The role of F A1:Ag+ defects in laser light generation and coadsorption of CO and halogen atoms at the KCl and KBr surface sites. First principles calculations

F _A1:Ag⁺ color center at the low coordination (100) and (110) surface sites of KCl and KBr thin films play an important role in providing tunable laser oscillation and adsorbatesubstrate interactions. Double-well potentials at this site are investigated using ab initio molecular electronic structure calculations. The calculated Stokes shifted (optical transition bands), opticaloptical conversion efficiencies, the probability of orientational destruction, exciton (energy) transfer and Glasner-Tompkins empirical rule suggest that laser light generation is sensitive to (i) the lattice anion, (ii) the coordination number of surface ions, and (iii) the choice of the basis set centered on the anion vacancy. The adsorbate-substrate interactions were found to be dependent on the electronegativity of the adatom and on the lattice anion. Optimised geometries and the coadsorption of CO and (F, Cl, Br, I) on KCl and KBr (100) crystals are presented. Calculated chemisorption energies for CO on the (halogen atom/defect free sites of KCl and KBr (100) crystals) showed that the coadsorption of halogen atom tends to block other adsorbate-substrate interactions at the nearest neighbour sites. Thus if halogen atom coverage increases, the CO prefers to be adsorbed on the K⁺ site of the KCl and KBr (100) surfaces and on KBr relative to KCl.      

Magnetic ordering of Vn/Mo(0 0 1) systems: Ab-initio calculations

A density-functional theory (DFT) study is performed using a full-potential linearized-augmented-plane-waves (FP-LAPW) method to investigate the magnetic structure of vanadium-molybdenum systems (V_n/Mo(0 0 1), n = 1, 2). The topmost V layers relax inward in both systems with a larger contraction in V₂/Mo(0 0 1) system. A p(1 × 1) in-plane ferromagnetic ordering with appreciable magnetic moments is obtained on V overlayers, which is found to be the ground state in both systems. The layers below the surface exhibit induced magnetism with antiferromagnetic interlayer coupling.     

Metastable magnetic configurations of (V, Cr, Mn and Fe) on Ir(0 0 1) surfaces

We present a theoretical study of the electronic and magnetic structure of the 3d-transition metals (M = V, Cr, Mn and Fe) in several overlayer systems. The electronic as well as magnetic structures are investigated for pseudomorphic overlayers (M/Ir(0 0 1)), ordered alloyed overlayers of the type M_0.5Ir_0.5/Ir(0 0 1) and ordered binary surface alloys of V, Cr, Mn and Fe transition metals on Ir(0 0 1) substrates. The calculations are performed with a self-consistent tight-binding method using the unrestricted Hartree-Fock approximation within the Hubbard model. We obtained metastable c(2 × 2) configurations for V, Cr and Mn and a p(1 × 1) configuration for Fe pseudomorphic overlayers. However, ferrimagnetic configuration has been obtained for the ordered surface alloys M_0.5Ir_0.5 and the binary alloyed overlayers on Ir(0 0 1) surfaces.     

Determination of flumequine in channel catfish by liquid chromatography with fluorescence detection.

Rapid methods are described for determination of flumequine (FLU) residues in muscle and plasma of farm-raised channel catfish (Ictalurus punctatus). FLU residues were extracted from tissues with an acidified methanol solution, and extracts were cleaned up on C18 solid-phase extraction cartridges. FLU concentrations were determined by liquid chromatography (LC) using a C18 analytical column and fluorescence detection (excitation, 325 nm; emission, 360 nm). Mean recoveries of FLU from fortified muscle were 87-94% at 5 levels ranging from 10 to 160 ppb (5 replicates per level). FLU recoveries from fortified plasma were 92-97% at 5 levels ranging from 20 to 320 ppb. Limits of detection (signal-to-noise ratio, 3:1) for the method as described were 3 and 6 ppb for muscle and plasma, respectively. Relative standard deviations (RSDs) for recoveries were < or = 12%. Live catfish were dosed with 14C-labeled or unlabeled FLU to generate incurred residues. Recoveries of 14C residues throughout extraction and cleanup were 90 and 94% for muscle and plasma, respectively. RSDs for incurred FLU at 2 levels in muscle and plasma ranged from 2 to 6%. The identity of FLU in incurred tissues was confirmed by LC/mass spectrometry.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Conversion of iminoacyl quinolinylpalladium (II) complexes into novel oxo‐pyrrolo[3,4‐b] quinolines via depalladation reactions

Oxidative addition reactions of quinolines 1a , b with Pd(dba)₂ in the presence of PPh₃ (1:2) in acetone gave dinuclear palladium complexes [Pd(C,N‐2‐C₉ H₄N‐CHO‐3‐R‐6)Cl(PPh₃)]₂ [(R = H ( 2a ), R = OMe ( 2b ), which were reacted with isocyanide XyNC (Xy = 2,6‐Me₂C₆H₃) to give novel iminoacyl quinolinylpalladium complexes 3a , b in good yields (81 and 77%). Cyclopalladated complexes 3a , b were also obtained in low yields (39 and 33.5%) via one‐pot reaction of 1a , b with isonitrile XyNC:Pd(dba)₂ (4:1). The reaction of 3a , b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of complexes to provide the corresponding organic compounds 4a , b , 5a , b and 6a , b in yields of 41, 27 and 18 ? 19%, respectively. The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures 2a , 3a and 3b were determined by X‐ray diffraction studies. Copyright © 2008 John Wiley & Sons, Ltd.     

Sur une tentative d'unification des théaories quantiques de la cancérisation par les polyacènes. II: Le rôle de la rèagion K dans le processus d'activation metabolique conduisant au cancérogène ultime. Théorie des régions M,L, et BK

This study is a unified approach to quantum theories of polyacen carcinogenesis. Part II is on the role of the K-region in metabolic activation process leading to ultimate carcinogen and discusses the M, L, and BK theory. The saturation of the polyacen K-region, or the transformation into a quinoid one, deactivates the carcinogenic process going through a diol epoxyde, which results in Bay-region carbocation. K and B regions must be considered as two interdependent parts of the same structural entity, which may be termed the BK-region. The M, L, and BK theory achieves a complete unification of the Pullman and Jerina and other theories.     

Conjugation of testosterone modifies the interaction of mono-functional cationic platinum(II) complexes with DNA, causing significant alterations to the DNA helix

Previously a range of androgen conjugates with non-conventional platinum(II) complexes have been synthesised with the aim of enhancing cellular delivery, and which have shown increased cytotoxic activity compared with non-steroidal compounds (M. J. Hannon et al., Dalton Trans., 2010, DOI: 10.1039/c0dt00838a). To further study this, the complexes have been assessed for their ability to bind to and alter the structure of DNA. All platinum(II) complexes studied herein bind to model nucleo-bases and DNA, but to our surprise, testosterone-based complexes caused the DNA helix to undergo significant unwinding and bending, whereas non-steroidal control complexes caused minimal structural alterations. These effects are similar to those cisplatin induces on DNA structure despite the fact that these compounds produce a monofunctional lesion. This ability attributed to interactions between the DNA helix and bulky steroidal skeleton of testosterone, coupled with the enhanced cellular delivery induced by the steroid make the steroid approach an exciting way to explore non-conventional platinum drug delivery.     

Extended phonon collapse and the origin of the charge-density wave in 2H-NbSe2

We report inelastic x-ray scattering measurements of the temperature dependence of phonon dispersion in the prototypical charge-density-wave (CDW) compound 2H-NbSe2. Surprisingly, acoustic phonons soften to zero frequency and become overdamped over an extended region around the CDW wave vector. This extended phonon collapse is dramatically different from the sharp cusp in the phonon dispersion expected from Fermi surface nesting. Instead, our experiments, combined with ab initio calculations, show that it is the wave vector dependence of the electron-phonon coupling that drives the CDW formation in 2H-NbSe2 and determines its periodicity. This mechanism explains the so far enigmatic behavior of CDW in 2H-NbSe2 and may provide a new approach to other strongly correlated systems where electron-phonon coupling is important.