Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.     

Electrostatic Interaction between Two Dissimilar Spheres with Constant Surface Charge Density

Explicit exact analytic expressions are obtained in the form of infinite series for the potential energy of the electrostatic interaction for the system of two dissimilar hard spheres with constant surface charge density in an electrolyte solution on the basis of the linearized Poisson-Boltzmann equation. The effects of the particle polarization, that is, the internal fields induced within tim interacting spheres, which are found to be of the order of instead of 1/κa (where κ is the Debye-Hückel parameter and a is the sphere radius), are taken into account. As in the case of the interaction at constant surface potential, the zeroth-order approximation to the interaction energy corresponds to the interaction energy that would be obtained if both spheres were ion-penetrable spheres ("soft" spheres) and to that obtained by the linear superposition approximation. The first-order approximation corresponds to the interaction energy that would be obtained if either sphere were a soft sphere, with the other being a hard sphere with constant surface charge density. The first-order correction term can be interpreted as the image interaction between the soft sphere and its image with respect to the hard sphere.     

Catalytic asymmetric epoxidation of alpha,beta-unsaturated esters using an yttrium-biphenyldiol complex

We succeeded in a catalytic asymmetric epoxidation reaction of alpha,beta-unsaturated esters via a conjugate addition of an oxidant using 2-10 mol % of the yttirium-chiral biphenyldiol catalyst. A variety of substrates with beta-aryl and beta-alkyl substituents were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy esters in up to 97% yield and 99% ee.     

Catalytic asymmetric synthesis of both syn- and anti-3,5-dihydroxy esters: application to 1,3-polyol/alpha-pyrone natural product synthesis

[reaction: see text] We describe a catalytic asymmetric synthesis of both syn- and anti-3,5-dihydroxy esters. The method relies upon catalytic asymmetric epoxidation of alpha,beta-unsaturated imidazolides and amides, using lanthanide-BINOL complexes, and diastereoselective reduction of ketones. The method was applied to the enantioselective syntheses of 1,3-polyol/alpha-pyrone natural products 9a, 9b, and strictifolione (10). The absolute stereochemistry of 9a and 9b was also determined.     

The effect of interfacial miscibility on the cell morphology of polyethylene terephthalate/bisphenol a polycarbonate blend foams

Annealing polyethylene terephthalate (PET)/polycarbonate (PC) blends enhance the transesterification reaction and increase the amount of copolymer at the interface of both polymers. The copolymer enhances the compatibility of PET with PC, because it contains both PET and PC blocks, which causes the interface between PET and PC to become fuzzy. When the PET/PC undergoes batch physical foaming with CO₂, the copolymer significantly changes the resulting cell morphology, that is, the annealing time. Before annealing or in the absence of the copolymer, bubble nucleation occurs and dominates growth at the interface. When the PET/PC blends are annealed, the interface impedes bubble nucleation and growth. The polymer is stretched at the interface by bubble growth, forming fibril‐like structures connecting two polymer domains at the interface. Increased annealing time causes the interface to become more homogeneous and makes heterogeneous bubble nucleation difficult. At higher copolymer concentrations, the interface of PET and PC becomes fuzzy and the cell morphology becomes like those of foamed homogeneous polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Approximate analytic expressions for the diffusiophoretic velocity of a spherical colloidal particle

The general expression is derived for the diffusiophoretic velocity of a spherical colloidal particle of radius a in a concentration gradient of symmetrical electrolyte. On the basis of this expression, simple approximate analytic expressions for the diffusiophoretic velocity correct up to the order of 1/κa is derived, where κ is the Debye-Hückel parameter. It is found that the approximate expression correct to order unity can be applied for κa ≥ 50 with negligible errors, while the approximate expression correct to order 1/κa can be applied for κa ≥ 20 with negligible errors.     

Chemoselective Catalytic Conjugate Addition of Alcohols over Amines

A highly chemoselective conjugate addition of alcohols in the presence of amines is described. The cooperative nature of the catalyst enabled chemoselective activation of alcohols over amines, allowing the conjugate addition to soft Lewis basic α,β‐unsaturated nitriles. Divergent transformation of the nitrile functionality highlights the utility of the present catalysis.     

Discrete charge effects on the Donnan potential and surface potential of a soft particle

The Donnan potential and surface potential of soft particles (i.e., polyelectrolyte-coated hard particles) in an electrolyte solution play an essential role in their electric behaviors. These potentials are usually derived via a continuum model in which fixed charges inside the surface layer are distributed with a continuous charge density. In this paper, for a plate-like soft particle consisting of a cubic lattice of fixed point charges, on the basis of the linearized Poisson–Boltzmann equation, we derive expressions for the electric potential distribution in the regions inside and outside the surface layer. This expression is given in terms of a sum of the screened Coulomb potentials produced by the point charges within the surface layer. We show that the deviation of the results of the discrete charge model from those of the continuous charge model becomes significant as the ratio of the lattice spacing to the Debye length becomes large.     

Phase transition of Ta2NiO6 with the trirutile-type structure under high pressure and high temperature

High-pressure phase transition of Ta₂NiO₆ with the trirutile-type structure was investigated from the viewpoint of crystal chemistry. A new quenchable high-pressure phase was found in the pressure range higher than 7 GPa and 900°C. The high-pressure phase has an orthorhombic cell (a=4.797(1) Å, b=5.153(2) Å and c=14.85(1) Å and space group; Abm2), and it is more dense by 9.6% than the trirutile-structured phase. Infrared spectra of the trirutile-type phase and the high-pressure phase show that Ni²⁺ ions in the high-pressure phase are still in octahedral sites. The crystal structure of the high-pressure phase is considered as a cation-ordering trifluorite-type structure, which can be stabilized by a crystal field effect of Ni²⁺ ions.     

Mechanisms of reduction in hole concentration in Al-doped 4H-SiC by electron irradiation

From the temperature dependence of the hole concentration in unirradiated lightly Al-doped 4H-SiC epilayers, an Al acceptor with E_V + 0.2 eV, which is an Al atom (Al_Si) at a Si sublattice site, and an unknown deep acceptor with E_V + 0.35 eV are found, where E_V is the top of the valence band. Both the densities are similar. With irradiation of 0.2 MeV electrons the Al acceptor density is reduced, while the unknown deep acceptor density is increased. Judging from the minimum electron energy required to displace a substitutional C atom (C_s) or the Al_Si, the bond between the Al_Si and its nearest neighbor C_s is broken due to the displacement of the C_s by this irradiation. Moreover, the displacement of the C_s results in the creation of a complex (Al_Si-V_C) of Al_Si and a carbon vacancy (V_C), indicating that the possible origin of the deep acceptor with E_V + 0.35 eV is Al_Si-V_C.