Enantioselective Protonation of Cyclic Carbonyl Ylides by Chiral Lewis Acid Assisted Alcohols

Chiral Lewis acid-catalyzed asymmetric alcohol addition reactions to cyclic carbonyl ylides generated from N-(α-diazocarbonyl)-2-oxazolidinones featuring a dual catalytic system are reported. Construction of a chiral quaternary heteroatom-substituted carbon center was accomplished in which the unique heterobicycles were obtained in good yields with high stereoselection. The alcohol adducts were successfully converted to optically active oxazolidine-2,4-diones by hydrolysis. Mechanistic studies by DFT calculations revealed that alcohols could be activated by Lewis acids, enabling enantioselective protonation of the carbonyl ylides.     

Asymmetric synthesis of bicyclo[n.1.0]alkanes by the enantioselective 1,3-CH insertion reaction of chiral magnesium carbenoids

Treatment of enantiomerically pure 1-chlorovinyl p-tolyl sulfoxides, derived from cyclic ketones and (R)-chloromethyl p-tolyl sulfoxide, with the lithium enolate of tert-butyl carboxylates gave adducts in quantitative yields as single diastereomers. The adducts were treated with i-PrMgCl in toluene to afford optically active bicyclo[n.1.0]alkanes bearing a tert-butyl carboxylate moiety in up to 99% enantiomeric excess through the enantioselective 1,3-CH insertion reaction of the generated chiral magnesium carbenoids. This is the first example of the enantioselective 1,3-CH insertion reaction of magnesium carbenoid.     

Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

Rapid evaluation of molecular shape similarity index using pairwise calculation of the nearest atomic distances

Rapid evaluation method for obtaining molecular shape similarity index using pairwise calculation of the nearest atomic distance respected to the template atoms was investigated. This method for calculations of similarity indices remarkably reduced required time compared with hitherto methods (especially 2 or 3 orders of magnitude faster than the previous grid-based evaluation technique) and gave without clear loss of preciseness. The potential of these improvements and possible further enhancements are discussed.     

Quasi-solid-state dye-sensitized solar cells using room temperature molten salts and a low molecular weight gelator

A dye-sensitized solar cell fabricated using the room temperature molten salt, 1-hexyl-3-methylimidazolium iodide, iodine and a low molecular weight gelator as a quasisolid-state electrolyte showed a 5.0% light-to-electricity conversion efficiency under AM 1.5 irradiation, and high-temperature stability.     

Effect of Immobilization on Insoluble Collagen Concentration and Type I and Type III Collagen Isoforms of Rat Soleus Muscle

Immobilization is often associated with decreased muscle elasticity. This condition is known as muscle contracture; however, the mechanism remains unclear. The purpose of this study was to clarify the mechanism governing muscle contracture in rat soleus muscle by identifying changes in ankle joint mobility, insoluble collagen concentration and type I and type III collagen isoforms following 1- and 3-week immobilizations. Following a 1-week immobilization, range of motion (ROM) of dorsiflexion declined to 90% of the control value; additionally, ROM dropped to 67.5% of the control value after a 3-week immobilization. This finding suggested that ankle joint mobility decreases in conjunction with extended periods of immobilization. Insoluble collagen concentration in soleus muscles, which was unchanged after 1 week of immobilization, increased 3 weeks after immobilization. These results may be indicative of collagen fibers with strong intermolecular cross-links contained in the muscle was made increased relatively by 3 weeks of immobilization. Therefore, the change in intermolecular cross-links may be significant in terms of progress of muscle contracture with longer periods of immobilization. On the other hand, the ratio of type III to type I collagen isoforms in muscular tissue increased following a 1-week immobilization; moreover, this ratio remained constant after 3 weeks of immobilization. These data suggested that muscle immobilization may induce type III collagen isoform expression. The increase in the ratio of type III to type I collagen isoforms do not change in parallel with the increase in the limitation in ROM; however, this phenomenon probably is not closely related to the progress of muscle contracture. The change of collagen isoform in immobilized muscle may be involved in the mechanism governing the progression of muscle fibrosis.     

Determination of sulphide ion at trace levels by ethylation and gas chromatography

Summary A method is described for the determination of sulphide ion in aqueous samples by gas chromatography. Sulphide is ethylated with diethyl sulphate and the resulting diethyl sulphide is extracted with chloroform and determined with a gas chromatograph equipped with a flame ionization or a flame photometric detector. In the case of a flame photometric detector, the detection limit for sulphide ion is 0.05 g/ml. Other anions commonly found with sulphide ion do not interfere. Sulphide ion in spring waters was analysed by this new method and for comparison also by colorimetry (methylene blue). The results revealed the reliability of the new method.

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Bestimmung von Sulfidspuren durch Ethylierung und Gas-Chromatographie

Zusammenfassung Sulfid wird mit Diethylsulfat ethyliert, das gebildete Diethylsulfid mit Chloroform extrahiert und gaschromatographisch mit Hilfe eines Flammenionisationsoder eines flammenphotometrischen Detektors bestimmt. Die Nachweisgrenze beträgt 0,05 g S/ml für den FPD. Anionen, die üblicherweise mit Sulfid zusammen vorkommen, stören nicht. Das Verfahren wurde, im Vergleich mit der colorimetrischen Methylenblaumethode, auf Quellwasser angewendet. Es wurde gute Übereinstimmung der Ergebnisse erzielt.