High-performance liquid chromatographic determination of boric acid and germanic acid with conductometric detection

Summary Boric and germanic acids were detected by a conductivity detector after ion-exclusion Chromatographic separation on a cation-exchange resin. Neither acid could be directly measured by a conductivity detector because they were very weak. However, use of eluents of polyol compounds permitted their determination by a conductivity detector. With 0.1 M of fructose as eluent, it was possible to detect 0.5 ppb of boric acid (as B) and 1.5 ppb of germanic acid (as Ge).

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HPLC-Bestimmung von Borsäure und Germaniumsäure mit konduktometrischer Detection

Zusammenfassung Beide Säuren wurden mit Hilfe eines Leitfähigkeitsdetektors nach Trennung durch Ionenausschluß-Chromatographie an einem Kationenaustauscher analysiert. Eine direkte Messung war wegen der Schwäche der Säuren nicht möglich; daher wurde eine Elution mit Polyolen durchgeführt. Mit 0,1 M Fructoselösung als Eluens konnten noch 0,5 ppb Borsäure (als B) und 1,5 ppb Germaniumsäure (als Ge) nachgewiesen werden.

     

Synthesis of a phosphorus-containing hybrid porphyrin

A phosphorus-containing hybrid porphyrin was successfully prepared via the BF3-promoted dehydrative condensation between sigma4-phosphatripyrrane and 2,5-bis[hydroxy(phenyl)methyl]thiophene. The NMR and UV-vis absorption spectra, electrochemical measurements, and DFT calculations revealed that the sigma3-P,N2,S-hybrid porphyrin exhibits high aromaticity as an 18pi-electron system in terms of both geometric and magnetic criteria. [structure: see text]     

A Novel Composite Poly-p-Phenylenebenzobisoxazole (PBO) Fiber Including Molecularly-Dispersed Copper Phthalocyanine in the Structure

The possibility to make a composite poly-p-phenylenebenzobisoxazole (PBO) fiber including a second component without distorting its original structures and mechanical properties was examined. Copper phthalocyanine was found to fulfill the above-mentioned condition and can be dispersed in the fiber molecularly. It was shown that part of the embedded copper phthalocyanine can be aligned one-dimensionally with periodicity along the fiber axis in the fiber. The color of the resultant fiber was dark blue, which is different from the original fiber having its yellowish golden color. According to X-ray diffraction analysis the preferential orientation of the a-axis of the PBO crystal was slightly more oriented by the addition of copper pthalocyanine than that of the pure PBO fiber, but the crystal size of PBO wasn't also affected. We thus show the possibility of adding a second material that can add additional properties to the fiber, but keeping the original high mechanical properties and oriented structures.     

Application of calorimetry and thermodynamics to critical problems in materials science

Calorimetry and thermodynamic studies have long been playing a very important role in the research fields of fundamental science and technology. Some topics and examples of thermodynamics studies are given, and the details are explained on the basis of the present author’s experience, focusing attention to application of adiabatic calorimetry and thermodynamics to solve critical problems in materials science: (1) condensed gas calorimetry and third law entropy, (2) phase transition and polymorphism in simple molecular crystals, (3) incommensurate phase transitions, (4) particle size effects on the phase transitions in ferroelectric/ferroelastic crystals, (5) relaxor ferroelectrics and multi-ferroics, and some other topics in materials science and technology.     

Hydrogen Effects for Propylene Polymerization with Ultra Low TiCl3 Loading MgCl2-Supported Catalyst

Hydrogen effects for propylene polymerization were investigated with ultra low TiCl₃ loading MgCl₂-supported catalysts in which the electric states of Ti species can be almost uniform. Hydrogen did not affect the catalyst activity, while the efficiency of hydrogen as a chain transfer agent was found to depend on the Ti content of the catalyst and the stereospecificity of the polymerization sites: Hydrogen was effective for isospecific sites independent of Ti contents, but inert for aspecific sites only at the extremely low Ti content. These results were explained within the island model, where isospecific sites may be located in the islands with other Ti species in their surroundings acting, as a steric hindrance for isospecific polymerization and as hydrogen dissociation sites after deactivation. Most of the aspecific sites should be isolated only at the extremely low Ti content. These isolated sites have no other Ti species in their surroundings, i.e. no hydrogen dissociation sites, and are inert to hydrogen.     

Electron spin resonance of the two-dimensional metallic state and the quantum Hall state in a Si/SiGe quantum well

We report electrically detected electron spin resonance (ESR) measurements of a high mobility two-dimensional (2D) electron system formed in a Si/SiGe quantum well, with millimeter wave in a high magnetic field . The negative ESR signal observed under an in-plane magnetic field gives direct evidence that the spin polarization leads to a resistance increase in the 2D metallic state. Suppression of spin decoherence was observed in the quantum Hall state at the Landau level filling factor ν=2. Strength of the nuclear magnetic field in the resonance is evaluated to be less than , much smaller than that reported for GaAs/AlGaAs heterostructures.     

Time-oscillating Lyapunov modes and the momentum autocorrelation function

The Lyapunov vectors corresponding to the steps of Lyapunov spectra for many-particle systems show time-oscillating behavior in two types of Lyapunov modes, one associated with time-translational invariance and the other with spatial translational invariance. Our result is that, for each coordinate direction, the longest period of the Lyapunov modes is twice as long as the period of the momentum autocorrelation function. A simple explanation for this relation is proposed and we argue that this result is generally true for many-particle systems. This gives the first quantitative connection between the Lyapunov modes and an experimentally accessible quantity.     

Near-Field and Polarized Evanescent Field Excited Fluorescence of Self-Organized Particle Arrays of Organic Dye

A wetting/dewetting process was utilized to prepare self-organized organic dye particles of micrometer and submicrometer size. Near-field scanning optical microscopy successfully identified near-field excited near-field fluorescence from single particles. The majority of the small particles with diameters around 2 mm or less, however, did not show fluorescence under near-field observation. In contrast, far-field fluorescence, when excited by a polarized evanescent field, was observed, with the intensity depending on the excitation polarization, indicating that molecules' transition moment within dye particles was oriented parallel to the substrate surface. Single particle fluorescence spectrum consistently showed an identical sharp peak with a large redshift, indicating that the particles were composed of identical dye aggregates similar to J-aggregates. These observations suggest that the near-field at the probe tip was polarized parallel to the probe axis. Another observation, that molecules were oriented in a similar direction among adjacent particles, suggests that the dewetting process contributed to the alignment of the molecular direction among adjacent particles, which further proves that the present specimen was formed by a self-organizing mechanism.     

Establishment of hybrid-derived offspring populations in the Ohomopterus ground beetles through unidirectional hybridization

An approach to deduce the mechanism of stabilization of the hybrid-derived populations in the Ohomopterus ground beetles has been made by comparative studies on the phylogenetic trees of the mitochondrial and nuclear DNA. A phylogenetic tree based on the internal transcribed spacer (ITS) of nuclear ribosomal gene roughly reflects the relations of morphological species group, while mitochondrial NADH dehydrogenase subunit 5 (ND5) gene shows a considerable different topology on the tree; there exist several geographically-linked lineages, most of which consist of more than one species. These results suggest that the replacement of mitochondria has occurred widely in the Ohomopterus species. In most cases, hybridization is unidirectional, i.e., the species A (♂) hybridized with another species B (♀) and not vice versa, with accompanied replacement of mitochondria of A by those of B. The results also suggest that partial or complete occupation of the distribution territory by a hybrid-derived morphological species. The morphological appearance of the resultant hybrid-derivatives are recognized as that of the original species A. Emergence of a morphological new species from a hybrid-derived population has been exemplified.     

1H NMR spectral analysis of physalin A,a 13,14-seco-16,24-cyclosteroid,based on crystal structure of (25R)-2,3,25,27-tetrahydrophysalin a dimethanol solvate

(25R)-2,3,25,27-Tetrahydrophysalin A dimethanol solvate, C₃₀H₄₂O₁₂, a derivative of 13,14-seco-16,24-cyclosteroid physalin A, crystallizes in the orthorhombic space groupP2₁2₁2₁, witha=15.486(5),b=14.794(4), 12.248(6) Å andZ=4. The crystal structure has been solved by direct methods, and refined to an R-value of 0.053 for 2345 observed reflections.¹H NMR spectral data of physalin A and its hydrogenated derivatives measured in dimethylsulfoxide-d₆ solutions have been elucidated, based on the crystal structure of the tetrahydrophysalin A, enabling the assignment of all the proton signals of physalin A. The-proton of C(11)-methylene has been shown to resonate at remarkably higher field due to anisotropic shielding effect of carbonyl group at C(15).