Local structure and photoluminescent characteristics of Eu<Superscript>3+</Superscript> in ZnO–SiO<Subscript>2</Subscript> glasses

The photoluminescence properties of xZnO–(100−x)SiO₂ (x = 0, 5, 10, 20) containing 1% Eu₂O₃ prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of ⁵D₀–⁷F_J transitions of Eu³⁺ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu³⁺ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu³⁺ ions occupied one site in SiO₂ glass and two sites in ZnO–SiO₂ glasses. The second-order crystal field parameters were calculated. B₂₀ and B₂₂ for site 1 increased with excitation energy, while ones hardly changed for site 2.     

Two-dimensional Monte Carlo simulations of a colloidal dispersion composed of polydisperse ferromagnetic particles in an applied magnetic field

We have investigated aggregation phenomena in a polydisperse colloidal dispersion of ferromagnetic particles simulated by employing the cluster-moving Monte Carlo method in an applied magnetic field. The influence of both particle-particle and particle-field interactions on the aggregate structures is analyzed in terms of a pair correlation function. The results obtained in this study are summarized as follows: Under a strong magnetic field, chainlike clusters are formed along the magnetic field direction, and they become thickly clustered with an increase in the strength of the external magnetic field. Moreover, the thickly clustered chains are formed for a polydisperse system that has a large standard deviation of particle diameters. In contrast, for a very weak magnetic field, the strong interaction between the larger particles gives rise to the formation of various shapes in the chainlike clusters, including bending, looping, and branching. With an increase in the external magnetic field, these structures reorganize to form straight chainlike clusters. Furthermore, the thickness of the chainlike clusters for the polydisperse system is found to depend on the standard deviation of the particle-size distribution but is found to be independent of the magnetic field strength.     

Synthesis of 2-, 4- and 5-(2-alkylcarbamoyl-1-methylvinyl)-7-alkyloxybenzo[b]furans and their leukotriene B4 receptor antagonistic activity

Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group.     

A new synthesis of key intermediates for the assembly of polycyclic ethers: Yb(OTf)3-promoted formation of O,S-acetals from α-fluorosulfides and alcohols

We report a new reaction for the direct construction of O,S-acetals, key intermediates in the assembly of fused polycyclic ethers. α-Fluorosulfides and secondary alcohols were coupled by the action of Yb(OTf)₃ to generate O,S-acetals in high yield. The neutral and selective nature of the reaction should be useful for synthesizing natural and artificial polyethers with multisensitive functionalities.     

Novel assembly of cyclic ethers by coupling alpha-chlorosulfides and alcohols

A novel protocol for assembling polycyclic ethers was developed and successfully applied to the synthesis of the EFGH ring system of ciguatoxin CTX3C. A key transformation involves construction of an O,S-acetal through coupling of alpha-chlorosulfide and a secondary alcohol under mild conditions. The method is highly applicable to use with sensitive substrates and will enable the synthesis of various natural and artificial polycyclic ethers. [reaction: see text]     

Synthesis of aryltriethoxysilanes via rhodium(I)-catalyzed cross-coupling of aryl electrophiles with triethoxysilane

The general and efficient silylation of aryl halides has been developed utilizing triethoxysilane and a rhodium catalyst. The substrate scope is broad and includes ortho-, meta-, and para-substituted electron-rich and -deficient aryl iodides. In addition, the silylation of aryl bromides and fluoroalkanesulfonates proceeded in the presence of tetra-n-butylammonium iodide.     

Programmable DNA translation system using cross-linked DNA mediators

The information of template DNA strands was converted into the specific sequences in a programmable way by following the mediation of cross-linked DNAs.     

The structures of macbecin I and II : New antitumor antibiotics

Macbecin I 1, C₃₀H₄₂N₂O₈, and macbecin II 2, C₃₀H₄₄N₂O₈, were shown to be 2,6-disubstituted benzoquinone and hydroquinone derivatives by an oxidation-reduction relationship, UV. ¹H and ¹³C NMR spectra. Alkaline methanolysis of 1 gave a 2-aminobenzoquinone derivative 5, suggesting an ansa-structure for 1, and acid hydrolysis of 1 gave decarbamoyl products 9,10 and 11, indicative of the location of carbamoyloxy group in allylic position. Spin decoupling studies on 1,3 and 5clarified the partial structures [A], [B], [C] and [D]. From their mutual disposition two structures 1a and 1b, were proposed out of which 1a has been selected for the structure of 1 on the basis of the structure of oxidative degradation product 12. X-Ray analysis of the bromoacetyl derivative of 1 confirmed the above proposed structure and determined the absolute stereochemistry of 1 and 2.     

PHOTOCHEMICAL REACTION OF 13-CIS-BACTERIORHODOPSIN STUDIED BY LOW TEMPERATURE SPECTROPHOTOMETRY

Abstract— The photoreaction cycle of 13- cis -bacteriorhodopsin (13- cis -bR) was investigated by low temperature spectrophotometry using two different preparations; 13- cis -bR constituted from bacterioopsin and 13- cis -retinal, and dark-adapted bacteriorhodopsin (bR^D), which is an equi-molar mixture of 13- cis -bR and trans -bR.
By irradiation with 500 nm light at — 190°C, 13- cis -bR was converted to its batho-product, batho-13- cis -bR (batho-bR¹³), which is different from batho-product from trans -bR, batho-bR^t. On warming batho-bR¹³ to -5°C in the dark, it completely changed to trans -bR. We estimated the composition of 13- cis -bR and trans -bR in the warmed sample spectrophotometrically and then the absorption spectrum of batho-bR¹³ was calculated. The absorption maximum lies at 608 nm, 1250 cm⁻¹ longer than that of 13- cis -bR; the molar extinction coefficient (ε) is about 74000 M ⁻¹ cm⁻¹, larger than that of 13- cis -bR (52000 M ⁻¹ cm⁻¹).
On the warming the sample containing batho-bR¹³ formed by irradiating 13- cis -bR or bR^D at — 190°C, we could not detect other intermediates such as the lumi- or meta-intermediates seen in trans-bR system.