Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions

Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.     

Synthesis of water-soluble C60-porphyrin hybrid compounds

Water-soluble C60-porphyrin hybrid molecules were first synthesized toward their pharmaceutical applications.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

Development of novel pyrrole synthesis for the preparation of intermediates of bioactive pyrrole alkaloids

We have developed a novel method for the synthesis of 3,4-diarylpyrrole-2,5-dicarboxylates via α-diazo esters, which are easily obtained from phenylalanine derivatives. Utilizing this method, intermediates of bioactive compounds having the structure of 3,4-diarylpyrrole-2,5-dicarboxylates were synthesized.     

Interfacial effects on thermoelectric functions

We investigated the effects of added oxide to FeSi₂ on thermoelectric properties in order to improve the figure of merit. The oxide was not suggested to chemically react with the mother material (FeSi₂), where the oxide materials existed in the grain boundaries. The oxide addition played a role to reduce thermal conductivity and possessed electrical resistivity as well as non oxide-added FeSi₂. Hereafter, the appropriate added amount of Yb₂O₃ showed the largest effect on the figure of merit among other oxides.     

An application of fragment interaction analysis based on local MP2

We have developed a method named ‘fragment interaction analysis based on local MP2’ (abbreviated as FILM). This method enables us to decompose the interaction energy associated with dispersion interactions into contributions of localized occupied orbitals. In this study, the basis set dependence of the results derived from FILM was examined. The results suggested that the individual ratio of pair correlation energies of selected orbital pairs to the total dispersion interaction was almost independent of the basis set size. As an illustrative example, detailed analysis was performed on the human immunodeficiency virus type 1 protease complexed with lopinavir molecule.     

Influence of head shape of solid body plunging into water on splash formation

Abstract  

We experimentally investigated the influence of a head shape of a solid body plunging into water on splash formation. Three different head shapes were tested: a hemisphere, cone, and circular cylinder. A hemisphere as a tail shape is common to all three head shapes. We captured images of splash formation using a high-speed CMOS camera. We found that a film flow generated at an early stage when a body impacts the water surface influences subsequent events until the splash sequence is completed. We explain the origin of the film flow according to the principle of conservation of momentum. The film flow as the primary splash originates from water displaced by the head. The meridian line, which connects the head to the tail of the body, affects separation of the film flow and causes the secondary splash. The air cavity generated when the body plunges into the water is also influenced by the head shape. The tertiary splash is formed by a reaction of the air cavity, which is detached from the body. We found that the secondary dome-type splash obstructs growth of the tertiary splash. Thus, we conclude that the head shape affects all events of the splash.     

Development and validation of a hydrophilic interaction chromatography–tandem mass spectrometry for quantification of nicotine and its metabolites in human maternal and cord sera

A selective and sensitive HILIC‐MS/MS method for the simultaneous quantification of nicotine and its metabolites in human maternal and cord sera was developed and validated. After solid‐phase extraction, LC separation was achieved on a hydrophilic interaction chromatography. The validated method is capable of selective identification as well as accurate and sensitive quantification. Analyte recovery ranged from 86.2 to 107.7% and intra‐ and inter‐day assay precision were less than 15% relative standard deviation. This sensitive HILIC‐MS/MS method can be used to determine nicotine and its metabolic profile in smokers. This validated method is useful for the determination of nicotine and its metabolites in human serum in future studies of the effects of nicotine exposure on neonatal outcome. Copyright © 2010 John Wiley & Sons, Ltd.