Migration mechanism of bases and nucleosides in oil-in-water microemulsion capillary electrophoresis.

The electrophoretic behaviors of five bases and corresponding nucleosides in the oil in water (o/w) microemulsion capillary electrophoresis, microemulsion electrokinetic chromatography (MEEKC), were examined in comparison with those in normal capillary zone electrophoresis (CZE). The microemulsion systems were composed of heptane, sodium dodecyl sulfate (SDS), 1-butanol and 10 mM phosphate buffer (pH 7.0) or toluene, SDS, 1-butanol and 5 mM carbonate buffer (pH 10.0). CZE was carried out in the range of pH 9.7-10.9, and the dissociation constants, pKa, of the bases and nucleosides and the electrophoretic mobilities of the anionic forms were determined. The electrophoretic behaviors of the solutes in the microemulsion systems were analyzed from their pKa, the electrophoretic mobilities of the anions determined by CZE, and the distribution constants, K(D), of the neutral forms between the microemulsion droplets and the outer aqueous phase. The importance of adsorption mechanism in MEEKC system was suggested from the correlation between log K(D) and log P.     

Measure Valued Solutions of the 2D Keller–Segel System

We develop a theory of global measure-valued solutions for the classical Keller–Segel model. These solutions are obtained considering the limit of solutions of a regularized problem. We also prove that different regularizations yield different limit measures in the case in which classical solutions of the Keller–Segel system are not globally defined in time.     

Numerical convergence of finite element solutions of nonrational B-spline element and absolute nodal coordinate formulation

In this investigation, numerical convergence of finite element solutions obtained using the B-spline approach and the absolute nodal coordinate formulation (ANCF) is discussed. Furthermore, equivalence of the two formulations with different orders of polynomials and degrees of continuity is demonstrated by several numerical examples. The degree of continuity can be easily controlled in B-spline elements by changing knot multiplicities, while continuity conditions associated with higher order derivatives need to be imposed to achieve C ² and higher continuities in ANCF elements. In order to compare element performances of the third and quartic B-spline and ANCF elements, the three-node quartic ANCF beam element is developed. It is demonstrated in several numerical examples that use of B-spline and ANCF elements with same orders and continuities leads to identical results. Furthermore, effects of polynomial orders and continuities on the accuracy and numerical convergence are demonstrated.     

Catalytic four-component assembly based on allenylboronate platform: new access to privileged allylic amine structures

We developed a novel palladium-catalyzed four-component assembly based on allenylboronate platform, by which privileged allylic amine structures can be constructed in a regioselective, stereoselective, and diversity-oriented manner. The boryl group acts not only as a useful group that can be transformed to various functional groups afterward but also as a stereochemical controller in the generation of key (pi-allyl)palladium intermediates. A short synthesis of rolipram (selective phosphodiesterase-4 inhibitor) is also demonstrated.     

Pressure effect on bulk weak ferromagnets: (BDH-TTP)[M(isoq)2(NCS)4] (M = Cr(III), Fe(III); isoq = Isoquinoline)

The pressure dependence of the magnetic properties of weak ferromagnets (BDH-TTP)[M(isoq)2(NCS)4] [BDH-TTP = 2,5-bis(1',3'-dithiolan-2'-ylidene)-1,3,4,6-tetrathiapentalene; M = Cr, Fe; isoq = isoquinoline] is discussed. These salts form two-dimensional magnetic sheets, where ferrimagnetic chains of donor cation radical (S = 1/2) and anion [S = 3/2 (Cr), 5/2 (Fe)] are antiferromagnetically connected by weak donor-donor and anion-anion interchain S...S contacts. Under ambient pressure, both the Cr and Fe salts undergo a weak ferromagnetic transition at Tc = 7.6 K, below which a spontaneous magnetization emerges along the direction perpendicular to the sheets. The application of the pressure elevates the transition temperatures up to 16.6 and 11.6 K at 9 kbar for M = Cr and Fe, respectively. As the pressure increases, the remanent magnetization M(r) decreases, whose pressure dependence for the Cr salt is larger than that for the Fe salt. This difference indicates that the spin-canting angle of the Cr salt is reduced because of the increase of antiferromagnetic interaction by applied pressure, in contrast to the Fe salt, where single-ion anisotropy contributes less. The quantitative analysis of the magnetization curves of the Cr salt using the mean-field approximation reveals that the intermolecular exchange interaction increases as the pressure increases, among which the interchain anion-anion interaction has the highest pressure sensitivity. This result is consistent with the temperature dependence of the crystal structure showing that the thermal contraction in the distances of interchain anion-anion S...S contacts is the most remarkable in intrachain S...S contacts. The large pressure dependence of the transition temperature of these salts is therefore explained as a result of the fact that the interchain interactions, the anion-anion interaction in particular, are strengthened by applied pressure.     

Propagation of Regularity and Persistence of Decay for Fifth Order Dispersive Models

This paper considers the initial value problem for a class of fifth order dispersive models containing the fifth order KdV equation

$$\begin{aligned} \partial _tu - \partial _x^5u -30u^2\partial _xu + 20\partial _xu\partial _x^2u + 10u\partial _x^3u = 0. \end{aligned}$$

The main results show that regularity or polynomial decay of the data on the positive half-line yields regularity in the solution for positive times.

     

Viscosity change in aqueous hectorite suspension activated by DC electric field

The change in the viscosity of deionized aqueous hectorite suspensions by applying an electric field was investigated. The deionized suspensions had low viscosity, which was almost the same as that of its solvent, water. Upon applying a DC electric field of the order of a few volt per millimeter to the deionized suspension, the viscosity started to increase gradually and reached a constant value that was high enough relative to the original value. Regarding the mechanism of the electrically induced stress increase, it is highly plausible that a three-dimensional network structure formed under the electric field due to a deformation of the electrical double layer.     

Cp(*)RuCl-catalyzed formal intermolecular cyclotrimerization of three unsymmetrical alkynes through a boron temporary tether: regioselective four-component coupling synthesis of phthalides

Highly substituted phthalides were efficiently synthesized by sequential Cp(*)RuCl-catalyzed cyclotrimerization of alkynylboronates, propargyl alcohols, and terminal alkynes and palladium(II)-catalyzed carbonylation of the resultant arylboronates. The intermediate arylboronate was isolated and unambiguously characterized by X-ray crystallography. The perfect regioselectivity of the ruthenium-catalyzed formal intermolecular cyclotrimerization was discussed on the basis of the density functional calculations of a boraruthenacycle intermediate.     

One-pot beta-substitution of enones with alkyl groups to beta-alkyl enones

Vinylic hydrogens at the beta-position of enones were effectively substituted with alkyl groups in a one-pot procedure to afford beta-alkyl enones in good to high isolated yields by conjugate addition of higher-order dialkyl cyanocuprates to enones, followed by a reaction with N-tert-butylbenzenesulfinimidoyl chloride at -78 degree C.