The system BaOGeO2 at high pressures and temperatures,with special reference to high-pressure transformations in BaGeO3, BaGe2O5, and Ba2Ge5O12

Phase relations in the system BaOGeO₂ were investigated in the pressure range 20–70 kbar in the temperature range 750–1200°C. Several new phases were identified in this system: an atmospheric phase of BaGe₂O₅ (monoclinic BaGe₂O₅ I), two high-pressure phases of BaGe₂O₅ (monoclinic BaGe₂O₅ II and tetragonal BaGe₂O₅ III), and a high-pressure phase of Ba₂Ge₅O₁₂. The phase boundary curve between BaGe₂O₅ II and BaGe₂O₅ III was preliminarily determined as P(kbar) = 7.7 + 0.047T (°C). The high-pressure phases of BaGeO₃, which were previously reported by Y. Shimizu, Y. Syono, and S. Akimoto (High Temp.-High Pressures2, 113 (1970)) in the pressure range 15–95 kbar, were interpreted to be not single-phase materials but complicated mixtures of more than two phases in the system BaOGeO₂. X-Ray powder diffraction data for the new compounds synthesized in this study are given.     

Novel synthesis and properties of 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate: autorecycling oxidation of some alcohols under photo-irradiation

Three-step reactions starting from 2-chlorotropone with barbituric acid afforded novel 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (9·BF₄⁻), which is the isoelectronic compound of the 5-ethyl-3-methyllumiflavinium ion. The stability of cation 9 is expressed by the pK_R+ value, which was determined spectrophotometrically, as ca. 6.0. The electrochemical reduction of 9 exhibited low reduction potential at −0.58 (V vs Ag/AgNO₃), upon cyclic voltammetry (CV). In a search for the reactivity, reactions of 9·BF₄⁻ with some nucleophiles, hydroxide, hydride, amines, thiols, and methanol, were carried out to exhibit that the introduction of nucleophiles is dependent on the nucleophile itself. The photo-induced oxidation reactions of some alcohols catalyzed by 9·BF₄⁻ under aerobic conditions were carried out to give the corresponding carbonyl compounds in more than 100% yield [based on compound 9·BF₄⁻], suggesting the oxidizing function of 9·BF₄⁻ toward alcohols in the autorecycling process. The UV-vis and fluorescence spectra of 9 were studied to suggest the electron transfer from alcohols to the excited 9.     

Formulation study for lansoprazole fast-disintegrating tablet. II. Effect of triethyl citrate on the quality of the products

The purpose of this study was to develop enteric-coated microgranules for the lansoprazole fast-disintegrating tablet (LFDT), which is a rapidly disintegrating tablet containing enteric-coated microgranules. In our previous study, it was clarified that sufficient flexibility of the enteric layer was achieved by the optimized combined ratio of methacrylic acid copolymer dispersion to ethyl acrylate-methyl methacrylate copolymer dispersion and adding the optimized concentration of triethyl citrate to reduce the damage during the compression process. However, since triethyl citrate has an unpleasant bitter taste and is especially incompatible with lansoprazole, it adversely affects the taste and stability of lansoprazole in the enteric-coated microgranules. The enteric layer containing macrogol 6000 was proven useful to improve the unpleasant bitter taste and stability of lansoprazole, because macrogol 6000 does not have an unpleasant bitter taste and is more compatible than triethyl citerate. By covering the inner (first enteric layer) and outer side (third enteric layer) of the enteric layer containing triethyl citrate (second enteric layer) with the enteric layer containing macrogol 6000, we resolved the stability problem of lansoprazole and the unpleasant bitter taste. Finally, we developed enteric-coated microgranules comprising seven layers: 1) core, 2) active compound layer, 3) intermediate layer, 4) first enteric layer, 5) second enteric layer, 6) third enteric layer, and 7) over coating layer. The enteric-coated microgranules have the multiple functions of reducing the damage to the enteric layer during the compression process, improving the stability of lansoprazole, and masking the unpleasant bitter taste.     

A mixed version of Menger's theorem

An(a, b)-n-fan means a union ofn internally disjoint paths. Menger's theorem states that a graphG has an(a, b)-n-fan if and only ifG isn-connected betweena andb. We show thatG contains edge-disjoint(a, b)-n-fans if and only if for anyk withk0min{n–1, |V(G)|–2} and for any subsetX ofV(G)-{a, b} with cardinalityk, G-X is (n-k)-edge-connected betweena andb.     

Correlation between oxygen consumption and photobleaching during in vitro photodynamic treatment with ATX-S10.Na(II) using pulsed light excitation: dependence of pulse repetition rate and irradiation time

We revealed that in ATX-S10.Na(II)(13,17-bis (1-carboxypropionyl) carbamoylethyl-8-etheny-2-hydroxy-3-hydroxyiminoethylidene-2,7,12,18-tetraethyl porphyrin sodium)-mediated photodynamic therapy using 667 nm nanosecond-pulsed light excitation at a peak intensity of 2.0 MW/cm(2), phototoxicity increased with decreasing pulse repetition rate in the range of 5-30 Hz for A549 cell cultures. To examine the relation between the reaction mechanism and measured phototoxicity, we carefully measured the kinetics of photochemical oxygen consumption and photobleaching during irradiation of ATX-S10.Na(II)-sensitized A549 monolayer cultures. Measurements of oxygen consumption with a microelectrode, which was performed just above the cells, showed that there was no significant difference between the magnitudes of decrease in oxygen at the three repetition rates at the same cumulative fluence. Loss of ATX-S10.Na(II) fluorescence intensity also exhibited little repetition rate dependence when compared at the same cumulative fluence. We investigated the correlation between oxygen consumption and photobleaching during irradiation and obtained "fluorescence-oxygen diagrams." The diagrams showed dynamic changes between oxygen-dependent and oxygen-independent photobleaching at the higher repetition rates of 10 and 30 Hz, whereas such change was not clearly seen over the whole irradiation time at 5 Hz. These results suggest that the reduced phototoxicity at high repetition rates might be due to an oxygen-independent reaction. We presumed that the change in the reaction mechanism was associated with the local concentrations of the photosensitizer and oxygen in cells during irradiation.     

An automated analyzer for vancomycin in plasma samples by column-switching high-performance liquid chromatography with UV detection

An automated analyzer for vancomycin in rat plasma by column-switching high-performance liquid chromatography (HPLC) with UV detection was developed. The method includes in-line extraction of vancomycin by ion-exchange cartridge column and a separation on a reversed-phase column with UV detection at 215 nm. Plasma samples were diluted by mobile phase solution and directly injected to HPLC. Vancomycin was quantitatively recovered from rat plasma samples. The separation was completed within 15 min. The calibration curve was linear over the range from 0.5 to 100 microg/mL with the detection and quantification limits of 0.5 microg/mL (2.5 ng on column; signal-to-noise ratio = 3). The values of precision in intra- and inter-day assays (n = 3) were less than 1.92 and 3.69%, respectively. This method does not require time-consuming pre-treatment and is suitable for the routine assay of plasma samples.     

Preferential hydration and the exclusion of cosolvents from protein surfaces

Protein stability is enhanced by the addition of osmolytes, such as sugars and polyols and inert crowders, such as polyethylene glycols. This stability enhancement has been quantified by the preferential hydration parameter which can be determined by experiments. To understand the mechanism of protein stability enhancement, we present a statistical mechanical analysis of the preferential hydration parameter based upon Kirkwood-Buff theory. Previously, the preferential hydration parameter was interpreted in terms of the number of hydration waters, as well as the cosolvent exclusion volume. It was not clear how accurate these interpretations were, nor what the relationship is between the two. By using the Kirkwood-Buff theory and experimental data, we conclude that the contribution from the cosolvent exclusion dominantly determines the preferential hydration parameters for crowders. For osmolytes, although the cosolvent exclusion largely determines the preferential hydration parameters, the contribution from hydration may not be negligible.     

An efficient novel synthesis of beta-(azuleno[1,2-b]benzothienyl)- and beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones by the tropylium ion-mediated intramolecular furan ring-opening reaction and X-ray investigation of methyl ketone derivative

Intramolecular reaction of 2-tropylio-3-(5-substituted 2-furyl)benzothiophenes (3), prepared from the corresponding 2-cycloheptatrienyl-3-(5-substituted 2-furyl)benzothiophenes (2), afforded the beta-(azuleno[1,2-b]benzothienyl)-alpha,beta-unsaturated ketones (4), which are otherwise difficult to obtain, in moderate yields. The reaction involves a ring-opening process of the furan ring by intramolecular attack of the tropylium ion onto the 2-position of the furan ring. Similarly, beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones (8) were obtained from the corresponding 3-tropylio-2-(5-substituted 2-furyl)benzothiophenes (7) albeit in lower yields. The molecular and crystal structures of the methyl ketone derivative, 8a, are discussed on the basis of X-ray structure analysis.