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81.
Tomohisa Yasuhara Katsumi Nishimura Ken-ichi Yamada Kiyoshi Tomioka 《Tetrahedron letters》2004,45(15):3043-3045
(±)-γ-Lycorane 3 was synthesized in 52% overall yield via seven steps from 5 by employing the highly stereoselective nitro-Michael cyclization of 5 to 9 and diastereoselective conjugate addition of aryllithium to a nitroolefin 10 as two key steps. 相似文献
82.
Hongo K Maezono R Kawazoe Y Yasuhara H Towler MD Needs RJ 《The Journal of chemical physics》2004,121(15):7144-7147
Hund's multiplicity rule is investigated for the carbon atom using quantum Monte Carlo methods. Our calculations give an accurate account of electronic correlation and obey the virial theorem to high accuracy. This allows us to obtain accurate values for each of the energy terms and therefore to give a convincing explanation of the mechanism by which Hund's rule operates in carbon. We find that the energy gain in the triplet with respect to the singlet state is due to the greater electron-nucleus attraction in the higher spin state, in accordance with Hartree-Fock calculations and studies including correlation. The method used here can easily be extended to heavier atoms. 相似文献
83.
Akio?OhtaEmail author Satoru?Nakashima Hiroki?Matsuyanagi Tsuyoshi?Asakawa Shigeyoshi?Miyagishi 《Colloid and polymer science》2003,282(2):162-169
The Krafft temperatures and enthalpies of solution of N-hexadecanoyl alaninate and valinate, and N-tetradecanoyl phenylalaninate were obtained from differential scanning calorimetry. The Krafft temperature of N-acyl amino acid surfactant increased with decreasing size of the counter ion, with some exceptions. The enthalpy of solution was endothermic and increased with decreasing size of the counter ion except for the cases of lithium salt. The results showed that the L-L interaction in the solid state of N-hexadecanoyl amino acid surfactant salt was superior to the D-L interaction for both the alanine and valine systems when the counter ion size increased. However, the D-L interaction was still advantageous for the phenylalanine system with Cs+ as a counter ion. Both Fourier transform infrared spectroscopy studies and theoretical calculations suggested that the difference in magnitudes of the interactions between peptide and counter ion was a dominant factor for the chiral effect. 相似文献
84.
Tsuji H Terada M Toshimitsu A Tamao K 《Journal of the American Chemical Society》2003,125(25):7486-7487
On the basis of the UV absorption spectra of the anti,cisoid alternating oligosilanes, the first experimental clear-cut evidence was presented for the generally accepted idea that the sigma conjugation in polysilanes does not effectively extend through a tetrasilane fragment with a small dihedral angle such as a cisoid turn. 相似文献
85.
Yasuhara T Nishimura K Yamashita M Fukuyama N Yamada K Muraoka O Tomioka K 《Organic letters》2003,5(7):1123-1126
[reaction: see text] An omega-nitro-alpha,beta,psi,omega-unsaturated ester underwent a chemoselective conjugate addition of a nitroolefin moiety with aryllithium to produce a psi-aryl-omega-nitro-alpha,beta-unsaturated ester, which was then stereoselectively cyclized by intramolecular nitro-Michael reaction giving a functionalized cyclohexane applicable to the total synthesis of (+/-)-alpha- and beta-lycoranes. 相似文献
86.
The ability of a developed capillary electrophoresis (CE) method for fast, efficient and reliable main component assay of ragaglitazar [NNC 61-0029/DRF(-)2725] has been demonstrated through documentation of the analytical performance and the results of a successful validation. The fast analysis time of around 1.2 min ensures a high analytical capacity, and the validation results show that the CE method is robust and gives reliable and precise results. The results from the validation of the CE method meet the acceptance criteria that are normally set for other main component assays such as high-performance liquid chromatography assays. 相似文献
87.
Theoretical calculations of ESR parameters for aminoxyl radicals have been widely studied using the density functional theory (DFT) calculations. However, the isomer N‐alkoxyaminyl radicals have been limitedly studied. With the use of experimental data for 46 N‐alkoxyaminyl and 38 aminoxyl radicals, the isotropic 14N hyperfine coupling constants (aN) and g‐factors have been theoretically estimated by several DFT calculations. The best calculation scheme of aN for N‐alkoxyaminyl radicals was PCM/B3LYP/6‐31 + + G(d,p) (R2 = 0.9519, MAE = 0.034 mT), and that for aminoxyl radicals was PCM/BHandHLYP/6‐31 + + G(3df,3pd) (R2 = 0.9336, MAE = 0.057 mT). For aminoxyl radicals, the solvation models in calculations enhanced the accuracy of reproducibility. In contrast, for N‐alkoxyaminyl radicals the calculations with solvation models provided no improvement. The differences in the best functionals between two types of radicals were thought to come from the contribution ratios of neutral and dipolar canonical structures in resonance forms. The aN for N‐alkoxyaminyl radicals that were stabilized by small contribution of dipolar canonical structures could be precisely reproduced by B3LYP with only 20% HF exact exchange. In contrast, the aN for aminoxyl radicals stabilized by large contribution of dipolar canonical structures was well reproduced by BHandHLYP with 50% HF exchange. The best calculation scheme of g‐factors was IEFPCM/B3LYP/6‐31 + G(d,p) (R2 = 0.9767, MAE = 0.0001) for not only aminoxyl but also N‐alkoxyaminyl radicals. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
88.
Link-homotopy and self Δ-equivalence are equivalence relations on links. It was shown by J. Milnor (resp. the last author) that Milnor invariants determine whether or not a link is link-homotopic (resp. self Δ-equivalent) to a trivial link. We study link-homotopy and self Δ-equivalence on a certain component of a link with fixing the other components, in other words, homotopy and Δ-equivalence of knots in the complement of a certain link. We show that Milnor invariants determine whether a knot in the complement of a trivial link is null-homotopic, and give a sufficient condition for such a knot to be Δ-equivalent to the trivial knot. We also give a sufficient condition for knots in the complements of the trivial knot to be equivalent up to Δ-equivalence and concordance. 相似文献
89.
Akio Nakajima 《Journal of Macromolecular Science: Physics》2013,52(4):715-721
Interactions between polyelectrolytes carrying opposite charges in aqueous media may lead to either complex coacervation or the formation of interpolymer complexes, depending on the charge density and concentration of polymer components, ionic strength, temperature, and pH. The liquid-liquid phase separation referred to as complex coacervation was thought by Oparin to be an origin of prebiological systems. This article summarizes our recent results on the intermolecular interactions between charged polymer molecules, from the point of view of biological interests. 相似文献
90.
Akio Tsuboi Petr Kol Takeshi Ishikawa Yoshinori Kamiya Hirokatsu Masuoka 《Journal of Polymer Science.Polymer Physics》2001,39(12):1255-1262
The sorption of C2 and C3 hydrocarbons in two ethylene–propylene copolymers and a propylene homopolymer and the simultaneous dilation of the polymers were measured at temperatures of 287–363 K and pressures up to 4 MPa. The sorption isotherms were well described by the Flory–Huggins theory of dissolution. Dilation isotherms in the form of elongation versus pressure were similar in shape to the corresponding sorption isotherms. Solubility coefficients, partial molar volumes, and Flory–Huggins interaction parameters were determined from these isotherms. The thermal expansivities of the hydrocarbons dissolved in the polymers were 0.002–0.005 K?1, and the Flory–Huggins interaction parameters depended not only on temperature but also on concentration. At 323 K, the calculated solubilities of propylene in the ethylene–propylene‐rubber regions of the copolymers were 1.8 times higher than in the amorphous regions of the propylene homopolymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1255–1262, 2001 相似文献