):2026-2028
Nanoparticles of Co and NiPd, derived from colloidal precursors and supported on commercially available non-ordered mesoporous silica, are highly effective, cheap, recyclable and industrially viable catalysts for the hydrogenation of a range of nitro-substituted aromatics under mild conditions. 相似文献
995.
Cacciarini M Azov VA Seiler P Künzer H Diederich F 《Chemical communications (Cambridge, England)》2005,(42):5269-5271
The partially bridged resorcin[4]arene cavitand featuring a cleft-shaped recognition site formed by two anti-quinoxaline bridges and four convergent HO-groups was prepared in three steps and characterised by X-ray crystallography; cavitand was found to be a selective receptor for steroidal substrates in CDCl3, with the best binding observed for steroids with a flat A-ring and two H-bonding sites on rings A and C/D. 相似文献
996.
Bernal I Mukhopadhyay U Virovets AV Fedin VP Clegg W 《Chemical communications (Cambridge, England)》2005,(30):3791-3792
Examination of the crystal structure of the adduct of hydronium tetrachloroferrate dichloride with cucurbituril resulted in the discovery that the hydronium cation present therein is not the well known H7O3+ species; rather, it is an unprecedented cyclic species of composition (H14O6)2+, templated by the formation of five hydrogen bonds to cucurbituril. 相似文献
997.
998.
Olli Martio Vladimir Miklyukov Matti Vuorinen 《Proceedings of the American Mathematical Society》2005,133(5):1451-1458
The system which yields Beltrami's system if , is considered. Under a condition for the coefficients a non-existence theorem is proved.
999.
Vladimir Andrievskii 《Journal of Approximation Theory》2005,133(2):1191-244
The Dzjadyk-type theorem concerning the polynomial approximation of functions on a continuum in the complex plane is generalized to the case of polynomial approximation of functions on a compact set in which consists of a finite number of continua. 相似文献
1000.