Zirconocene-Catalyzed Silylation of Alkenes with Chlorosilanes

Vinylsilanes and/or allylsilanes are formed upon silylation of terminal alkenes with R₃^′SiCl in the presence of a Grignard reagent and a catalytic amount of [Cp₂ZrCl₂] [Eq. (a)]. The reaction also proceeds under mild conditions when silylsulfides (X=SPh), silylselenides (X=SePh), and silyltellurides (X=TePh) are used in place of chlorosilanes (X=Cl). R″=alkyl, aryl, alkylsilyl; R′=Me, Et, nPr; R=CH₂R″, aryl, H.     

Modulation Frequency Characteristics of Erbium-Doped Fiber Amplifier

The modulation frequency characteristics of an erbium-doped fiber amplifier are analyzed theoretically and experimentally for various values of modulation frequency. The theoretical predictions by the approximate equations in the low and high frequency modulation and that by the Runge-Kutta method for all modulation frequencies are in good agreement with the experimental results. In the low frequency modulation, the population inversion is depleted because of the saturation effect due to the instantaneous power of the incident light, and a distorted output is obtained without phase delay. In the high frequency modulation, the linear amplification is obtained with the gain depletion determined by the time averaged power of the incident signal. In the intermediate frequency modulation, the highly distorted output is obtained with phase delay.     

A mild and practical deprotection method for benzyl thioethers

A highly effective and mild deprotection method was developed for benzyl thioethers using dibutylmagnesium in the presence of a catalytic amount of titanocene dichloride. This methodology is applicable to both aromatic and aliphatic benzyl thioethers.     

Canonical discriminant analysis of cadmium content levels in unpolished rice using a portable near-infrared spectrometer.

Near-infrared analysis (NIRA) was applied to discriminate and determine the cadmium content levels of unpolished rice using canonical discriminant analysis (CDA). The overall correct classification rate was 85.2% for 318 NIR spectra, repeated three times for 106 samples. After a further improvement through decreased misclassification rates, NIRA could be useful as a rapid, nondestructive and convenient analytical method for primary screening and detecting of cadmium-polluted rice.     

Selenoimidoylation of alcohols with selenium and isocyanides and its application to the synthesis of selenium-containing heterocycles

The reaction of alcohols with selenium and isocyanides in the presence of DBU gave oxyimidoylselenoates 6. Trapping of 6 with BuI resulted in high-yield formation of selenocarbonimidates 4. When alk-2-yn-1-ols 9 were allowed to react with selenium and isocyanides under similar conditions, new selenium-containing heterocycles 10, 2-imino-4-alkylidene-1,3-oxaselenolanes, were obtained via cycloaddition of oxyimidoylselenoates 13 generated in situ by intramolecular addition of selenolates to carbon-carbon triple bonds.     

Quantitative determination of paclitaxel and its metabolites, 6α‐hydroxypaclitaxel and p‐3′‐hydroxypaclitaxel,in human plasma using column‐switching liquid chromatography/tandem mass spectrometry

A column‐switching liquid chromatography/electrospray ionization tandem mass spectrometry to determine paclitaxel and its metabolites, 6α‐hydroxypaclitaxel and p‐3′‐hydroxypaclitaxel, in human plasma was developed. The analytical system had a Shim‐Pack MAYI‐ODS (10 × 4.6 mm i.d.) trapping column with deproteinization ability that concentrates analytes and removes water‐soluble components. This method covered a linearity range of 5–5000 ng/mL of concentrations in plasma for paclitaxel, a range of 0.87–870 ng/mL for 6α‐hydroxypaclitaxel and a range of 0.87–435 ng/mL for p‐3′‐hydroxypaclitaxel. The intra‐day precision and inter‐day precision of analysis were less than 11.1%, and the accuracy was within ±14.4% at concentrations of 5, 50, 500 and 5000 ng/mL for paclitaxel, 0.87, 8.7, 87 and 870 ng/mL for 6α‐hydroxypaclitaxel, and 0.87, 8.7, 87 and 435 ng/mL for p‐3′‐hydroxypaclitaxel. The total run time was 30 min. Our method was successfully applied to clinical pharmacokinetic investigation. Copyright © 2012 John Wiley & Sons, Ltd.