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51.
The solubilization of n-alkylbenzenes (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene) into an aqueous micellar solution of sodium cholate was carried out. Solubilizate concentrations at equilibrium were determined spectrophotometrically at 293.2, 298.2, 303.2, 308.2, and 313.2 K. The first stepwise association constants (K(1)) between solubilizate monomers and vacant micelles were evaluated from the equilibrium concentrations and found to increase with increasing hydrophobicity of the solubilizate molecules. From the Gibbs energy change for solubilization at different micelle aggregation numbers and from the molecular structure of the solubilizates, the function of sodium cholate micelles as solubilizer was discussed. Enthalpy and entropy changes of solubilization were calculated from the temperature dependence of the K(1) values, and the solubilization was found to be enthalpy-driven for the solubilizates with shorter alkyl chains. The results obtained were also compared with those for conventional aliphatic micelles. 相似文献
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A new effective copper catalyzed CO coupling reaction using excess amount of strongly coordinating monodentate ligands was successfully developed. Among the DMAP-type monodentate ligands, 4-pyrrolidinopyridine afforded the best results. The developed reaction is widely applicable for the synthesis of various hindered or acyclic secondary alkyl-aryl ethers. In this study, a novel and remarkable acceleration of the coupling reaction using excess amount of monodentate ligands was discovered. 相似文献
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The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double‐zeta (DZ) and triple‐zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian‐3X and Gaussian‐2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts. © 2015 Wiley Periodicals, Inc. 相似文献