Synthetic studies on carbapenem antibiotics from penicillins.II. regio- and stereoselective aldol reaction of a chiral azetidinone: a synthesis of optically active 6-epicarpetimycins

Aldol and alkylation reactions of the chiral 4-allylazetidinone 1 gave 3,4-trans-azetidinones as major products, in which 10 was converted in several steps to the optically active 6-epicarpetimycins 2.     

Sacculatal and isosacculatal,two new exceptional diterpenedials from the liverwort, trichocoleopsis sacculata

The stereostructures of the two new exceptional diterpene dialdehydes from the liverwort, Trichocoleopsis sacculata: sacculatal (1), responsible for the characteristic pungent taste, and isosacculatal (2) have been determined by the spectral evidence and by comparison with polygodial (3), isopolygodial (4), and drimanediol (6) of known relative configurations.     

Elastic anomaly in K2ZnCl4 around the normal-incommensurate-commensurate phase transition points

The ultrasonic velocities in K₂ZnCl₄ were measured as functions of temperature. At the incommensurate-commensurate phase transition point the velocity of the c₅₅ mode showed a clear anomaly, whereas anomalies were hardly observable in all other modes. The results are analyzed in terms of a phenomenological theory.     

Synthesis of spirocyclic C-arylribosides via cyclotrimerization

[reaction: see text] Spirocyclic C-arylribosides were synthesized from the known gamma-ribonolactone derivative. Lithium acetylide addition followed by glycosylation with 3-(trimethylsilyl)propargyl alcohol converted the ribonolactone to silylated diynes. After desilylation or iodination, subsequent ruthenium-catalyzed cycloaddition of resultant diynes with alkynes or chloroacetonitrile gave spirocyclic C-arylribosides.     

Electrical breakdown of microwave plasma in water

The electrical breakdown of microwave plasma in water was investigated between 1 and 30 kPa. The dependency of the ignition power for generating plasma on the size of coaxial electrode was measured. The ignition power decreases with a decrease of the diameter of the inner electrode. The behavior of microwave plasma in water was observed using a high-speed camera. The plasma ignites in a bubble generated by microwave heating. The model for calculating the electric field was created on the basis of the captured images of the bubble just before plasma ignition. The method presented can be used to visualize the electrical field distribution in the bubble. The electric field breakdown was calculated using the measured ignition power. The electric field breakdown of plasma in water is of the same order as gas phase plasma.     

Synthesis and photophysical properties of dinaphtho[2,3-b:2′,3′-i]dihydrophenazine derivatives

A dinaphtho[2,3-b:2′,3′-i]dihydrophenazine (DNP) derivative was synthesized by Buchwald-Hartwig cross-coupling, and its electronic spectrum was compared with that of dinaphtho[b,i]dihydrophenazine-5,18-dione (DNP-dione) as an anthraquinone analog. An absorption band of DNP is attributed to extension of π-conjugation over the entire molecule via the N atom. DNP-dione showed a broad absorption band in the range 450–490?nm due to intramolecular charge-transfer interactions. Additionally, the absolute fluorescence quantum yield of DNP was larger than that of DNP-dione. DNP-dione exhibited reversible oxidation peaks and a similar oxidation potential to DNP, since there are very weak electronic interactions between the anthracene and anthraquinone units across the N atoms with the 4-octyloxyphenyl substituent.     

Determination of structures of cobalt(II)-chloro complexes in hydrochloric acid solutions by X-ray absorption spectroscopy at 298 K

The anion exchange reaction is fundamental to the adsorption and desorption of a specific species from a solution phase to an extracting phase, and it is widely used for separation and waste fluid treatment in industrial fields. However, the details of the anion exchange reaction are poorly understood. Quantitative thermodynamic analysis needs a precise solution condition before and after the exchange reaction. Identification of species adsorbed on the anion exchanger is also necessary because there are multiple species in the solution phase in general. Cobalt is a base metal that is widely used in modern society. One of the authors determined the distribution of cobalt-chloro complexes in hydrochloric acid solutions. It is necessary to know what species are adsorbed on anion exchangers for the thermodynamic analysis of the anion exchange reaction. The comparison in structures between the species in the solution phase and adsorbed on anion exchangers reveals what species are adsorbed. Therefore, the determination of the structures of cobalt-chloro complexes in the solution phase is the next step for quantitative analysis. X-ray absorption spectroscopy (XAS) was used for the structure analysis. Factor analysis can decompose extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectra consisting of multiple species into individual spectra of single species using the distribution determined using UV-Vis absorption spectra. Fitting EXAFS theoretical models to the decomposed individual spectra determined the structures of three cobalt-chloro complexes: an octahedron of [Co^II(H₂O)₆]²⁺, a distorted octahedron of [Co^II(H₂O)₅Cl]⁺, and a tetrahedron of [Co^IICl₄]^2?. The XANES spectra showed us that the Cl ligand in [Co^II(H₂O)₅Cl]⁺ was attracted to the center atom of Co^II by an electrostatic force, and the bonding system between Cl ligands and Co^II in [Co^IICl₄]^2? involved covalency.

     

Electron-boson coupling and oxygen-isotope effect in the optical conductivity of high-Tc superconductors

We have investigated electron-boson coupling in the optical conductivity of high-T_c superconductors through the optical self-energy. The real part of the self-energy (ReΣ^op(ω)) of YBa₂Cu₃O_y (YBCO) shows a characteristic doping dependence. In the optimally doped YBCO, ReΣ^op(ω) has a single peak around 65 meV, which corresponds to the kink structure of the band dispersion. On the other hand, in the under-doped YBCO, the peak structure of ReΣ^op(ω) splits into two parts. To evaluate contribution from the phonons in electron-boson coupling, we have measured oxygen-isotope effects by substituting ¹⁶O→¹⁸O for the optimally doped and under-doped YBCO.