Photoluminescence and energy transfer in transparent glass-ceramics based on GdF3:RE3+ (RE = Tb,Eu) nanocrystals

In the present work,the transparent oxyfluoride glass-ceramic samples containing GdF_3:RE~(3+)(RE=Tb,Eu) nanocrystals(nGCs) were fabricated via controlled heat-treatment of precursor xerogels prepared using a sol-gel method.The formation of GdF_3 nanocrystalline phase from gadolinium(III) trifluoroacetate was verified based on XRD measurements.The average crystal sizes calculated from Scherrer formula were estimated to～10 nm as well as～6 nm for Tb~(3+)-and Eu~(3+)-doped samples,respectively.The optical behavior of prepared sol-gel samples was evaluated based on photoluminescence excitation(PLE) and emission spectra(PL) as well as luminescence decay analysis.Obtained samples exhibit the ~5D_4→~7F_J(J=6-3,Tb~(3+))and the ~5D_0→~7F_J(J=0-4,Eu~(3+)) emission bands recorded within the visible spectral area under excitation at near-UV(393 nm(Eu~(3+)),351,369,378 nm(Tb~(3+))) as well as middle-UV illumination(273 nm(Gd~(3+))).Additionally,based on recorded decay curves,the luminescence lifetimes(τ_m) for the ~5D_4(Tb3+) and the ~5D_0(Eu~(3+))excited states were also evaluated.In general,recorded luminescence spectra and double-exponential character of decay curves for nGCs indicate a successful migration of Tb~(3+) and Eu~(3+) dopant ions from amorphous silicate framework to lowphonon energy GdF_3 nanocrystal phase.     

High-Performance Liquid Chromatography Method for the Monitoring of the <Emphasis Type="Italic">Allium</Emphasis> Derivative Propyl Propane Thiosulfonate Used as Natural Additive in Animal Feed

A new simple analytical method for monitoring propyl propane thiosulfonate (PTSO) in animal feed is presented. PTSO is an active ingredient from Allium spp. (like onion and shallot), proposed as a natural additive for feed being an efficient alternative to antibiotics used as growth promoter due to its efficiency improving animal health. Reversed-phase liquid chromatography with UV detection has been used and a previous sample treatment based on solid-liquid extraction has been developed and optimized in order to extract PTSO from a feed for laying hens using acetone as extraction solvent. The method has been characterized obtaining limits of detection and quantification of 11.2 and 37.3 mg kg^?1, respectively, which are lower than the concentrations expected in samples containing this additive. The intra- and interday relative standard deviations (RSDs) were lower than 8.3 % in all the cases, and recoveries varied from 90.2 to 94.6 %. Finally, in order to check the unequivocal identification of PTSO, mass spectrometry detection was applied. The proposed method is a simple procedure for monitoring PTSO in commercial feed, being possible to implement it in routine laboratories for quantification purposes and stability studies of the distributed products.     

Disruption management in the airline industry—Concepts,models and methods

This paper provides a thorough review of the current state-of-the-art within airline disruption management of resources, including aircraft, crew, passenger and integrated recovery. An overview of model formulations of the aircraft and crew scheduling problems is presented in order to emphasize similarities between solution approaches applied to the planning and recovery problems. A brief overview of research within schedule robustness in airline scheduling is included in the review, since this proactive measure is a natural complement to disruption management.     

Profiling glucosinolates in vegetative and reproductive tissues of four Brassica species of the U‐triangle for their biofumigation potential

Glucosinolates are amino acid derived allelochemicals present in all plants of the order Capparales. These compounds are degraded by myrosinase isoenzymes, releasing a series of biologically active products defined by the parent glucosinolate and the reaction conditions. Species within the Brassicaceae are found to differ in their glucosinolate profile and glucosinolate concentrations. Different tissues within a single plant also show such variations, which are further influenced by the growth stage and environmental conditions. In the experiments described in this paper, four Brassica species of the U‐triangle (B. carinata, B. nigra, B. juncea and B. rapa) were compared with respect to their glucosinolate profiles in roots, stems, leaves and reproductive organs at different developmental stages. The glucosinolate profile of corresponding ripe seeds was also determined. Prop‐2‐enylglucosinolate was identified as the major glucosinolate in the three mustards, where it represented over 90% of the total glucosinolate concentration of ripe seeds and over 50% of green tissues. The relative concentration of this glucosinolate increased in all tissues during plant growth. Brassica rapa showed a different glucosinolate profile than the three mustards, with higher concentrations of but‐3‐enylglucosinolate, 2‐hydroxybut‐3‐enylglucosinolate and 2‐hydroxypent‐4‐enylglucosinolate. The concentration of indol‐3‐ylmethylglucosinolates was also higher in B. rapa than in the mustard plants, with 4‐hydroxyglucobrassicin representing 30% of the total glucosinolate concentration in ripe seeds. The total glucosinolate concentration of the species studied varied with growth stage and the mustards achieved a maximum towards the end of the period monitored. Glucosinolate concentration decreased in roots and leaves but increased in reproductive tissues. The determined glucosinolate profiles are an initial step in assessing the biofumigation potential of these species of the Brassicaceae family. Copyright © 2007 Society of Chemical Industry     

Influence of branching regularity on the behavior of hyperbranched polymers in solution

A carbosilane pseudo‐dendrimer with irregular structure and degree of branching DB = 1 was synthesized and fractionated. The molar masses of the obtained fractions ranged from 5000 to 490 000 g mol^?1. The hydrodynamic and conformational properties were studied by the methods of light scattering, sedimentation‐diffusion analysis and viscometry in dilute hexane and toluene solutions. The Mark ? Kuhn ? Houwink dependences were obtained. The results for the pseudo‐dendrimer are compared with the data for the initial hyperbranched poly(diallylcarbosilane) with DB = 0.5 and carbosilane dendrimer. It is shown that the solution properties of the pseudo‐dendrimer are close to those for the irregular hyperbranched polymer and differ significantly from the dendrimer behavior. Hence, it is branching regularity rather than the degree of branching that determines the conformational and hydrodynamic properties of hyperbranched polymers with a high degree of branching DB ≥ 0.5. © 2014 Society of Chemical Industry     

Polarizability,Susceptibility, and Dielectric Constant of Nanometer‐Scale Molecular Films: A Microscopic View

The size‐dependence of the polarizability, susceptibility, and dielectric constant of nanometer‐scale molecular layers is explored theoretically. First‐principles calculations based on density functional theory are compared to phenomenological modeling based on polarizable dipolar arrays for a model system of organized monolayers composed of oligophenyl chains. Size trends for all three quantities are primarily governed by a competition between out‐of‐plane polarization enhancement and in‐plane polarization suppression. Molecular packing density is the single most important factor controlling this competition and it strongly affects the bulk limit of the dielectric constant as well as the rate at which it is approached. Finally, the polarization does not reach its “bulk” limit, as determined from the Clausius–Mossotti model, but the susceptibility and dielectric constant do converge to the correct bulk limit. However, whereas the Clausius–Mossotti model describes the dielectric constant well at low lateral densities, finite size effects of the monomer units cause it to be increasingly inaccurate at high lateral densities.     

Effect of metal purity and testing procedure on surface tension measurements of liquid tin

The surface tension of liquid tin of three different grades of purity (99.85, 99.96, and 99.999%) was measured by the classical sessile drop method over the temperature range 523–1023 K, in heating and cooling regimes. The results obtained show that the metal purity affects the values of surface tension and its temperature dependence. The highest values of surface tension and smooth linear temperature dependence were obtained in cooling regime for tin of the highest purity. With increasing content of impurities, both surface tension and its temperature coefficient decrease while the scatter of the data increases. The surface tension values measured on heating regime show higher scatter, compared to those obtained in cooling regime, and the temperature dependence of the surface tension is curvilinear rather than linear.     

Structure and phase behavior of a disk-necklace polymer: Cyclolinear polymethylsiloxane

The structure and phase transitions of cyclolinear polyorganosiloxane copolymer containing 12-member polysiloxane rings have been studied using synchrotron WAXS, DSC, TEM, variable-temperature AFM and polarized optical microscopy. The primary structure of this polymer can be viewed as a necklace of disk-shaped entities (cyclic groups) connected via flexible linkers.In the mesomorphic state, the presence of two different LC phases has been derived from the analysis of WAXS fiber diffractograms. The morphology of one of the phases shows a conventional hexagonal packing of LC chains where the chain axes are perpendicular to the plane of the 2D hexagonal lattice. The other one, so-called R-phase, has a vertically oriented rectangular 2D lattice formed by inter-chain correlations between the bulky polysiloxane cycles (disks). To our knowledge, such a disk-necklace mesophase in which the LC lattice is parallel to the backbone direction has not been reported in the literature so far.     

Hydrocarbon-ammonia moulding-a new technology for production of combustion catalysts

Fluidized bed catalytic combustion has proved to be very promising for industrial application. The milestone problem is development of support and catalyst with high mechanical and thermal stability. We have developed a new technology for production of alumina supports with desired spherical shape, texture and structure. Properties of spherical granules depend on the method of granulation and most attention has been paid to development and optimization of hydrocarbon-ammonia moulding to produce uniform alumina spheres. Optimization of high quality spheres production focused on study of effect of initial hydroxide properties and molding conditions on properties of final product. Modification of spherical alumina with oxides of Mg, La, Ce, and Si proved to be effective to substantially improve the mechanical and thermal stability. This effect is most pronounced when, pairs of these dopes are introduced simultaneously.     

Control of polyaniline conductivity and contact angles by partial protonation

Many studies require a specific value of conductivity when investigating conducting polymers. The conductivity of polyaniline can efficiently be controlled by partial protonation of the polyaniline base. Although this is a simple task in principle, practical guidelines are missing. In the present study, the changes in the conductivity of polyaniline base after immersion in aqueous solutions of various acids are reported. Polyaniline base has been reprotonated in aqueous solutions of picric, camphorsulfonic and phosphoric acids. The conductivity of partially reprotonated polyaniline varied between 10⁻⁹ and 10⁰ S cm⁻¹. The relation between the pH of a phosphoric acid solution, which was in equilibrium with polyaniline, and the conductivity σ is pH = 0.77 − 0.64 log(σ [S cm⁻¹]). The wettability, i.e. water contact angles, can similarly be set by partial protonation to between 78° for polyaniline base and 44° for polyaniline reprotonated in 1 mol L⁻¹ phosphoric acid. In solutions of picric acid, the transition from the non‐conducting to the conducting state occurs over a narrow range of acid concentrations, and the tuning of conductivity is consequently difficult. Phosphoric acid is well suited for the control of conductivity of polyaniline because of the moderate dependence of the conductivity on the acid concentration or pH. Copyright © 2007 Society of Chemical Industry