Theoretical studies on the geometric and electronic structure of substituted SCN isomers: Part 1. Non-empirical and MNDO results for some thiocyanates

Some well known thiocyanates have been studied by non-empirical and MNDO methods. The reliability of the adopted basis set and the unimportance of d orbitals on sulfur in describing thiocyanates have been tested on the HSCN molecule.The geometrical parameters computed at the STO—3G level are in good agreement with experimental data and indicate that thiocyanates are w shaped molecules with a high bending constant around the sulfur atom and quite important coupling between CSC and SCN angles.The MNDO method gives similar results, except for CS bond lengths, which are systematically underestimated.The correlation between geometry and electronic structure of thiocyanates is discussed, with special reference to cyanates, on the basis of PMO theory, Walsh diagrams and Mulliken population analysis.     

Nonlinear transmission in fibres at 308 nm

Intensity-induced variations in the energy transmittivity and temporal shape of pulses emerging from a 200-m-diameter core silica fibre have been investigated with a single-pulse XeCl laser. By coupling an XeCl laser pulse of 3mJ with a temporal width of 20 ns into a 30-m-long all-silica fibre, a total laser pulse of 1 mJ and 3 ns duration has been extracted at the fibre end. A pulse shortening larger than 80% has been observed. It is shown that the shape variations in the transmitted laser pulses are mainly due to stimulated Raman scattering processes. Substantial shape variations have been observed even at energy conversion efficiencies to the Stokes radiation of lower than 10%. The drop in energy transmittivity at higher fluences seems mainly due to two-photon absorption processes.     

Cobalt(II) dioxygen carriers based on simple diamino ligands: kinetic and ab initio studies

The kinetics of the oxygenation reaction of CoL2(2+) complexes (L=ethylenediamine (en), N,N'-dimethylethylenediamnine (dmen)) have been investigated in dimethyl sulfoxide (dmso) at 298 K and in a medium adjusted to 0.1 mol dm(-3) with Et4NClO4 by means of a UV-vis spectrophotometric technique. The reaction mechanisms are consistent with the fast formation of superoxo 1:1 initial CoL2-O2 species (L=en, dmen), whereas the dimeric mu-peroxo (CoL2)2O2 adduct is formed only when L=en, in the rate determining step. The kinetic results are discussed taking into account the effects of ligand/solvent substitution. EPR results give information on the electronic structure and the coordination geometry of the Co(II) complexes and further confirm the stoichiometry of the species formed. Ab initio calculations provide insights on the geometrical parameters of all the complexes investigated and allow us to draw some hypotheses about the influence of H.H nonbonded interactions in the eventual formation of the dimeric mu-peroxo (CoL2)2O2 complexes. Solvational effects are also considered. The formation of the (CoL3)2O2 adduct is also proved when L=en by means of O2 volumetric absorption.     

Phytotoxic metabolites by nine species of Botryosphaeriaceae involved in grapevine dieback in Australia and identification of those produced by Diplodia mutila,Diplodia seriata,Neofusicoccum australe and Neofusicoccum luteum

Botryosphaeria dieback is one of the main trunk diseases of grapevine caused by several species of Botryosphaeriaceae. Twenty-four fungal isolates representing the eight most widespread and most virulent Botryosphaeriaceae were tested for their ability to produce phytotoxic metabolites. The chromatographic profiles of their culture filtrates organic extracts showed the ability of all isolates to produce several and different metabolites. When tested on grapevine leaves and tomato cuttings the organic extracts phytotoxicity varied among isolates and species. To our knowledge, this is the first study on phytotoxic compounds produced by Botryosphaeriaceae species found in Australian vineyards. The phytotoxic metabolites produced by Diplodia seriata, Diplodia mutila, Neofusicoccum australe and, for the first time, by Neofusicoccum luteum were isolated and chemically identified essentially by spectroscopic methods.

     

Imidazo[2,1-b]thiazole carbamates and acylureas as potential insect control agents

Imidazo[2,1-b]thiazole carbamates and acylureas were prepared by reaction of 5-hydroxymethylimidazo-[2,1-b]thiazole and imidazo[2,1-b]thiazole-5-carboxyamide with arylisocyanates. The products formed depend from the substituent bonded at the 6 position of the imidazothiazole moiety, and from the reaction conditions.     

Comparing propene polymerization with 1-butene polymerization catalyzed by MAO-activated C2- and C1-symmetric zirconocenes: An experimental and computational study on the influence of olefin size on stereoselectivity

Polypropene and poly(1-butene) have been synthesized under very similar experimental conditions with a series of MAO-activated C₂-symmetric and C₁-symmetric ansa-zirconocenes. The C₁-symmetric zirconocenes bearing the bilaterally symmetric fluorenyl or bis(2-methylthieno)cyclopentadienyl ligand connected through a dimethylsilyl bridge to substituted indenyl ligands produce isotactic polybutene of similar or higher molecular mass and with noticeably higher isotacticity, compared to isotactic polypropene prepared with the same catalysts under comparable conditions. Structural and mechanistic reasons for such behavior are discussed on the basis of QM/MM calculations.     

Validation of a new HPLC‐UV method for determination of the antibiotic linezolid in human plasma and in bronchoalveolar lavage

A rapid and selective HPLC‐UV method was developed for the quantification of linezolid (LNZ) in human plasma and bronchoalveolar lavage (BAL) at the concentrations associated with therapy. Plasma samples were extracted by solid‐phase extraction followed by evaporation to dryness and reconstitution in mobile phase solution. The chromatographic separation was carried out on a C₁₈ column with an isocratic mobile phase consisting of dihydrogen phosphate buffer 50 mm (pH 3.5) and acetonitrile (60:40 v/v). The detection was performed using a photodiode array. Under these conditions, a single chromatographic run could be completed within 12 min. The method was validated by estimating the precision and the accuracy for inter‐ and intra‐day analysis in the concentration range of 25–25600 ng/mL. The method was linear over the investigated range with all the correlation coefficients R > 0.999. The intra‐ and inter‐day precision was within 8.90% and the accuracy ranged from ?4.76 to +5.20%. This rapid and sensitive method was fully validated and could be applied to pharmacokinetic study for the determination of LNZ levels in human plasma and BAL samples. Copyright © 2013 John Wiley & Sons, Ltd.     

Mg based photocathodes for high brightness RF photoinjectors

Advanced high brightness radio frequency (RF) gun injectors require photocathodes with a fast response, high quantum efficiency (QE) and good surface uniformity. Metal films deposited by various techniques on the gun back wall could satisfy these requirements. A new deposition technique has been recently proposed, i.e. pulsed laser ablation. Several Mg samples have been deposited by this technique: the emission performance and morphological changes induced on the cathode surface during laser activation are compared and discussed.     

Parallel solution in time of ODEs: some achievements and perspectives

The parallel solution of initial value problems for ordinary differential equations (ODE-IVPs) has received much interest from many researchers in the past years. In general, the possibility of using parallel computing in this setting concerns different aspects of the numerical solution of ODEs, depending on the parallel platform to be used and/or the complexity of the problem to be solved. In particular, in this paper we examine possible extensions of a parallel method previously proposed in the mid-nineties [P. Amodio, L. Brugnano, Parallel implementation of block boundary value methods for ODEs, J. Comput. Appl. Math. 78 (1997) 197–211; P. Amodio, L. Brugnano, Parallel ODE solvers based on block BVMs, Adv. Comput. Math. 7 (1997) 5–26], and analyze its connections with subsequent approaches to the parallel solution of ODE-IVPs, in particular the “Parareal” algorithm proposed in [J.L. Lions, Y. Maday, G. Turinici, Résolution d'EDP par un schéma en temps “pararéel”, C. R. Acad. Sci. Paris, Ser. I 332 (2001) 661–668; Y. Maday, G. Turinici, A parareal in time procedure for the control of partial differential equations, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 387–392].