The key Cl− ligand for metal‐to‐ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

Electronic structures of binuclear ruthenium complexes [Ru₂(terpy)₂(tppz)]⁴⁺ ( 1A ) and [Ru₂Cl₂(L)₂(tppz)]²⁺ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)₂]²⁺ ( 1B ) and [RuClL(terpy)]⁺ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF₆)₄ was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl^? ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.     

Optical detection of DNA translocation through silicon nanopore by ultraviolet light

In this paper, we propose a new optical detection scheme for nanopore-based DNA sequencing with high resolution towards eventual base identification. We use ultraviolet light for excitation of a fluorescent probe attached to DNA and a nanopore in the silicon membrane that has a significantly large refractive index and an extinction coefficient at ultraviolet wavelengths. In this study, numerical electromagnetic simulation revealed that the z-polarization component (perpendicular to the membrane plane) of the electric field was dominant near the nanopore and generated a large electric field gradient at the nanopore exit, typically with a decay length of 2 nm for a nanopore with diameter of 7 nm. The large extinction coefficient contributed to reduction in background noise coming from fluorophore-labeled DNA strands that remain behind the membrane (the cis side of the membrane). We observed a high signal-to-noise ratio of single DNA translocation events under the application of an electric field.     

A Bohr-Mottelson model of nuclei at finite temperature

Starting from Boltzmann-Langevin equation and performing a fluid dynamical reduction, a system of coupled Langevin equations is derived for a multipolar velocity field. This system is then applied to monopole andβ-,γ-quadrupole resonances, making a link between microscopic approaches and phenomenological macroscopic ones.     

A,B,D,F-tetrasubstituted β-cyclodextrin as artificial channel compound

As a channel forming compound, β-cyclodextrin having four hydrophobic tails and three metal binding sites, 1, [A,C,D,F,-tetra-6-(6-n-butyrylamino-n-hexylsulfenyl)-β-cyclodextrin] was synthesized as a “half channel”. Artificial liposome modified with 1 transported Co⁺⁺ efficiently with the rate, 4.5 × 10^?4sec^?1 for 55 μM 1, much faster tahn the rate for the unmodified liposome.     

Efficiency of Blazed Diffractive Optics Produced by Diamond Turning

In blazed diffractive optics produced by the diamond turning process, the finite size of the tool causes a decrease in diffraction efficiency. To analyze the influence of the tool, we evaluate first-order diffraction efficiency of periodic gratings based on the electromagnetic theory. The design indices of the diffractive optics for higher efficiency are shown. Even with the same power of diffractive optics, the efficiency differs with the front or back side of the surface. The efficiency of a diffractive-refractive hybrid lens depends on the curvature of the refractive surface.     

A STUDY OF THE KINETICS OF INCLUSION OF HALONAPHTHALENES WITH ß-CYCLODEXTRIN VIA TIME CORRELATED PHOSPHORESCENCE

Abstract— The phosphorescence of 1-bromonaphthalene and 1-chloronaphthalene is readily observable in nitrogen purged aqueous solutions containing ß-cyclodextrin. Addition of acetonitrile increases both the phosphorescence intensity and lifetime. The quenching of halonaphthalene phosphorescence in aqueous solution by nitrite is substantially inhibited upon addition of ß-cyclodextrin, as a result of a guest-host complex. The rate constants for formation and dissociation of the l-bromonaphthalene/ß-cyclodextrin complex are evaluated from an analysis of the dependence of phosphorescence lifetimes on nitrite concentration.     

Simultaneous determination of YM-64227, a phosphodiesterase type 4 inhibitor, and its five metabolites in dog plasma by high-performance liquid chromatography with fluorescence detection

We developed and validated a reversed-phase high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of YM-64227 [4-cyclohexyl-1-ethyl-7-methylpyrido(2,3-d)pyrimidin-2-(1H)-one], a novel and selective phosphodiesterase type 4 inhibitor, and its fi ve hydroxylated metabolites in dog plasma. The plasma samples were extracted with tert-butyl methyl ether under alkali conditions. The analytes were well separated on a phenyl ethyl column (5 microm, 250 x 4.6 mm i.d.), opreating at 40 degrees C and using an acetonitrile-acetic acid gradient at a fl ow rate of 1.0 mL/min. The fluorescence signal was monitored at an excitation and emission wavelength of 330 and 400 nm, respectively. No interfering peak was observed at the retention time of YM-64227, its metabolites or the internal standard. The validated quantitation range of the method was 0.4-200 ng/mL for all analytes using 0.5 mL of the plasma sample. The recovery of analytes in the extraction process was more than 65.5%. The intra- and inter-assay precision was less than 5.1 and 12.6%, respectively, and the intra- and inter-assay accuracy ranged from -8.1 to 11.8% and -8.0 to 9.9%, respectively. Using this assay, the plasma concentration of YM-64227 and metabolites can be determined after the oral administration of YM-64227 to beagle dogs.