Convenient synthesis of cyclic carbonates from CO2 and epoxides by simple secondary and primary ammonium iodides as metal‐free catalysts under mild conditions and its application to synthesis of polymer bearing cyclic carbonate moiety

Hydroiodides of secondary and primary amines effectively catalyzed the reaction of carbon dioxide and epoxides under mild conditions such as ordinary pressure and ambient temperature, to obtain the corresponding five‐membered cyclic carbonates in moderate to high yields. Detailed investigation showed that the catalytic activity was highly affected by the counter anions of the ammonium salts; the iodides catalyzed efficiently the carbonate‐forming reactions, whereas the bromide and chloride counterparts exhibited almost no catalysis. We also revealed that two important factors on the amine moieties that affected the catalytic reactions. First, the catalytic activity increased with increasing bulkiness of the substituents on the ammonium nitrogen atoms. Second, the catalysis became more efficient as the parent amines become more basic. Dicyclohexylammonium iodide was the best catalyst among the ammonium salts investigated in this study. As an application of this reaction system, we synthesized homo‐ and copolymers bearing epoxide pendant groups as substrates, which were converted with high efficiency into the corresponding homo‐ and copolymers bearing cyclic carbonate pendant groups under 1 atm at 45 °C. All polymers were easily purified simply by precipitation in water, and were isolated in high yields (>95%). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Proton-nucleus inelastic cross section at ultra high energy

Energy dependence of proton-nucleus reaction cross section at very high energy is discussed. It is stressed that depending on the gluon distribution near the nuclear surface, proton-nucleous total cross section increases much more rapidly compared to the usual Glauber independent nucleon estimate. The recent observation of smaller X _max than the expected value at UHECR domain can be an indication for such a mechanism.     

Polymorphisms of 4,5-Bis(4-Methoxyphenyl)-2-(3-Nitrophenyl)-1H-Imidazole as Studied by Solid State NMR

Abstract

Solid state NMR measurements are carried out for polymorphs and inclusion complexes of 4,5-bis(4-methoxyphenyl)-2-(3-nitrophenyl)-1H-imidazole. Observed ¹³C and ¹⁵N chemical shifts are characteristic of each polymorph A, B, C and D. In addition, ¹⁵N chemical shift was a good index for understanding hydrogen bond. VT measurements revealed that B transforms to C between 93 and 113°C. From PSTMAS and ¹H solid echo measurements for AcOET inclusion complex, host molecules have almost same structure as B and guest molecules have the highest mobility of all inclusion complexes.     

Thermal stability of alignment of a nematic liquid crystal induced by polyimides exposed to linearly polarized light

The thermal stability of alignment of a nematic liquid crystal (LC) on three polyimide (PI) films exposed to linearly polarized light at 366 nm was investigated. Polarizing optical microscopy analysis indicates that the thermal stability of the LC alignment on the PI film without significant structural change was higher than that with obvious structural change.     

Micro determination of cortisol and cortisone in umbilical cord blood by chemiluminescent high‐performance liquid chromatography

A simple, sensitive and specific chemiluminescent high‐performance liquid chromatography method, based on the luminol reaction, for determination of serum cortisol and cortisone, was established. In infants, placental 11β‐hydroxysteroid dehydrogenase type 2 enzyme (11β‐HSD2) activity may affect adrenal function early after birth. The cortisol–cortisone ratio of serum concentrations in umbilical cord blood is an indicator of placental 11β‐HSD2 activity. The optimum conditions for the luminol reaction were determined to be 1.5 mM luminol, 0.6 M sodium hydroxide, 0.15 mm potassium hexacyanoferrate(III) and 200 mM potassium hexacyanoferrate (II). The calibration curves for cortisol and cortisone exhibited good linearity. The correlation coefficients of the calibration curves were 0.996. The intra‐ and inter‐day precisions were in the ranges: cortisol 7.0–12.2 and 4.4–9.2%, cortisone 5.3–7.0 and 6.2–9.9%. The recoveries of these steroids were in the ranges: cortisol 97–105%, cortisone 94–102%. The limits of detection were as follows: cortisol, 0.17 μg/dl; cortisone 0.15 μg/dl. This assay could be successfully applied to determination of the cortisol–cortiosone ratio of serum concentrations in umbilical cord bloods. Copyright © 2009 John Wiley & Sons, Ltd.