Cohaerins C-F, four azaphilones from the xylariaceous fungus Annulohypoxylon cohaerens

Four azaphilones named cohaerins C-F, along with 4,5,4′,5′-tetrahydroxy-1,1′-binaphthyl were isolated from the methanolic extract of the stromata of Annulohypoxylon cohaerens (Ascomycetes, Xylariaceae). Cohaerins C-E constitute typical azaphilones, bearing a γ-lactone ring, while cohaerin F has an unprecedented carbon skeleton, lacking the lactone ring of the azaphilones and with an aliphatic side chain being attached directly to the azaphilone backbone by a C-C bond. Their structures were determined by 2D NMR, IR, UV, and CD spectroscopy. They showed moderate inhibitory activity of nitric oxide production in RAW cells, and strong and nonselective antimicrobial effects.     

On some slowly convergent series involving the Hurwitz zeta-function

We shall extract the essence of the Adamchik–Srivastava generating function method (Analysis (Munich) 18 (1998) 131) by proving the most far-reaching Ramanujan–Yoshimoto formula and by showing that some of the results stated in Srivastava and Choi (Series Associated with the Zeta and Related Functions, Kluwer Academic Publishers, Dordrecht, 2001) are simple consequences of the above-mentioned formula.     

Synthetic studies of carzinophilin. Part 1: Synthesis of 2-methylidene-1-azabicyclo[3.1.0]hexane systems related to carzinophilin

Synthesis of the model compounds of carzinophilin carrying 2-methylidene-1-aza-bicyclo[3.1.0]hexane systems was achieved. Formation of malonylidenes or N-acyl-glycinylidenepyrrolidines was carried out by utilizing Eschenmoser's sulfide contraction or Herdeis's condensation between the 2-methylthio-Δ¹-pyrrolone derivatives and ethyl nitroacetate, respectively. The 1-azabicyclo-[3.1.0]hexane systems were constructed by base-promoted aziridine formation.     

Crystal structure of the clathrate of 5,12-dihydro-5,12-o-benzenonaphthacene-1,4-dione with benzene (2:1).

In the crystal of the title compound, the quinone fragment of the host (1) participates in weak D-A interactions with a neighboring naphthalene moiety of 1 and with the guest molecule via fairly short intermolecular face-to-face contacts. An intermolecular electrostatic interaction between a quinone-oxygen atom and a neighboring quinone ring is suggested by short O...C contacts. There exist several C-H...O hydrogen bonds, one of which seems to contribute to the formation of a centrosymmetric dimer of 1.     

Synthesis and Optical Properties of SiO2-Coated CeO2 Nanoparticles

Silica (SiO₂)-coated ceria (CeO₂) nanoparticles were prepared using water-in-oil microemulsion. Polyoxyethylene (15) cetylether and cyclohexane were used as a surfactant and organic solvent. SiO₂-coated CeO₂ nanoparticles were obtained by hydrolysis of metal alkoxide (tetraethylorthosilicate, TEOS) in the solution containing CeO₂ precursor nanoparticles. The effects of CeO₂ sources (Ce metal salt) and CeO₂ particle-forming agents on the morphology of SiO₂–CeO₂ particles were investigated. Observation via transmission electron microscopy revealed that the type of particle-forming agent affected the nanoparticles' morphology and that CeO₂ nanoparticles were spherically coated with SiO₂ when using oxalic acid ((COOH)₂) as a particle-forming agent of CeO₂. Furthermore, the transmittance of the particles was high in the visible region (above 400 nm) and decreased in the ultraviolet region.     

Thermosensitive polyalcohols: Synthesis via living cationic polymerization of vinyl ethers with a silyloxy group

Thermosensitive homopolymers and copolymers with hydroxy groups were synthesized via the living cationic polymerization of Si‐containing vinyl ethers. The cationic homopolymerization and copolymerization of five vinyl ethers with silyloxy groups, each with a different spacer length, were examined with a cationogen/Et_1.5AlCl_1.5 initiating system in the presence of an added base. When an appropriate base was added, the living cationic polymerization of Si‐containing monomers became feasible, giving polymers with narrow molecular weight distributions and various block copolymers. Subsequent desilylation gave well‐defined polyalcohols, in both water‐soluble and water‐insoluble forms. One of these polyalcohols, poly(4‐hydroxybutyl vinyl ether), underwent lower‐critical‐solution‐temperature‐type thermally induced phase separation in water at a critical temperature (T_PS) of 42 °C. This phase separation was quite sensitive and reversible on heating and cooling. The phase separation also occurred sensitively with random copolymers of thermosensitive and hydrophilic or hydrophobic units, the T_PS values of which in water could be controlled by the monomer feed ratio. The thermal responsiveness of this polyalcohol unit made it possible to prepare novel thermosensitive block and random copolymers consisting solely of alcohol units. One example prepared in this study was a 20 wt % aqueous solution of a diblock copolymer consisting of thermosensitive poly(4‐hydroxybutyl vinyl ether) and water‐soluble poly(2‐hydroxyethyl vinyl ether) segments, which transformed into a physical gel above 42 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3300–3312, 2003     

Stereochemistry of reduction of the C-24,25 double bond in the conversion of desmosterol into cholesterol

Feeding of the chemically prepared [24-¹³C, 24-²H]desmosterol to cell-free systems derived from rat liver and silkworm gut and to cultured cells of Oryza sativa followed by deuterium-decoupled ¹H, ¹³C shift correlation NMR analysis of the biosynthesized cholesterol revealed the stereospecific incorporation of hydrogen atoms from the re-face of the C-24 position of desmosterol.     

Thermal phase transition of RbMnFe(CN)6 observed by X-ray emission and absorption spectroscopy

The thermal phase transition of RbMnFe(CN)₆ has been observed by Mn and Fe 3p-1s X-ray emission spectroscopy (XES) and 1s X-ray absorption spectroscopy (XAS). The thermal variations of the spin states and the valences of Mn and Fe were determined to be Mn²⁺(S=5/2)-NC-Fe³⁺(S=1/2) for the high-temperature (HT) phase and Mn³⁺(S=2)-NC-Fe²⁺(S=0) for the low-temperature (LT) phase. These transitions are thus caused by charge transfer between Mn and Fe. The temperature dependences of Mn and Fe 3p-1s XES and 1s XAS were observed as the composition of the spectra of the HT and LT phases. The ratios of the HT component in each spectrum show good agreement with the thermal transition curves observed with magnetic susceptibility measurements.