Tailoring of Deep‐Red Luminescence in Ca2SiO4:Eu2+

We report a new dicalcium silicate phosphor, Ca_2?xEu_xSiO₄, which emits red light in response to blue‐light excitation. When excited at 450 nm, deep‐red emission at 650 nm was clearly observed in Ca_1.2Eu_0.8SiO₄, the external and internal quantum efficiencies of which were 44 % and 50 %, respectively. The red emission from Ca_2?xEu_xSiO₄ was strongly related to the peculiar coordination environments of Eu²⁺ in two types of Ca sites. The red‐emitting Ca₂SiO₄:Eu²⁺ phosphors are promising materials for next‐generation, white‐light‐emitting diode applications.     

Efficient synthesis of useful heterocycles via transition metal-catalyzed cascade processes

This paper reports our recent results from synthesis of some useful heterocycles, for example oxazolidinones, indoles, and quinoxalinones, by transition metal-catalyzed cascade processes. The scope and limitations of these procedures and the reaction mechanism for formation of the heterocycles are also discussed.     

DMSO-Quenched H/D-Exchange 2D NMR Spectroscopy and Its Applications in Protein Science

Hydrogen/deuterium (H/D) exchange combined with two-dimensional (2D) NMR spectroscopy has been widely used for studying the structure, stability, and dynamics of proteins. When we apply the H/D-exchange method to investigate non-native states of proteins such as equilibrium and kinetic folding intermediates, H/D-exchange quenching techniques are indispensable, because the exchange reaction is usually too fast to follow by 2D NMR. In this article, we will describe the dimethylsulfoxide (DMSO)-quenched H/D-exchange method and its applications in protein science. In this method, the H/D-exchange buffer is replaced by an aprotic DMSO solution, which quenches the exchange reaction. We have improved the DMSO-quenched method by using spin desalting columns, which are used for medium exchange from the H/D-exchange buffer to the DMSO solution. This improvement has allowed us to monitor the H/D exchange of proteins at a high concentration of salts or denaturants. We describe methodological details of the improved DMSO-quenched method and present a case study using the improved method on the H/D-exchange behavior of unfolded human ubiquitin in 6 M guanidinium chloride.     

Gold(I) Complexation of Phosphanoxy-Substituted Phosphaalkenes for Activation-Free LAuCl Catalysis

The phosphanoxy-substituted phosphaalkene bearing the P=C−O−P skeleton can be prepared from diphosphene Mes*P=PMes* (Mes*=2,4,6-tBu₃C₆H₂), and their use for catalysis is of interest. In this paper, complexation of the phosphanoxy-substituted phosphaalkenes with gold are investigated, and the catalytic activity of the mono- and bis(chlorogold) complexes are subsequently evaluated. Reaction of the P=C−O−P compound with (tht)AuCl (tht=tetrahydrothiophene) showed dominant coordination on the sp³ phosphorus, and complete coordination on the sp² phosphorus required removal of tetrahydrothiophene. Atoms In Molecules (AIM) analysis based on the X-ray structure of the mono(chlorogold) complex indicated a pseudo coordinating interaction between the gold center and the P=C unit. The bis(chlorogold) complexes displayed conformational isomerism, and catalyzed the cycloisomerization/alkoxycyclization of 1,6-enyne and for hydration of terminal alkyne without activation treatment. Even the mono(chlorogold) complexes catalyzed the alkoxycyclization reactions without a silver co-catalyst, indicating that the alcohols were effective in activating the AuCl unit.     

Flow-injection spectrophotometric determination of enalapril in pharmaceuticals with bromothymol blue

Enalapril (1.5–60 μ gl^?1) in aqueous solution is extracted into dichloromethane as its ion-pair with bromothymol blue in an unsegmented flow system and quantified spectrophotometrically. Up to 80 samples h^?1 can be processed, with r.s.d. of 1.0–3.4%. The degradation products of enalapril and excipients in the pharmaceutical dosage form do not interfere.     

Formation of a direct mutagen, diazo-N-nitrosoetilefrin, by interaction of etilefrin with nitrite

Reaction of an antihypotensive drug, etilefrin [alpha-[(ethylamino)methyl]-m-hydroxybenzyl alcohol], with nitrite under mildly acidic conditions produced N-nitrosoetilefrin [alpha-[(N-nitrosoethylamino)methyl]-m-hydroxybenzyl alcohol] (a mixture of syn and anti forms) (Iab) and diazo-N-nitrosoetilefrin [1-(4-diazo-3-oxo-1,5-cyclohexadienyl-2-(N-nitrosoethylamino )ethanol] (a mixture of syn and anti forms) (IIab). Treatment of etilefrin with an equivalent amount of nitrite at pH 3 and 37 degrees C for 4 h gave Iab (yield, 30%) and IIab (yield, 5%). Treatment of etilefrin with 4 eq of nitrite under the same conditions gave Iab (23%) and IIab (53%). Compounds Iab and IIab were each composed of two isomers due to the configuration of the N-nitroso group. While compound Iab was not mutagenic, compound IIab showed mutagenicity to Salmonella typhimurium TA98 and TA100 strains without metabolic activation. Specific mutagenic activity of IIab was 300 his+ revertant colonies for both TA98 and TA100 strains with a dose of 0.1 mumol. Addition of a microsomal activation system little affected the activity. It is noteworthy that this orally administered drug can produce a direct-acting mutagen by reaction with nitrite, which is present in the digestive tract.