Reversed-phase HPLC separation of the enantiomers of denopamine after derivatization with GITC chiral reagent

Summary A reversed-phase high-performance liquid chromatographic (HPLC) method was developed to determine the optical purity of denopamine, which is a new cardiotonic agent having an asymmetric carbon in a molecule. The enantiomers were converted to diastereomeric thiourea derivatives using 2,3,4,6-Tetra-O-acetyl--D-glucopyranosyl isothiocyanate (GITC) reagent. Separation of the enantiomers of denopamine as diastereomers was successfully achieved by reversed-phase HPLC within 10 min using an ODS column and UV detection. Derivatization of denopamine proceeded rapidly under the alkaline conditions and the ambient temperature. This method was applied to the determination of the optical purity of denopamine drug substances and those in tablets. The favorable UV absorption of the derivatives enabled the optical antipode to be determined down to the 0.2% level.     

Photodissociation of molecular beams of halogenated hydrocarbons at 193 nm

Molecular beams of halogenated hydrocarbons containing chlorine and bromine atoms were photodissociated using an excimer laser at 193 nm. Molecules photodissociated were HCCBr, HCCCH₂Br, HCCCH₂Cl, CH₃Cl, C₂H₅Cl and i-C₃H₇Cl. The time-of-flight distributions of the photofragments were measured in order to study the primary processes and the dissociation dynamics. Generalizations consistent with the data are that atomic products (RX → R + X) result from direct dissociation of the CX repulsive singlet state, molecular elimination (RX → R′ + HX) is a result of a crossover to the ground state and triplet states are involved in the photodissociation of alkyne compounds.     

On linear classification procedures between two categories with known mean vectors and covariance matrices

Summary This paper is concerned with probabilities (error probabilities), caused by misclassification, of linear classification procedures (linear procedures) between two categories, whose mean vectors and covariance matrices are assumed to be known, while the distribution of each category may well be continuous or discrete. The tightest upper bounds on the largest of two kinds of error probability of each linear procedure and on the expected error probability for any apriori probabilities are obtained. Moreover in some cases of interest, theoptimal linear procedure (in the sense of attaining the infimum out of all the upper bounds) is given.     

Emission spectra in orthorhombic PbCl2 at low temperature

The emission spectra and its time decay in PbCl₂ at low temperature are reported. Three emission bands lying at 3.81 (uv), 2.93 (blue) and 2.60 eV are found for the photo-excitation in the intrinsic absorption region, at 4.2 K. An exponential decay with decay time of 11.4 μs is observed for the uv emission. For the blue emission two kinds of time decay spectra are observed: a second order process below 10 K and an exponential decay above 14 K. The mechanisms of these emission are discussed by taking into account the above results.     

Consecutive elongation of alanine oligopeptides at the second time range under hydrothermal conditions using a microflow reactor system

During the course of the study of the hydrothermal stability of alanine oligopeptides, a small amount of oligopeptides longer than the starting oligopeptides was found in the reaction products. On the basis of this unexpected finding and the investigation of the reaction mechanism, the elongation of oligopeptides using (Ala)3, (Ala)4, and (Ala)5 was attempted in aqueous solution at 275-310 degrees C within the second time range using a microflow reactor system. The elongation of (Ala)4 and (Ala)5 succeeded in the presence of an excess amount of Ala monomer. This is probably due to the fact that the elongation rate is competitive or somewhat faster than the degradation of peptide bonding. On the contrary, the elongation of (Ala)3 was not possible since it was immediately converted to diketopiperazine.     

Synthesis and characterization of beta-haloalkenyl-lambda3-bromanes: stereoselective Markovnikov addition of difluoro(aryl)-lambda3-bromane to terminal acetylenes

Reported here for the first time are the synthesis, isolation, and characterization of hypervalent beta-haloalkenyl-lambda3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-lambda3-bromane activated by BF3-i-Pr2O resulted in fluoro-lambda3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-beta-fluoroalkenyl-lambda3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino lambda3-bromanation-chlorine shift-fluorination or lambda3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-beta-chloroalkenyl-lambda3-bromanes stereoselectively in high yields. The beta-chloroalkenyl-lambda3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule.     

Solid-liquid interfacial energy In Fe40at%Ni14at%P6at%B alloy glass

Based on nucleation theory, the solid-liquid interfacial energy is estimated to be about 87 ± 2 mJ/m² by the use of the nucleation frequency, supercooled liquid viscosity, and the melting point of Fe40at%Ni14at%P6at%B alloy glass. The value of this energy is found to be quite close to that estimated by means of Turnbull's assumption applied in covalent elements.     

Spatial arrangement of metal nanoparticles supported by porous polymer substrates studied by transmission electron microtomography

Fine metal particles (nanoparticles) stabilized on porous (polymeric) substrates can be considered as a model system of a high-performance catalyst. In the present study, the substrate was made using the periodic microphase-separated structure of a block copolymer as the template, and the Pd nanoparticles were formed inside the porous material by reduction of the Pd2+ ions with 1-propanol as the reductant. The three-dimensional morphology of such a polymer-Pd hybrid material was studied by transmission electron microtomography. The characteristic structural parameters of the hybrid, e.g., the penetration of the Pd nanoparticles into the polymer substrate, number density of the Pd nanoparticles, and size distribution of the Pd nanoparticles, were measured for the first time.     

Pressure-induced weak moment in the two-dimensional antiferromagnet (C2H5NH3)2CuCl4

Abstract

The two-dimensional Heisenberg antiferromagnet (C₂H₅NH₃)₂CuCl₄ has the ferromagnetic intralayer exchange interaction, while the extremely weak interlayer exchange interaction is antiferromagnetic. Neutron scattering experiments under high pressures have been performed on this compound. We confirm that the spin structure changes around 1～2 GPa from the collinear alignment along the a-axis to a spin-canting one. The weak moment due to the canting is parallel to the c-axis. The results indicate that the ferromagnetic intralayer and the antiferromagnetic interlayer exchange interactions are maintained up to 1～2 GPa. Why the weak ferromagnetic moment along the c-axis occurs is due to a lowering of crystal symmetry by pressure.     

Evaluation of Successive Fractions for Optimum Quantification of Bergenin and Gallic Acid in Three Industrially Important Bergenia species by High-Performance Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC -