Development and validation of stable‐isotope dilution liquid chromatography–tandem mass spectrometric method for determination of salivary progesterone

A method for the quantification of progesterone (PROG) in human saliva using liquid chromatography–electrospray ionization–tandem mass spectrometry (LC‐ESI‐MS/MS) has been developed and validated. The saliva was deproteinized with acetonitrile, purified using a Strata™‐X cartridge, and subjected to LC‐ESI‐MS/MS. Quantification was based on selected reaction monitoring, and deuterated PROG was used as the internal standard. This method allowed the reproducible (intra‐ and inter‐assay relative standard deviations, <2.2%) and accurate (analytical recovery, 96.6–99.7%) quantification of the salivary PROG using a 400 μL sample, and the limit of quantification was 12.5 pg/mL. The developed method enabled detection of the variation in the salivary PROG concentrations of healthy volunteers during the menstrual cycle and measurement of the salivary concentrations of pregnant women. The method is expected to be an alternative to the blood PROG monitoring in clinical examinations, because saliva collection is easy, non‐invasive and repeatable. Copyright © 2011 John Wiley & Sons, Ltd.     

Syntheses, crystal structures and Si solubilities of new layered carbides Zr2Al4C5 and Zr3Al4C6

Two types of new ternary carbides, Zr₂Al₄C₅ and Zr₃Al₄C₆, have been synthesized and characterized by X-ray powder diffraction. The crystal structures were refined from laboratory X-ray powder diffraction data (CuKα₁) using the Rietveld method. These carbides form a homologous series with the general formula (ZrC)_mAl₄C₃ (m=2 and 3). The crystal structures can be regarded as intergrowth structures where the Al₄C₃-type [Al₄C₄] layers are the same, while the NaCl-type [Zr_mC_m+1] layers increase in thickness with increasing m value. The new carbides are most probably the end members of continuous solid-solutions (ZrC)_m[Al_4−xSi_x]C₃ with 0?x?0.44.     

Cationic polyrotaxanes effectively inhibit uptake via carnitine/organic cationic transporters without cytotoxicity

We examined the inhibitory effect of cationic polyrotaxanes, which consist of alpha-cyclodextrins threaded on a poly(ethylene glycol) (PEG) chain, on the activity of the intestinal carnitine/organic cation transporter, OCTN2, in OCTN2 gene-transfected HEK293/PDZK1 cells. The cationic polyrotaxanes effectively inhibited the OCTN2-mediated carnitine transport. Polyrotaxanes with a longer PEG chain exhibited a greater inhibitory effect, possibly owing to multivalent interactions with binding sites on OCTN2. These cationic polyrotaxanes were far less cytotoxic than conventional polycations, and are therefore interesting candidates as low-toxicity inhibitors of cation transport at cell surfaces.     

Sorption behavior of selenide on montmorillonite

Batch sorption experiments were performed to investigate the sorption mechanism of Se on montmorillonite under reducing conditions in deep geological environments. Based on E_h–pH diagrams and ultraviolet–visible spectra, Se was dissolved as selenide (Se(–II)) anions under the experimental conditions. The distribution coefficients (K_d; m³ kg^?1) of Se(–II) indicated ionic strength independence and slight pH dependence. The K_d values of Se(–II) were higher than those of Se(IV), which also exists as an anionic species. X-ray absorption near edge spectroscopy showed that the oxidation state of Se-sorbed on montmorillonite was zero even though selenide remained in the solution. These results suggest that Se(–II) was oxidized and precipitated on the montmorillonite surface. Therefore, it is implied that a redox reaction on the montmorillonite surface contributed to high K_d values for Se(–II).

     

Synthesis of Polymeric Microspheres with Narrow Size Distributions Employing Microchannel Emulsification

Polymeric divinylbenzene microspheres (MS) of narrow size distributions were prepared by microchannel (MC) emulsification and subsequent polymerization. Using two types of MC plates, large MS with 9.2 μm diameter on average and 5.7% coefficient of variation, as well as small MS with 3.4 μm diameter on average and 7.4% coefficient of variation were prepared. The MS diameter can be controlled by the size of the MC. This method is advantageous for synthesizing polymeric MS of narrow size distributions because of its simplicity.     

New entry to the Pauson-Khand reaction: trimethylgermyl group at the triple bond terminus as a latent functional group

The Pauson-Khand reaction of enynes possessing a trimethylgermyl group at the alkyne terminus afforded the corresponding bicyclo[3.3.0]octenone and bicyclo[4.3.0]nonenone skeletons in a stereoselective manner. The resulting trimethylgermyl group of the bicyclic compounds was then converted to the iodo group, which was used for further elaboration. Thus, the trimethylgermyl group at the triple bond terminus was shown to be a precursor for other appendages.