Ring opening reaction of N-substituted dihydropyrimidines with metal hydride complexes

N-Substituted dihydropyrimidines, 1, 3 , and 4 , easily afforded N,N′-disubstituted 2,4-diaminopentanes 2 in good yield by the ring opening reaction with sodium borohydride. The reaction with lithium aluminum hydride was also examined.     

Enhanced dissolution and oral bioavailability of α-tocopheryl esters by dimethyl-β-cyclodextrin complexation

Inclusion complexation of heptakis (2,6-di-O-methyl)--cyclodextrin (DM--CyD) with -tocopheryl acetate and -tocopheryl nicotinate in aqueous solution was studied by the solubility method. The aqueous solubilities of the esters were about 10⁵ times increased by DM--CyD complexation. The phase-solubility diagram of the tocopheryl ester-DM--CyD systems showed a typicalA _p type, and the stability constants (K) of high-order complexes were estimated by analyzing the upward curvature of the diagrams. The solid complex of -tocopheryl nicotinate with DM--CyD in a molar ratio of 12 was prepared by the kneading method. The dissolution rate of the solid complex was much greater than that of the drug itself, and the rapidly dissolving form of -tocopheryl nicotinate, as an example, showed a markedly increased bioavailability (about 70-fold) after oral administration to fasted dogs.     

Enantioselective synthesis of axially chiral biaryls through rhodium-catalyzed complete intermolecular cross-cyclotrimerization of internal alkynes

[reaction: see text] We have developed a cationic rhodium(I)/H8-BINAP complex-catalyzed complete intermolecular cross-cyclotrimerization of internal alkynes with dialkyl acetylenedicarboxylates. This reaction was successfully applied to enantioselective synthesis of axially chiral biaryls utilizing internal alkynes bearing ortho-substituted phenyl and acetoxymethyl in each terminal position. The axial chirality is constructed at the formation of benzene rings with high enantioselectivity (up to 96% ee).     

The passivation phenomenon of rhodium in fused lithium chloride + potassium chloride eutectic

The passivation phenomenon of rhodium was investigated in fused lithium chloride + potassium chloride eutectic by means of the potential sweep method. The current-potential curve obtained showed a typical N-shaped negative impedance. An anodic current rise was observed at +0.3 V vs. Ag/AgCl (0.1). The current was controlled by mass transfer and was ascribed to the dissolution of rhodium into rhodium(III) ions. The observed Flade potential was +0.45 V at 400°C. The passivation was found to occur due to the precipitation of supersaturated Rh(III) chloride onto the electrode surface. The residual current for the passivation was fairly high and the current increased significantly as the temperature was made higher. The dissolution current of rhodium into Rh(III) ions decreased with increase in the concentration of oxide ions. The fact revealed that the rhodium was passivated preferentially due to the formation of Rh(III) oxide. The residual current of the oxide passivation film was low enough. The thickness of the film corresponded to 10–20 atomic layers of the parent metal. Rhodium showed another anomalous passivation due to the formation of oxide. The oxide was formed at ?0.3 V and was reduced at ?0.6 V. It was considered to be a low valence rhodium oxide, RhO or Rh₂O. Rhodium was found to have a low chlorine overpotential. However, it was redissolved at the chlorine evolution region, above +1.25 V. The dissolution was not prevented even in the oxide ion containing melts.     

Numerical Study of a Free-Burning Argon Arc with Anode Melting

Numerical modeling of free burning arcs and their electrodes is useful for clarifying the heat transfer phenomena in the welding process and to elucidate those effects which determine the weld penetration. This paper presents predictions for a stationary welding process by the free-burning argon arc. The whole region of the welding process, namely, tungsten cathode, arc plasma and stainless steel anode is treated in a unified numerical model to take into account the close interaction between the arc plasma and the molten anode. The time dependent development of two-dimensional distributions of temperature and velocity, in the whole region of the welding process, are predicted at a current of 150 A. The weld penetration geometry as a function of time is thus predicted. It is shown also that different surface tension properties can change the direction of re-circulatory flow in the molten anode and dramatically vary the weld penetration geometry.     

Studies on tacticity of polyacrylonitrile. II. High-resolution nuclear magnetic resonance spectra of 2,4-dicyanopentanes

The NMR spectra of 2,4-DCNP were measured in CCl₄, NaCNS–D₂O, DMSO-d₆, and other solutions. The spectra of the meso form show no significant change with the solvent, but the racemic form shows two kinds of spectra, one of which is observed in a solvent for PAN and the other in a nonsolvent. In the solution, the meso 2,4-DCNP is considered to have two equivalent conformations, TG and G'T, which are the mirror images with each other. The racemic 2,4-DCNP, however, might have predominantly either the TT or GG conformation in CCl₄, pyridine, and benzene, while it has the two conformers with almost equal probability in NaCNS–D₂O and DMSO-d₆. The results obtained from the calculation assuming appropriate constants are in fairly good agreements with the observed spectra of the 2,4-DCNP isomers. The values of chemical shifts and coupling constants used in the calculation correspond to those of PAN which were obtained previously from the analysis of the NMR spectra.     

Light Dose and Time Dependency of Photodynamic Cell Membrane Damage

We have investigated the light dose and time dependency of photodynamic cell membrane damage using electrophysiological methods. This study controls the level of cell membrane damage by precisely administration of the light dose. The photosensitizer used was 5′,5″-bis(aminomethyl)-2,2′:5′,2″-terthiophene dihydrochloride (BAT). A confocal laser scanning microscope was used to provide rapid light activation (<1 s) and the subsequent membrane damage was monitored using standard patch clamp techniques. In the presence of 49 μM BAT, light levels less than 0.94 J/cm² led to a reversible depolarization (20 mV) and reduction of resistance (10%) within 3 s of illumination. Higher intensities of illumination (1.57 J/cm²) caused a complete and irreversible loss of membrane potential and cell membrane resistance within 8 s of illumination. The threshold dose of light required to induce cell death by illumination in the presence of BAT was increased in the presence of the antioxidant Trolox-C.     

Cp2TiCl2-catalyzed grignard exchange reactions with 1,3-dienes or styrenes. Preparation of allylic and α-arylethyl grignard reagents by a convenient and quantitative method

The addition of a catalytic amount of Cp₂TiCl₂ to an ether solution of propylmagnesium bromide and 1,3-dienes brings about an exchange reaction forming allylic Grignard reagents.Styrene also undergoes the exchange reaction under the same conditions affording α-phenethylmagnesium bromide.     

Molecular dynamics simulation study on the phase behavior of the Gay-Berne model with a terminal dipole and a flexible tail

To study the effect of the alkyl tail and the terminal dipole on the stability of the liquid crystalline phase of mesogens, we have carried out molecular dynamics simulations for 1CB(4-methyl-4'-cyanobiphenyl) and 5CB(4-n-pentyl-4'-cyanobiphenyl) by using a coarse-grained model. In the coarse-grained model, a 5CB molecule is divided into the rigid part of 1CB moiety, which is represented by an ellipsoid, and the remaining flexible part which is represented by a chain of united atoms. The nonbonded potential between coarse-grained segments is represented by the generalized Gay-Berne (GB) potential and the potential parameters are determined by directly comparing the GB potential with the atomistic potentials averaged over the rotation of the mesogen around its axis. In addition, a dipole moment is placed at one end of the ellipsoid opposite to the flexible tail. The ordered state obtained in the polar 5CB model was assigned as the nematic phase, and the experimental static and dynamical properties were reproduced well by using this coarse-grained model. Both the dipole-dipole interactions and the thermal fluctuation of the flexible tail increase the positional disorder in the director direction, and stabilize the nematic phase. Thus, the nematic phase in the polar 5CB is induced by a cooperative effect of the flexible tail and the terminal dipole. It is noted that a local bilayer structure with head-to-head association is formed in the nematic phase, as experimentally observed by x-ray diffraction measurements.     

Relationship between electrical resistivity and particle dispersion state for carbon black filled poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate)/poly (<Emphasis Type="SmallCaps">L</Emphasis>-lactic acid) blend

It is known that the electrical volume resistivity of insulating polymers filled with conductive fillers suddenly decreases at a certain content of filler. This phenomenon is called percolation. Therefore, it is known that controlling resistivity in the semi-conductive region for carbon black (CB) filled composites is very difficult. When poly (ethylene-co-vinyl acetate) (EVA) is used as a matrix, the percolation curve becomes gradual because CB particles disperse well in EVA. In this study, the relationship between the dispersion state of CB particles and electrical resistivity for EVA/poly (L-lactic acid) (PLLA) filled with CB composite was investigated. The apparent phase separation was seen in the SEM photograph. It was predicted that the CB particles located into the EVA phase in the light of thermodynamical consideration, which was estimated from the wetting coefficient between polymer matrix and CB particles. The total surface area per unit mass of dispersed CB particles in the polymer blend matrix was estimated from small-angle X-ray scattering and the volume resistivity decreased with increasing CB content. The values of the surface area of CB particles in CB filled EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) polymer blends showed a value similar to that of the CB filled EVA single polymer matrix. In electrical volume resistivity measurement, moreover, the slopes of percolation curves of EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) filled with CB composite are similar to that of EVA single polymer filled with CB composite. As a result, it was found that CB particles selectively locate in the EVA phase, and then the particle forms conductive networks similar to the networks in the case of EVA single polymer used as a matrix.