Investigation of crystal/electronic structure effects on the photoluminescence properties in the BaO–SiO2:Eu2+ systems

BaO–SiO₂:Eu²⁺ phosphors with different Ba/Si mole ratio were prepared using a solid-state reaction method, and their crystal structure dependent-photoluminescence properties were investigated. The prepared phosphor powders were characterized using X-ray diffraction (XRD), field-emission electron microscopy (FE-SEM) and fluorescence spectroscopy. The emission band of the Eu²⁺ activator varied from orange to blue with varying crystal structure of the host materials, which was related to the crystal field splitting of the Eu 5d orbitals. These emission color changes were examined by calculating the electronic band structure properties such as the density of the state. Moreover, the host material with Ba/Si=1 (BaSiO₃) for Eu²⁺, which exhibited a yellow emission when excited with near UV light, was further characterized for enhancing its emission intensity.     

Poly(diphenylacetylene)s with Electron‐Donating Alkoxy and Electron‐Withdrawing Fluoroalkyl Groups: Effect of the Substituent on Fluorescence

New poly(diphenylacetylene)s with alkoxy and fluoroalkyl groups as electron‐donating and electron‐withdrawing groups, respectively, were synthesized by using a WCl₆‐n‐Ph₄Sn catalyst. The polymer solutions emitted strong, bluish‐green lights when photo‐excited. The polymers that contained the electron‐donating alkoxy groups showed longer fluorescence‐maximum peaks when compared to the polymers that contained the electron‐withdrawing fluoroalkyl groups. However, such an effect of the substituent on the absorption property was not clearly seen. The emission bands of the solid films did not show any significant red shift, relative to that of the dilute solution.

     

A Unique Tryptophan C‐Prenyltransferase from the Kawaguchipeptin Biosynthetic Pathway

Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides.     

All-solid-state carbonate-selective electrode based on a molecular tweezer-type neutral carrier with solvent-soluble conducting polymer solid contact

Carbonate-selective membranes were prepared by incorporating a molecular tweezer-type carbonate-selective neutral carrier [N,N-dioctyl-3alpha,12alpha-bis(4-trifluoroacetylbenzyloxy)-5beta-cholan-24-amide] into a room temperature vulcanizing-type silicone rubber (3140 RTV-SR) matrix, and deposited on the planar-type electrodes (Pt containing Ag/AgCl electrodes formed on a ceramic plate) with and without an intermediary conducting polymer layer. Two types of solvent-soluble conducting polymers [poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) or poly(3-octylthiophene-2,5-diyl)] have been examined as the solid contact material. Potentiometric properties of the resultant all-solid-state electrodes were evaluated in terms of their carbonate selectivity, response slope, potential stability and reproducibility. The sensitivity and carbonate selectivity of the SR membrane-based all-solid-state electrodes with conducting polymer solid contact were comparable to those of conventional electrodes. Experimental results also showed that the intermediary conducting polymer layer used in the all-solid-state electrodes greatly reduces the interference from dissolved oxygen.     

Mixed finite volume methods on nonstaggered quadrilateral grids for elliptic problems

We construct and analyze a mixed finite volume method on quadrilateral grids for elliptic problems written as a system of two first order PDEs in the state variable (e.g., pressure) and its flux (e.g., Darcy velocity). An important point is that no staggered grids or covolumes are used to stabilize the system. Only a single primary grid system is adopted, and the degrees of freedom are imposed on the interfaces. The approximate flux is sought in the lowest-order Raviart-Thomas space and the pressure field in the rotated- nonconforming space. Furthermore, we demonstrate that the present finite volume method can be interpreted as a rotated- nonconforming finite element method for the pressure with a simple local recovery of flux. Numerical results are presented for a variety of problems which confirm the usefulness and effectiveness of the method.

     

Infrared emission and defect centres in Er and Yb codoped Y3Al5O12 phosphors

YAG phosphor powders doped/codoped with Er³⁺/(Er³⁺ + Yb³⁺) have been synthesised by using the solution combustion method. The effect of direct pumping into the ⁴I_11/2 level under 980 nm excitation of doped/codoped Er³⁺/Yb³⁺−Er³⁺ in Y₃Al₅O₁₂ (YAG) phosphor responsible for an infrared (IR) emission peaking at ∼1.53 μm corresponding to the ⁴I_13/2→⁴I_15/2 transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140°C, 210°C and 445°C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O⁻ ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.     

A formal construction of a divergence-free basis in the nonconforming virtual element method for the Stokes problem

Numerical Algorithms - We develop a formal construction of a pointwise divergence-free basis in the nonconforming virtual element method of arbitrary order for the Stokes problem introduced in Zhao...     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

On translation lengths of Anosov maps on the curve graph of the torus

Geometriae Dedicata - We show that an Anosov map has a geodesic axis on the curve graph of the torus. The direct corollary of our result is the stable translation length of an Anosov map on the...