Substoichiometric precipitation of silicon as barium fluorosilicate

Distillation and substoichimetric precipitation for silicon have been developed for the determination of trace amounts of silicon. It is based on substoichiometric precipitation as barium fluorosilicate and the distillation of silicon tetrafluoride. The separation has been applied for the determination of silicon in gallium arsenide and NBS steel as standard reference material.     

Synthesis of (-)-aphanorphine using aryl radical cyclization

[structure: see text] The synthesis of (-)-aphanorphine was achieved by using Bu(3)SnH-mediated aryl radical cyclization of 1-benzyloxycarbonyl-2-(2-bromo-4-methoxyphenylmethyl)-2-methoxycarbonyl-4-(phenylthiomethylene)pyrrolidine, leading to exclusive formation of the 6-exo cyclization product.     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.     

A concept for controlling singlet oxygen (1 Delta g) yields using nitroxide radicals: phthalocyaninatosilicon covalently linked to nitroxide radicals

In this study, we have investigated the singlet oxygen ((1)Delta(g)) generation mechanism using phthalocyaninatosilicon (SiPc) covalently linked to nitroxide radicals (NRs), and we succeeded in increasing the singlet oxygen quantum yield (Phi(Delta)) by linking the NRs. This originates from both an increase in the triplet quantum yield and excited-state lifetimes long enough to utilize photochemical reactions. Because the electron exchange interactions with paramagnetic species were known to result only in very fast excited-state relaxation, leading to a decrease in photochemical reaction yields, this increase in Phi(Delta) is an unusual and precious example for increasing photochemical reaction yields by electron exchange interactions with paramagnetic species. In addition, our experiments and theoretical analyses show that the spin-selective energy transfer rate constant is not influenced by linking the NRs and can be evaluated by the product of spin-statistical factors and matrix elements between the initial and final states.     

Oxysulfide Sm(2)Ti(2)S(2)O(5) as a stable photocatalyst for water oxidation and reduction under visible light irradiation (lambda < or = 650 nm)

A Ti-based oxysulfide, Sm(2)Ti(2)S(2)O(5), was studied as a visible light-driven photocatalyst. Under visible light (440 nm < or = lambda < or = 650 nm) irradiation, Sm(2)Ti(2)S(2)O(5) with a band gap of approximately 2 eV evolved H(2) or O(2) from aqueous solutions containing a sacrificial electron donor (Na(2)S-Na(2)SO(3) or methanol) or acceptor (Ag(+)) without any noticeable degradation. This oxysulfide is, therefore, a stable photocatalyst with strong reduction and oxidation abilities under visible-light irradiation. The electronic band structure of Sm(2)Ti(2)S(2)O(5) was calculated using the plane-wave-based density functional theory (DFT) program. It was elucidated that the S3p orbitals constitute the upper part of the valence band and these orbitals make an essential contribution to the small band gap energy. The conduction and valence bands' positions of Sm(2)Ti(2)S(2)O(5) were also determined by electrochemical measurements. It indicated that conduction and valence bands were found to have satisfactory potentials for the reduction of H(+) to H(2) and the oxidation of H(2)O to O(2) at pH = 8. This is consistent with the results of the photocatalytic reactions.     

Oxime-based salen-type tetradentate ligands with high stability against imine metathesis reaction

Although salen and its analogues are versatile chelate ligands in inorganic and organometallic chemistry, synthesis of unsymmetrical salen derivatives consisting of two different salicylideneimine moieties is difficult because of the C=N bond recombination. To develop stable analogues of salen-type ligands, we synthesized a series of new ligands salamo (=1,2-bis(salicylideneaminooxy)ethane) on the basis of O-alkyl oxime instead of the imine moiety. Eight salamo ligands 1a-h were prepared in 64-88% yields as colorless crystals from the corresponding salicylaldehydes 2a-h. The crystal structure of 1a-c suggests that the oxime-OH form is more predominant than the keto-NH form. The reaction of 2a-e with excess 1,2-bis(aminooxy)ethane gave monooximes 3a-e in 59-86%, which further reacted with a different salicylaldehyde to afford unsymmetrical salamo ligands 4-8 as stable crystals in 51-70%. No reaction took place when a mixture of salamo derivatives 1a and 1b was treated at 40 degrees C in H2O/MeCN (5:95). However, the metathesis reaction of salen derivatives 9a and 9b completed in 2 h to give a statistical mixture. Monooxime 3b was much more stable than monoimine 11 which is difficult to be isolated. These results indicate the extremely high stability of the salamo derivatives 1 and precursors 3.     

Diffusion coefficients of positronium in polycarbonate at low temperatures

Diffusion coefficients of positronium (Ps) in polycarbonate (PC) have been determined at temperatures between 20 and 300 K by means of positron lifetime spectroscopy. 2,2-dinitrobiphenyl (DNB) was added to the polymer as a Ps quencher and the diffusion coefficients were determined from measured Ps quenching rate constants, assuming that the reaction between Ps and DNB is completely diffusion-controlled.     

A fundamental and clinical study of ferritin 'Eiken' radioimmunoassay kit

We have measured serum ferritin level using double antibody radioimmunoassay kit (Eiken ICL) and evaluated the characteristics of the kit and clinical usefulness. Satisfactory results were observed in standard curve, reproducibility, dilution and recovery test. In clinical evaluation, we have measured in normal subjects and patients with various diseases. The range in normal males and females were 13.0-158.7 ng/ml and 7.3-73.0 ng/ml, respectively. Serum ferritin level was elevated in patients with hepatoma, biliary cancer, lung cancer and other malignant diseases. Measurement of serum ferritin value would be useful in the monitoring of cancer patients.     

Absolute stereochemistry of citrinadins a and B from marine-derived fungus

[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively).