Copper-catalyzed dimerization of chromium Fischer carbene complexes: synthesis of dialkoxytrienes and their Nazarov-type cyclization to 2-alkoxy-2-cyclopentenones

Fischer carbene complexes 1 underwent a clean ligand dimerization reaction yielding functionalized olefins and trienes 4 in the presence of copper (I) catalysts. If treated with trifluoroacetic acid (TFA), trienes 4c, d, f undergo a cyclization process (Nazarov reaction) which furnishes cyclopentenone derivatives 6c, d, 7c, d and 8 in good yields. Finally, the Fischer aminocarbene 9 efficiently cyclodimerizes to the substituted arene 10 in the presence of CuBr.     

Plastic crystals and their potential use in new technologies

The paper gives some comments about the potential use of plastic crystals in energy storage. The main point deals with the possibilities of binary solid solution formation. Three binary phase diagrams in the pentaerythritol series are commented on.     

Convergent stereocontrolled synthesis of substituted exo-glycals by Stille cross-coupling of halo-exo-glycals and stannanes

(Z)-exo-Glycals can be conveniently prepared in a convergent manner by Stille cross-coupling of (Z)-halo(Br,I)-exo-glycals and aryl or alkenyl stannanes, the latter are readily obtained by addition of tributylstannyl radicals to terminal alkynes.     

Study of medieval enamelling on gilded objects combining SEM-EDAX and PIXE

A set of fragments of metallic artefacts from the medieval period excavated from Ciudad Real in Spain has been studied. The objects are gilded copper buckles with a champlevé enamelling decoration. The composition of predominantly blue-coloured enamels has been analysed using three non-destructive techniques, SEM-EDAX (scanning electron microscopy coupled with energy-dispersive X-ray analysis), X-ray fluorescence (XRF) and PIXE (particle-induced X-ray emission). Analyses show that Co is responsible for the blue colour. The results of the two techniques are compared, as well as the main components which constitute the enamel. Analyses suggest that Cu is responsible for red colour.     

Optimization and validation of a method of analysis for fenitrothion and its main metabolites in forestry air samples using sorbent tubes with thermal desorption cold trap injection and gas chromatography-mass spectrometry

An analytical methodology using thermal-desorption cold trap (TCT) and GC-MS was developed for the determination of the insecticide fenitrothion and its main metabolites, 3-methyl-4-nitrophenol and fenitrooxon, in forestry atmospheres. The sampled atmosphere was pumped through a glass tube containing 100 mg of Tenax adsorbent at a flow rate of 50 ml min(-1). Adsorption/thermal desorption and breakthrough experiments were performed to test the ability to quantitatively trap the compounds. The detection limits of method for these compounds ranged between 1.6 and 2.1 ng m(-3). This methodology was developed to evaluate the persistence of fenitrothion in forest atmospheres after treatment. Spray application at 21.5 mg active ingredient m(-2) resulted in atmosphere levels of the insecticide of 78.3 ng m(-3) (after 2 h of application). Within 2-4 days following treatment, the presence of fenitrooxon fell to 50-55%. During this period residues of metabolites began to appear, disappearing 19 days later.     

Measurements of the Decay KL-->e+ e- mu+ mu-

The KTeV experiment at Fermilab has isolated a total of 132 events from the rare decay K(L)-->e+ e- mu+ mu-, with an estimated background of 0.8 events. The branching ratio of this mode is determined to be [2.69+/-0.24(stat)+/-0.12(syst)]x10(-9), with a radiative cutoff of M(2)(ee mu mu)/M(2)(K)>0.95. The first measurement using this mode of the parameter alpha from the D'Ambrosio-Isidori-Portolès (DIP) model of the K(L)gamma*gamma* vertex yields a result of -1.59+/-0.37, consistent with values obtained from other decay modes. Because of the limited statistics, no sensitivity is found to the DIP parameter beta. We use this decay mode to set limits on CP and lepton violation.     

Diblock copolymer–azobenzene complexes through hydrogen bonding: Self‐assembly and stable photoinduced optical anisotropy

We have demonstrated the preparation of a series of photoaddressable supramolecular block copolymers by mixing a carboxy‐terminated azobenzene derivative, 6‐[4‐(4′‐cyanophenylazo)phenyloxy]hexanoic acid (AZO), and two polystyrene‐b‐poly(4‐vinylpiridine) (PS‐b‐P4VP) block copolymers. AZO can be selectively attached to the P4VP block of PS‐b‐P4VP through hydrogen bonding interactions. The assembly of AZO with vinylpyridine group‐containing polymers was initially investigated on a model system composed of P4VP homopolymer and AZO. Homogeneous liquid crystalline materials were obtained for ratios of AZO to vinylpyridine repeating unit, x, lower or equal to 0.50. Mixtures with higher x resulted in heterogeneous materials showing clear macrophase separation. Accordingly, a series of hydrogen‐bonded complexes of PS‐b‐P4VP and AZO, PS‐b‐P4VP(AZO)_x, with x = 0.25 and x = 0.50 were prepared. Lamellar and spherical morphologies were observed for the complexes based on PS24‐b‐P4VP9.5 (M_n,PS = 24,000, M_n,P4VP = 9500) and PS24‐b‐P4VP1.9 (M_n,PS = 24,000, M_n,P4VP = 1900), respectively. Photoinduced orientation of the azobenzene units was obtained in films of P4VP(AZO)_x and PS‐b‐P4VP(AZO)_x with x = 0.25 and 0.50 by using 488 nm linearly polarized light and characterized through birefringence and dichroism measurements. This investigation shows a versatile and less laborious approach to azobenzene‐containing polymer materials with low chromophore content, of interest in optical application. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Effects of ozone in surface modification and thermal stability of SEBS block copolymers

SEBS block copolymers were treated under mild conditions in an ozone atmosphere, producing very slightly chemically-modified surfaces. The thermal stability was analysed by chemiluminescence and related to morphological changes observed by AFM. The intrinsic thermal stability was diminished by ozone exposure, but the oxidation induction times were delayed which indicates an enhancement of thermal stability under oxidative conditions. Also, chemiluminescence analysis showed the presence of a typical order-disorder transition at temperatures around 120 °C. Two different sets of samples which showed different morphological patterns were imaged by AFM. The effects of micro-domain separation and inter-domain structure on thermal properties are discussed and explained by a coarsening of the internal interface induced by ozone. A detailed 2D Fourier transformed analysis of AFM images allowed us to identify a regular wrinkled nano-pattern induced by uniaxial strain combined with ozone treatment, offering new opportunities in applications ranging from organic electronics to bio-patterning.