Ab initio molecular dynamics study of H2 formation inside POSS compounds

The mechanism and dynamics of the formation of a hydrogen molecule by incorporating two hydrogen atoms in a stepwise manner into the cavity of some POSS (polyhedral oligomeric silsesquioxanes) compounds has been investigated by ab initio molecular orbital and ab initio molecular dynamics (AIMD) methods. The host molecules in the present reactions are two types of POSS, T(8) ([HSiO(1.5)](8)) and T(12)(D(2d)) ([HSiO(1.5)](12)). AIMD simulations were performed at the CASSCF level of theory, in which two electrons and two orbitals of the colliding hydrogen atoms are included in the active space. The trajectories were started by inserting the second hydrogen atom into the hydrogen atom-encapsulated-POSS (H + H@T(n) → H(2)@T(n); n = 8 and 12). In many cases, the gradual formation of a hydrogen molecule has been observed after frequent collisions of two hydrogen atoms within the cages. The effect of the introduction of an argon atom in T(12) is discussed as well.     

Unique inclusion properties of crystalline powder p-tert-butylthiacalix[4]arene toward alcohols and carboxylic acids

Powdery crystals of p-tert-butylthiacalix[4]arene (2) selectively include EtOH from 1:1 mixtures of MeOH-EtOH and EtOH-PrOH, and EtCO(2)H from HCO(2)H-EtCO(2)H. On the other hand, no acid is included from HCO(2)H-MeCO(2)H, even though MeCO(2)H is included from the neat acid. The origins of these phenomena are discussed based on X-ray analysis of inclusion crystals prepared separately by crystallization.     

Rh-doped SrTiO3 photocatalyst electrode showing cathodic photocurrent for water splitting under visible-light irradiation

A Rh-doped SrTiO(3) (SrTiO(3):Rh) photocatalyst electrode that was readily prepared by pasting SrTiO(3):Rh powder onto a transparent indium tin oxide electrode gave a cathodic photocurrent under visible-light irradiation (λ > 420 nm), indicating that the SrTiO(3):Rh photocatalyst electrode possessed p-type semiconductor character. The cathodic photocurrent increased with an increase in the amount of doped Rh up to 7 atom %. The incident-photon-to-current efficiency at 420 nm was 0.18% under an applied potential of -0.7 V vs Ag/AgCl for the SrTiO(3):Rh(7 atom %) photocatalyst electrode. The photocurrent was confirmed to be due to water splitting by analyzing the evolved H(2) and O(2). The water splitting proceeded with the application of an external bias smaller than 1.23 V versus a Pt counter electrode under visible-light irradiation and also using a solar simulator, suggesting that solar energy conversion should be possible with the present photoelectrochemical water splitting.     

Microbial conversion of curcumin into colorless hydroderivatives by the endophytic fungus Diaporthe sp. associated with Curcuma longa

We investigated the microbial conversion of curcumin (1) using endophytic fungi associated with the rhizome of Curcuma longa (Zingiberaceae). We found that Diaporthe sp., an endophytic filamentous fungus, converts curcumin (1) into four colorless derivatives, namely (3R,5R)-tetrahydrocurcumin (2), a novel (3R,5S)-hexahydrocurcumin (3) named neohexahydrocurcumin, (3S,5S)-octahydrocurcumin (4) and meso-octahydrocurcumin (5).     

Molecular-shape selectivity by molecular gel-forming compounds: bioactive and shape-constrained isomers through the integration and orientation of weak interaction sites

A molecular gel system was assembled on carrier particles and the integrated effect of weak interaction sites enabled highly efficient separation of the bioactive and shape-constrained isomers of tocopherols, β-carotene, and polycyclic aromatic hydrocarbons (PAHs) by multiple interaction mechanisms.     

A novel homoisocarbacyclin analog with potent and long-lasting activity.

A synthesis of a novel and chemically stable homoisocarbacyclin analog, TY-11223 (3), has been accomplished. The analog (3), given intravenously or orally, showed potent and long-lasting activities in inhibiting platelet aggregation and, in addition, a good selectivity in biological activities.     

Dependence of thermal conductivity on electrical resistivity in Bismuth-Tellurides

The p-type (Bi_0.25Sb_0.75)₂Te₃ doped with 3-12 wt% excess Te alone and n-type Bi₂(Te_0.94Se_0.06)₃ codoped with 0.017-0.026 wt% Te and 0.068-0.102 wt% I were prepared by the Bridgman method, to produce intentionally polycrystalline. Some of the as-grown specimens were annealed, in order to prepare specimens with much different ρ. These polycrystalline specimens have almost the same degree of alignment of the c plane parallel to the freezing direction. The electrical rersistivity ρ and thermal conductivity κ were measured at 298 K along the freezing direction and κ was plotted as a function of ρ. As a result, the lattice components κ_ph obtained by subtracting the electronic component κ_el from the observed κ were found to decrease almost linearly with a decrease of ρ in both p- and n-type specimens, where κ_el was calculated using Wiedemann-Franz law. This tendency is consistent with the conventional result that κ_ph becomes negligible small in metals. The significant decrease in κ_ph with decrease in ρ is considered to be caused predominantly by the phonon scattering due to dopants. The relationship between κ_ph and ρ was first clarified in the intermediate region between the metal and insulator.