Photoelectrochemistry of p-type Cu2O semiconductor electrode in ionic liquid

We investigated the photoelectrochemical characteristics and photo-stability of Cu₂O layered on a copper plate using a hydrophobic ionic liquid. Our findings revealed that Cu₂O is stable under white light irradiation, provided water is removed from the electrolyte. Methyl viologen derivative, a well-established electron acceptor, was introduced to the ionic liquid electrolyte, allowing the photo-induced electron transfer reaction at the Cu₂O/electrolyte interface to be characterized. The methyl viologen derivative exhibited two distinct redox reactions at −0.56 V and −0.98 V vs. Ag/AgCl, clearly indicating that no dimer formation or co-proportionation reaction occurred. The excessive photocurrents being continuously generated resulted from a viable photo-induced electron transfer reaction from the Cu₂O to the acceptor. However, in contrast, the reduction of the Cu₂O by water in the aqueous solution causes this electron transfer to be inhibited. We further demonstrate that these findings are vital to understanding the role of the Cu₂O and its photoelectrochemical applications.     

Electrodeposition of manganese and molybdenum mixed oxide thin films and their charge storage properties

Manganese and molybdenum mixed oxides in a thin film form were deposited anodically on a platinum substrate by cycling the electrode potential between 0 and +1.0 V vs Ag/AgCl in aqueous manganese(II) solutions containing molybdate anion (MoO(4)2-). A possible mechanism for the film formation is as follows. First, electrooxidation of Mn2+ ions with H2O yields Mn oxide and protons. Then, the protons being accumulated near the electrode surface react with MoO(4)2- to form polyoxomolybdate through a dehydrated condensation reaction (by protonation and dehydration). The condensed product coprecipitates with the Mn oxide. Cyclic voltammetry of the Mn/Mo oxide film-coated electrode in aqueous 0.5 M Na2SO4 solution exhibited a pseudocapacitive behavior with higher capacitance and better rate capability than that of the pure Mn oxide prepared similarly, most likely as a result of an increase in electrical conductivity of the film. Electrochemical quartz crystal microbalance and X-ray photoelectron spectroscopy clearly demonstrated that the observed pseudocapacitive behavior results from reversible extraction/insertion of hydrated protons to balance the charge upon oxidation/reduction of Mn3+/Mn4+ in the film.     

Mechanism of gold adsorption by persimmon tannin gel.

Gold adsorption by persimmon tannin (PT) gel from a solution containing hydrogen tetrachloroaurate(III) was examined. A flow-rate examination in a column system indicated the reduction of Au(III) ion to Au(0). XRD patterns clarified the existence of Au(0) on the gel which adsorbed gold. The gel could also adsorb colloidal Au(0) prepared independently. A model consisting of ligand exchange, Au(III) reduction to Au(0), and resulting Au(0) adsorption by PT gel was presented for the gold adsorption mechanism.     

Polymerization of tetrahydrofuran by AlEt3–H2O promoter system: Rate of propagation reaction

Kinetic studies were carried out on the polymerization of tetrahydrofuran with catalyst systems of aluminum alkyl–epichlorohydrin. As aluminium alkyl species AlEt₃, AlEt₃–H₂O (1:0.1 to 1:1.0), and “oxyaluminum ethyl” were employed. The polymerizations with these catalysts are characterized by a mechanism of stepwise addition without chain transfer or termination, which is expressed by the kinetic relation R_p = K_p[P*] ([M]–[M]_e), where [M] and [M]_e are the instantaneous and equilibrium concentrations of monomer and [P*] is the concentration of propagating species calculated from the amount and molecular weight of the product polymer. The determination of the rate constant k_p for these catalysts has shown that the polymerization rate varied considerably with the change of aluminum alkyl species, i.e., with the water-to-aluminum ratio, but the propagation rate constant itself varied very little. The variation of polymerization rate was, therefore, attributed primarily to the differences in concentration of the propagating species, i.e. the efficiency of the catalyst in forming propagating species. The catalyst efficiency was closely related to the acid strength of the aluminum alkyl species, which was estimated from the magnitude of shift of the xanthone carbonyl band in the infrared spectrum of its coordination complex with aluminum alkyl. The maximal catalyst efficiency was attained at about [H₂O]/[AlEt₃] = 0.75.     

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.     

Polyesters containing ring units in main chains. I. Preparation and stereochemistry of monomers and polyesters

Cycloalkanone (C₅–C₈, C₁₂, and C₁₅) or cycloalkane (C₅ and C₆) ring-containing monomeric diesters and the polyesters derived from them were prepared, and their configurations were studied by ¹³C-NMR spectroscopy. Absolute configurations were determined for ring sizes 5, 6, and 7. Configurational change during reduction of a ketonic group of monomeric diesters with ring sizes 5 and 6 was discussed in terms of the steric effect of ring substituents on the ketonic group. In the polycondensation reaction epimerization of the ring units was observed in 5-, 6-, and 7-membered cycloalkanones and not in others, which is explained by steric hindrance by the ring substituents against attack of tetrabutyl titanate catalyst on the ketonic group.     

Isolation and Stereostructures of Dolastatin G and Nordolastatin G, Cytotoxic 35-Membered Cyclodepsipeptides from the Japanese Sea Hare Dolabella auricularia

A bioassay-directed fractionation of the cytotoxic constituents of the Japanese sea hare Dolabella auricularia resulted in the isolation of two 35-membered depsipeptides dolastatin G (1) and nordolastatin G (2), which showed cytotoxicity against HeLa S(3) cells with IC(50) values of 1.0 and 5.3 &mgr;g/mL, respectively. The gross structures of these substances were established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure of 1 was determined by chiral HPLC analysis of amino acid components obtained from acid hydrolysis of 1 and by the enantioselective syntheses of two degradation products arising from polyketide portions. Nordolastatin G (2) is a congener that has the same absolute stereochemistry as that of 1.