A first high enantiocontrol of an asymmetric tertiary carbon center attached with a fluoroalkyl group via Rh(I)-catalyzed conjugate addition reaction

Treatment of fluoroalkylated electron-deficient olefins with various boronic acids in the presence of a catalytic amount of Rh(I) coordinated with (S)-BINAP in toluene/H₂O at the reflux temperature for 3 h gave the corresponding conjugate addition products with high enantioselectivity in high yields.     

Characterization and quantification of fluoxymesterone metabolite in horse urine by gas chromatography/mass spectrometry

Fluoxymesterone, an anabolic steroid with the 17alpha-methyl,17beta-hydroxy group, has been developed as an oral formulation for therapeutic purposes. However, it is also used illegally in racehorses to enhance racing performance. In this study, we detected 9alpha-fluoro-17,17-dimethyl-18-norandrostane-4,13-dien-11beta-ol-3-one by gas chromatography/mass spectrometry (GC/MS), which has not been reported as a fluoxymesterone metabolite so far in horse. It was synthesized for use as a reference standard, and characterized on the basis of (1)H NMR and (13)C NMR spectra, as well as GC/MS EI mass spectra of TMS derivatives. It was excreted as the main metabolite in horse urine, and its reference standard could be synthesized easily. Therefore, this metabolite could be a useful target for a doping test of fluoxymesterone in racehorses.     

Discovery of Hexagonal Structured Pd–B Nanocrystals

We report on hexagonal close-packed (hcp) palladium (Pd)–boron (B) nanocrystals (NCs) by heavy B doping into face-centered cubic (fcc) Pd NCs. Scanning transmission electron microscopy–electron energy loss spectroscopy and synchrotron powder X-ray diffraction measurements demonstrated that the B atoms are homogeneously distributed inside the hcp Pd lattice. The large paramagnetic susceptibility of Pd is significantly suppressed in Pd–B NCs in good agreement with the reduction of density of states at Fermi energy suggested by X-ray absorption near-edge structure and theoretical calculations.     

Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.     

A Nadel vanishing theorem via injectivity theorems

The purpose of this paper is to establish Nadel type vanishing theorems with multiplier ideal sheaves of singular metrics admitting an analytic Zariski decomposition (such as, metrics with minimal singularities and Siu’s metrics). For this purpose, we generalize Kollár’s injectivity theorem to an injectivity theorem for line bundles equipped with singular metrics, by making use of the theory of harmonic integrals. Moreover we give asymptotic cohomology vanishing theorems for high tensor powers of line bundles.     

Resistivity control of sputtered amorphous-silicon by ion-implantation

The resistivity of a hydrogenated sputtered amorphous-silicon is controlled by using room temperature implantation of P⁺. It is found that the defects produced by implantation can be minimized by annealing at 300°C in an H₂ atmosphere, and also found that there is a threshold implanted dose, beyond which the resistivity begins to be controlled by changing the dose.     

Synthesis of a proposed structure for the diffusible extracellular factor of Xanthomonas campestris pv. campestris

A proposed structure for the diffusible extracellular factor (DF) of Xanthomonas campestris pv. campestris (Xcc) has been synthesized. Its MS spectrum and biological activity, however, contradict those of the natural product previously reported, suggesting that the structure for DF of Xcc must be reexamined.     

Initial step of anthracene‐sensitized photoacid generation from diphenyliodonium hexafluorophosphate in an epoxy matrix studied by steady‐state and laser‐flash photolyses

The anthracene‐sensitized photodecomposition of diphenyliodonium hexafluorophosphate was studied in an epoxy matrix. From steady‐state photolysis, the generation of protons, which are considered to be the actual initiators of the polymerization of epoxides, was confirmed. In addition, 9‐phenylanthracene was detected as a main product from anthracene. From time‐resolved laser‐flash photolysis, a broad absorption band with a peak at about 500 nm was observed that was thought to be due to the precursor of 9‐phenylanthracene. On the basis of these results, we propose electron transfer from anthracene in the excited singlet state to the diphenyliodonium cation as the initial step of photoacid generation. This process is followed by fast chemical reactions, which generate 9‐phenylanthracene and protons, and back electron transfer from the diphenyliodine radical to the anthracene cation radical. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2937–2946, 2001