Monte Carlo (MC) simulations were performed for hard spheres (with diameter sigma and mass m) placed between well-separated upper and lower hard walls. A periodic boundary condition was imposed in the horizontal direction. The system was exposed to the gravitational field with the acceleration due to gravity g. After preparing a melt as the initial state, g was increased stepwise up to mgsigma/k(B)T(identical with g(*))=1.5 or 2.0 with an increment Deltag(*) = 0.1; k(B)T is the temperature multiplied by Boltzmann's constant. We maintained g(*) at each value for 2.0 x 10(5) MC cycles. The transition of the system into a metastable state such as a polycrystalline state due to trapping phenomena was successfully avoided. A monotonic increase and subsequent saturation were observed for the development of the crystalline region formed at the bottom of the system. The development of this region accompanied a shrinkage of the defective (or less ordered) crystalline region that was formed between the bottom region and the fluid phase. As the development of the bottom region almost saturated, the defective region grew upward again.

Disappearance of a stacking fault in the hard-sphere crystal under gravity, such as reported by Zhu et al. [Nature 387, 883 (1997)], has successfully been demonstrated by Monte Carlo simulations. We previously found that a less ordered (or defective) crystal formed above a bottom ordered crystal under stepwise controlled gravity [Mori et al. J. Chem. Phys. 124, 174507 (2006)]. A defect in the upper defective region has been identified with a stacking fault for the (001) growth. We have looked at the shrinking of a stacking fault mediated by the motion of the Shockley partial dislocation; the Shockley partial dislocation terminating the lower end of the stacking fault glides. In addition, the presence of crystal strain, which cooperates with gravity to reduce stacking faults, has been observed.

No abstract

Birefringence measurements have been carried out on the Pb-doped silica hydrogels prepared under various magnetic fields up to 5T. The silica gels prepared at 5T were used as a medium of crystal growth of PbBr2, whose result implied the structural anisotropy; an aligned array of crystallites was obtained by transmission electron microscopy. While the samples prepared at 0, 1, and 3T have no birefringence, we found that the samples have negative birefringence on the order of magnitude 10 −6 as if the direction of the magnetic field is the optic axis of a uniaxal crystal. To the authors' knowledge, the birefringent silica hydrogels were obtained by gelation under magnetic field for the first time. Also, scanning microscopic light scattering experiments have been performed. The results indicate that the characteristic length distribution for birefringent samples is narrower than that for non-birefringent ones.

One-pot Julia olefination using ribofuranosyl sulfones is described. The α-anomers of the ribofuranosyl sulfones were synthesized with complete α-selectivity via the glycosylation of heteroarylthiols using ribofuranosyl iodides as glycosyl donors and the subsequent oxidation of the resulting heteroaryl 1-thioribofuranosides with magnesium monoperphthalate (MMPP). The Julia olefination of the α-ribofuranosyl sulfones with aldehydes proceeded smoothly in one pot to afford the thermodynamically less stable (E)-exo-glycals with modest-to-excellent stereoselectivity (up to E/Z = 94:6) under the optimized conditions. The E selectivity was especially high for aromatic aldehydes. In contrast, the (Z)-exo-glycal was obtained as the main product with low stereoselectivity when the corresponding β-ribofuranosyl sulfone was used (E/Z = 41:59). The remarkable impact of the anomeric configuration of the ribofuranosyl sulfones on the stereoselectivity of the Julia olefination has been rationalized using density functional theory (DFT) calculations. The protected ribose moiety of the resulting exo-glycals induced completely α-selective cyclopropanation on the exocyclic carbon–carbon double bond via the Simmons–Smith–Furukawa reaction. The 2-cyanoethyl group was found to be useful for the protection of the exo-glycals, as it could be removed without affecting the exocyclic CC bond.