Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species

A treatment of cobalt oxide supported gold nanoparticles (Au/Co₃O₄) under syngas atmosphere effectively generated a cobalt carbonyl-like active species in the reaction vessel. The preparation of Au/Co₃O₄ was quite simple and the in situ generated cobalt species could be used as a stable and easy handling alternative for dicobalt octacarbonyl without bothersome purification prior to use. The reactions, which are sensitive to the purity of the dicobalt octacarbonyl, such as the alkoxycarbonylation of epoxides and the Pauson-Khand reaction, smoothly progressed with Au/Co₃O₄.     

Effect of preparative conditions on crystallinity of apatite particles obtained from simulated body fluids

Preparation of colloidal hydroxyapatite (HAp) particles under body fluid conditions was investigated with focusing on the effect of preparative conditions on crystallinity of the resulting particles. Tris(hydroxymethyl)aminomethane was added to 1.5SBF (a solution having 1.5 times higher ion concentrations than those of a simulated body fluid, SBF) to increase the solution pH, which resulted in induction of homogeneous nucleation of HAp in the solution. Colloidal HAp particles having diameters about 300 nm were obtained. When the reaction was proceeded at 70°C and the sample was dried by heating, it was effective to obtain HAp particles having high crystallinity. Experimental results support that remaining water in the sample contributed to increase HAp crystallinity.     

Antitrypanasomal activity of novel benzaldehyde-thiosemicarbazone derivatives from kaurenoic acid

A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM.     

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).     

Fabrication and evaluation of photonic metamaterial crystal

Many researching efforts have been reported to seek various fundamental LC resonance structures, recently. But still the Split Ring Resonator (SRR) is the most famous and major fundamental LC-resonance structure used in the metamaterial. We employed SRR structure as the fundamental LC-resonance mechanism to fabricate photonic crystal with periodic arrangement of two different metamaterial areas composed from SRR arrays on the dielectric substrate. We developed Photonic Metamaterial Crystal (PMC) to realize the more advanced and versatile functions of the metamaterial by 1 dimensional or 2 dimensional periodic arranging of two metamaterial sections which have different dispersion properties due to the different size of SRR structures each other. In this paper, we report the fabrication process, estimation of PMC properties and some possible future application prospects, for instance the PMC waveguide structures and nonlinear properties of PMC observed as selective LC-resonant properties in Raman mapping analysis of PMC. These are quite interesting characters of PMC and the attractive applications as the PMC devices.     

Magnetic Field and Magnetic Isotope Effects upon Reactions of Heavy Atom-Centered Radicals

We present our recent studies on magnetic field effects (MFEs) observed in reactions of heavy atom-centered radicals such as Si-,P-, Ge-, and Sn-radicals with a ns-laser photolysis technique under magnetic fields of 0–10 T. Although the MFES of heavy atom-centered radicals are much smaller than those of C-radicals due to the spin-orbit interaction of heavy atoms, we have found appreciable MFEs in many reactions of such heavy atom-centered radicals. Comparing the MFES of C-radicals with those of heavy atom-centered ones, we have explained the MFEs of heavy atom-centered radicals in terms of the Δg and relaxation mechanisms. We have found that the separation between the MFES due to the Δg mechanism and those due to the relaxation one is possible with the enhancement of spin relaxation by the addition of a paramagnetic ion. We have also tried to enrich magnetic isotopes of heavy atoms with the magnetic isotope effect (MIE), using the reactions which show fairly large MFES. Recently, we have succeeded in enriching ⁷³Ge. This is the heaviest isotope which has so far been enriched with the MIE from samples of natural abundance.     

Electrochemical cells with multilayer functional electrodes

Microstructural and chemical changes in a NiO-YSZ electrocatalytic electrode were studied. The microstructural changes in the NiO-YSZ electrocatalytic electrode after the cell operation was compared with the electrode quenched under the applied voltage to suppress the oxidation process. The reversible reduction of NiO into Ni and the formation of intergranular Ni layers at the NiO/YSZ interface were investigated. It was shown that in a compositional range of the NiO-YSZ electrodes from 1/3 to 2/3 the value of the ambipolar conductivity increased with increasing voltage applied to the electrochemical cell. The observed reversible increase in the value of ambipolar conductivity of the electrocatalytic electrode is described in frames of the model of reversible reduction of NiO into Ni under the conditions of cell operation.     

Asymptotic expansions of the distributions of some test statistics for Gaussian ARMA processes

Let {X_t} be a Gaussian ARMA process with spectral density f_θ(λ), where θ is an unknown parameter. The problem considered is that of testing a simple hypothesis H:θ = θ₀ against the alternative A:θ ≠ θ₀. For this problem we propose a class of tests , which contains the likelihood ratio (LR), Wald (W), modified Wald (MW) and Rao (R) tests as special cases. Then we derive the χ² type asymptotic expansion of the distribution of T up to order n⁻¹, where n is the sample size. Also we derive the χ² type asymptotic expansion of the distribution of T under the sequence of alternatives A_n: θ = θ₀ + /√n, ε > 0. Then we compare the local powers of the LR, W, MW, and R tests on the basis of their asymptotic expansions.     

The site distribution of Ti and V and the metal-metal interaction in the ternary system (V,Ti)5S8

The phase relations of the ternary system V_1?xTi_xS_1.57 are presented on the basis of X-ray diffractometry. The site distribution of Ti and V atoms in the structure is clarified through an NMR absorption study at room temperature. The phase relations and the site distribution of Ti and V, which appear to be closely related to each other, are discussed in terms of the metal-metal interaction of the face-shared octahedra in the metal-deficient distorted NiAs structure.     

Magnetic field effect on the hydrogen abstraction of xanthone from xanthene in SDS micelles

The magnetic field effect (<800 G) on the hydrogen abstraction of xanthone from xanthene in SDS aqueous micellar solutions was studied using laser flash photolysis. The rate of triplet-singlet intersystem crossing of the radical pair of xanthone ketyl and 9-xanthenyl formed upon photolysis decreases from 1.4 × 10⁶ s^?1 at O G to 0.4 × 10⁶ s^?1 at 640 G.