Rhenium-catalyzed synthesis of multisubstituted aromatic compounds via C-C single-bond cleavage

A reaction between a beta-keto ester and an acetylene in the presence of a rhenium complex, [ReBr(CO)3(thf)]2, as a catalyst, provided a 2-pyranone derivative in excellent yield via retro-aldol reaction (C-C single bond cleavage). By adding an acetylene-bearing ester group(s) after the formation of 2-pyranones, an aromatization reaction proceeded and multisubstituted aromatic compounds were obtained in good to excellent yields.     

Single‐step enrichment of basophils from human peripheral blood by a novel method using a Percoll density gradient

We have developed a novel continuous flow‐through cell separation method using a Percoll density gradient. This method can continuously separate a large number of cells into five fractions according to their densities. To apply this method to the separation of basophils, Percoll density gradients were modified to improve basophil enrichment. When a set of Percoll density gradients was prepared (1.071, 1.075, 1.080, 1.084, and 1.090 g/mL) the basophils in a healthy volunteer were enriched by an average of 23.1 and 63.5% at Percoll densities of 1.075 (fraction 3) and 1.080 g/mL (fraction 4), respectively. On average, the yield of basophils was 1.66 × 10⁵ cells in fraction 3 and 1.61 × 10⁵ cells in fraction 4 from 9 mL of peripheral blood. The expression of CD203c (cluster of differentiation 203c) on separated basophils was upregulated by anti‐immunoglobulin E stimulation similar to basophils in whole blood. Histamine release induced by calcium ionophore was also observed in the separated basophils. The present method will be useful for basophil enrichment since it preserves their function without using counterflow elutriation and immunological reagents, and this method will be effective as a preparative separation for cell purification by flow cytometry.     

Comprehensive separation of secondary metabolites in natural products by high-speed counter-current chromatography using a three-phase solvent system

High-speed counter-current chromatography (HSCCC) using the three-phase solvent system n-hexane-methyl acetate-acetonitrile-water at a volume ratio of 4:4:3:4 was applied to the comprehensive separation of secondary metabolites in several natural product extracts. A wide variety of secondary metabolites in each natural product was effectively extracted with the three-phase solvent system, and the filtered extract was directly submitted to the HSCCC separation using the same three-phase system. In the HSCCC profiles of crude natural drugs listed in the Japanese Pharmacopoeia, several physiologically active compounds were clearly separated from other components in the extracts. The HSCCC profiles of several tea products, each manufactured by a different process, clearly showed their compositional difference in main compounds such as catechins, caffeine, and pigments. These HSCCC profiles also provide useful information about hydrophobic diversity of whole components present in each natural product.     

Colony-forming cell assay for human hematopoietic progenitor cells harvested by a novel continuous-flow cell separation method

In order to prove the functional potentiality of cells separated according to their densities by a novel continuous-flow cell separation method, the colony-forming cell (CFC) assay was performed on the harvested cells from peripheral blood and umbilical cord blood. The number of colony-forming unit-granulocyte, erythroid, macrophage, megakaryocyte (CFU-GEMM), which are considered to be stem cells, was approximately 3% of colonies developed from the peripheral blood and approximately 4% of colonies from the umbilical cord blood. It appears that this new method could allow us for harvesting of hematopoietic progenitor cells without losing their native ability to proliferate.     

In situ photolysis of CD3I in solid orthodeuterium

Photochemical reactions of molecules in solid orthodeuterium (o-D2) have been studied by high-resolution infrared spectroscopy and compared with previous results obtained in solid parahydrogen (p-H2). Ultraviolet photolysis of CD3I molecules in solid o-D2 yielded CD3 radicals and iodine atoms efficiently, which indicates a small cage effect in solid o-D2, as in the case of solid p-H2. The Fourier transform infrared spectrum of the nu3 vibrational band of CD3 showed a rotational structure with additional splitting due to crystal field interactions. The magnetic dipole transition (2P1/2<--2P3/2) of the I atom isolated in solid o-D2 was observed together with a strong rotational satellite of deuterium molecules through the electron-roton coupling in solid hydrogen. The tunneling reaction between CD3 and D2 was not observed in a time scale of a few days, which gives the upper limit of the tunneling reaction rate of 10(-8) s(-1) at 4.2 K.     

Exploring a critical diameter for thermo-acoustic instability of downward propagating flames in tubes

Thermo-acoustic oscillations are observed when a flame ignited at open end of a tube propagates towards the closed end due to interaction between unsteady heat release rate fluctuations from flame and acoustic fluctuations. In our past work, it was found that thermo-acoustic instability increases with decreasing diameter from 7.0 cm to 3.0 cm. A recent study in flame propagation in Hele–Shaw cells showed that thermo-acoustic instability is not observed for plate separation less than or equal to 0.4 cm. Thermoacoustic instabilities cannot be observed in very narrow tubes due to excessive damping from the wall. This opens up the possibility of a critical diameter where thermo-acoustic instability would be maximum. In this work we perform flame propagation experiments with diameter of combustion tube in the range 0.5 cm to 3 cm for a fixed length of 70.2 cm. It was found that thermo-acoustic parametric instability begins at lowest laminar burning velocity when the diameter is around 1.0 cm. This diameter is termed as critical diameter. Critical diameter is found to be independent of Lewis number of mixtures. Existence of a critical diameter is thus proved experimentally. Growth rates of primary instability increase with decreasing diameter and show a maximum around the critical diameter and decrease with further decrease in tube diameter. But, growth rates of secondary instability as well as maximum pressure fluctuation amplitude decreases continuously with decreasing diameter. Mechanisms responsible for these observations and existence of a critical diameter are clarified.     

Studies on the performance of different coiled column configurations for compact type-I countercurrent chromatography

Three types of novel coiled column configurations, i.e. a triangular coiled column and elliptical coiled columns I and II, were designed for type-I countercurrent chromatography and their performances were evaluated with two solvent systems each with suitable test samples. Three dinitrophenyl (DNP) amino acids (DNP-DL-glu, DNP-β-ala and DNP-L-ala) were separated with a moderately hydrophobic two-phase solvent system composed of hexane-ethyl acetate-metanol-0.1 M hydrochloric acid (1:1:1:1, v/v), while two dipeptides (tryptophyl-tyrosine and valyl-tyrosine) were separated with a polar solvent system composed of 1-butanol-acetic acid-water (4.75:0.25:5, v/v). The overall results indicated that the performance of compact type-I countercurrent chromatography was improved by elliptical coiled column I which was mounted with its maximum coil diameter perpendicular to the surface of the column holder. Hydrodynamic effects involved in these separations were discussed.     

Polarization and temperature dependent spectra of poly(3-hydroxyalkanoate)s measured at terahertz frequencies

Temperature-dependent terahertz (THz) absorption spectra of poly(3-hydroxyalkanoate)s (PHAs) were measured by using a Fourier transform far-infrared (FT-FIR) spectrometer and a THz time-domain spectrometer over a temperature range of 10 K to 465 K with a liquid helium cryostat and a heating cell. Clear differences were observed between the spectra of crystalline and amorphous polyhydroxybutyrate (PHB), indicating that the absorption peaks observed in the THz spectra originated in the higher-order conformation of PHB. The polarization spectra of a stretched PHB sample were measured, and the direction of the vibrational transition moment was determined. The temperature dependences of the spectra reveal frequency shifts and broadening of the absorption peaks with temperature, suggesting large anharmonicity of the vibrational potential. The temperature shift behaviour is quite different in each transition. Some of the transitions show a blue shift, which cannot be explained by a simple anharmonic potential model. Frequency shifts of the peaks were mainly observed below 10 THz, which suggests a large anharmonicity of the vibrational potential at lower frequencies.