Near ultraviolet excitable cyan-green phosphors of Ba6La2Al3ScO15:Ce3+ and Ba6La2Al3ScO15:Ce3+,Tb3+: investigations on the crystal structure, site assignment of Ce3+ and Tb3+ ions, and an energy transfer process from Ce3+ to Tb3.

An energy transfer from Ce3+ to Tb3+ is feasible in energy transition processes for the development of optical devices, especially phosphor-converted white LEDs (pc-wLEDs). Most of the energy transfer phosphors co-doped with Ce3+ and Tb3+, unfortunately, have weak absorption under a near-ultraviolet light of around 405 nm and blue light excitation, making them incapable for use as near ultraviolet or blue LEDs. In this study, novel energy transfer luminescent materials, Ba6La2Al3ScO15:Ce3+,Tb3+, isostructural with existing Ba6La2(Al,Fe)4O15, were successfully synthesized through a conventional solid-state reaction as a single phase. The phosphors showed a broad cyan emission of Ce3+ and narrow green emissions of Tb3+ under a near-ultraviolet light of 405 nm, which was nearly located at an emission wavelength of near-ultraviolet LEDs. The occurrence of energy transfer from Ce3+ to Tb3+ was evidenced by emission lifetime measurements. The lifetime analysis based on formulated energy transfer models, such as Inokuti-Hirayama, Yokota-Tanimota and Martin models, revealed that an energy transfer process from Ce3+ to Tb3+ took place dominantly by a dipole-dipole interaction with low migration among the donors of Ce3+.

Structure and Luminescence Studies of a Ce3+-Activated Ba5La3MgAl3O15 Green-Emitting Phosphor.

Novel green-emitting Ba5La3MgAl3O15:Ce3+ (BLMAO:Ce3+) is successfully obtained by a solid-state reaction. In this study, BLMAO, which is inspired from the Ba6La2A1.5Fe2.5O15 crystal structure, shows a green emission approximately peaked around 500 nm under near-ultraviolet light excitation at 412 nm by Ce3+ doping. Moreover, internal and external quantum efficiencies of BLMAO:0.02Ce3+ are found to be 27 and 22%, respectively. The emission peak deconvolution and Dorenbos model calculation reveal that the Ce3+ ion occupies on two different crystallographic sites. The potential of BLMAO:Ce3+ for phosphor-converted white LEDs (pc-wLEDs) is systematically evaluated from the results of Rietveld refinement and luminescence measurement.

Porous Lanthanide Metal-Organic Frameworks Using Pyridine-2,4-dicarboxylic Acid as a Linker: Structure, Gas Adsorption, and Luminescence Studies.

Two types of new lanthanide coordination networks, [Ln3(pdc)4(Hpdc)(H2O)3]·8H2O [H2pdc = pyridine-2,4-dicarboxylic acid; Ln = Ce (1), Pr (2), Sm (3), Eu (4); type A) and [Tb5(pdc)4(Hpdc)]·3H2O (type B), have been synthesized using a hydrothermal synthetic method. The former type A compound has an unfamiliar architecture, even basically comprised of primitive cubic (pcu) topology, and demonstrate porous gas adsorption behavior, giving several hundreds of square meters per gram surface areas after evacuation of the water molecules, while the latter type B compound does not show any porous properties. Most interestingly, the solvothermal synthetic method using N,N-dimethylformamide (DMF) as a solvent gives compounds that crystallize in a structure analogous to that of type A for Ln = La-Ho, probably formulated as [Ln3(pdc)4(Hpdc)·(DMF)m]·nDMF. These compounds also exhibit large surface areas after evacuation of the DMF molecules and also moderate amounts of hydrogen gas uptake at 77 K. The luminescence properties were investigated for Eu and Tb analogues at elevated temperatures, at which an unusual increase in the emission intensity was observed upon the release of solvents, and discussed based on their porous structure.

Molecular sexing in Japanese murrelet (Synthliboramphus wumizusume) and a tandem-repeat polymorphism on the W chromosome.

The Japanese murrelet (Synthliboramphus wumizusume) is an endangered small seabird species in Japan. Molecular sexing using PCR targeting of the gene encoding chromodomain helicase DNA-binding protein 1(CHD1) has been used for sex identification. Specifically, PCR using any of three commonly used primer sets (CHD1F/1R, 2550F/2718R and P2/P8) has permitted sexing in many bird species. CHD1F/1R and 2550F/2718R permitted molecular sexing in Japanese murrelet; however, P2/P8 did not permit. To generate a primer pair that permits efficient molecular sexing in this species, a new primer set, CHD1F1/1R1, was prepared to permit amplification of smaller products from degraded DNA samples. The electrophoretic patterns of PCR products amplified with the new primer set were easily classified as female or male. Additionally, the PCR product indicated the presence of a polymorphism in the fragment from chromosome W. The PCR fragments of long-type (WL) and short-type (WS) polymorphisms were observed only in females. When the distribution of the CHD1 gene on chromosome W of 61 female Japanese murrelet on Biroujima Island in Miyazaki Prefecture, WL and WS were observed in 90.2% and 9.8%. The DNA polymorphism is derived from the number of copies of a 32-bp-repeat unit, with WL and WS corresponding to two and one 32-bp-repeats, respectively.

Hepatic neuroendocrine carcinoma with metastases to the lymph nodes in a sika deer (Cervus nippon yakushimae).

A 26-year and 6-month-old male sika deer that was kept at the Showa Park, Tokyo, Japan, collapsed and died of severe disease wasting and severe tabefaction. Grossly, numerous masses, 0.3-1.0 cm diameter, were dispersed throughout the liver. The multiple masses were composed of tumor cells, which had hypochromatic nuclei and abundant faintly eosinophilic cytoplasm, arranged in nests of various sizes. Immunohistochemically, tumor cells were positive for cytokeratin, chromogranin A, synaptophysin and gastrin. Ultrastructurally, the cytoplasm of the tumor cells contained abundant membrane-bound electron-dense granules. A metastatic lesion was observed in the renal, hepatic and pancreatic lymph nodes. On the basis of these findings, this tumor was diagnosed as a neuroendocrine carcinoma with metastases to the lymph nodes.

Single Crystal Growth and Crystal Structure Analysis of Novel Orange-Red Emission Pure Nitride CaAl2Si4N8:Eu2+ Phosphor.

Single crystal of novel orange-red emission CaAl2Si4N8:Eu2+ phosphor was grown by our original vapor phase technique, and the precise crystal structure was investigated for the first time by single crystal X-ray diffraction analysis. The crystal structure of CaAl2Si4N8:Eu2+ single crystal was verified to be an α-Si3N4-type trigonal structure (space group P31c) with a = 0.79525(9) nm, c = 0.57712(8) nm, and z = 2. The Ca atoms were coordinated to seven nitrogen atoms and located in the three-dimensional framework formed by (Al, Si)N4 tetrahedra. The single-crystal CaAl2Si4N8:Eu2+ phosphors exhibited a broad reddish-yellow emission with a peak at 600 nm under near-UV and blue light excitation. When increasing the temperature up to 150 °C, the emission intensity of the CaAl2Si4N8:Eu2+ phosphor decreased to 88% of the initial value at 25 °C.

Rare-earth-free white emitting Ba2TiP2O9 phosphor: revealing its crystal structure and photoluminescence properties.

A high intensity bluish-white emitting Ba2TiP2O9 phosphor was synthesized by a conventional solid-state reaction method and the precise crystal structure was investigated for the first time by Rietveld refinement analysis. Ba2TiP2O9 has a monoclinic crystal structure with a space group C2/c (no. 15), which is built out of PO4 tetrahedra and TiO5 pyramidal polyhedra connected to form a chain structure along the c-axis. The emission of Ba2TiP2O9 is due to a charge transfer transition between Ti(4+)-O(2-) in the pyramidal TiO5. The obtained Ba2TiP2O9 was excited efficiently by UV and VUV and displayed a bright bluish-white luminescence.

Hydrothermal synthesis of meso/macroporous BiVO4 hierarchical particles and their photocatalytic degradation properties under visible light irradiation.

An ordered hierarchical meso/macroporous monoclinic bismuth vanadate (BiVO4) particle was fabricated for the first time by a simple two-step melamine template hydrothermal method followed by calcination. The physiochemical parameters of as-prepared porous materials were characterized by means of X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, Raman, Barrett-Emmett-Teller, and UV-vis techniques. The nitrogen adsorption-desorption measurement and pore size distribution curve suggest that meso/macropores exist in these hierarchical microarchitectures. Further, it is found that melamine plays a significant role in the formation of porous BiVO4 particles, and when a known amount of melamine was added, the surface area and pore size of such porous BiVO4 particles were increased. The photocatalytic activities of the as-prepared hierarchical BiVO4 samples were measured for the photodegradation of Congo red aqueous dye solution under visible light irradiation. Surprisingly, the porous BiVO4 particles showed outstanding photocatalytic activities than polycrystalline BiVO4 sample. The possible enhancement of such catalytic performance has also been further discussed.

Long phosphorescent Ca2SnO4 with minuscule rare earth dopant concentration.

Rare-earth doped Ca2SnO4 phosphors were synthesized using a conventional solid state reaction method. The red phosphorescence of Eu(3+) was observed in this system with persistence time. In the as-prepared samples, the doped rare earth ions occupied both Ca and Sn sites in the host lattice. The longest phosphorescent persistence property can be achieved for the Ca2SnO4 phosphors with a 0.1% Eu dopant. Depending on the doped rare earth ions, afterglow emissions of various colors were observed.

Redetermination of the low-temperature polymorph of Li(2)MnSiO(4) from single-crystal X-ray data.

Crystals of dilithium manganese(II) silicate were grown under high-temperature hydro-thermal conditions in the system LiOH-MnO(2)-SiO(2). The title compound crystallizes in the ß(II)-Li(3)PO(4) structure type. The coordination polyhedra of all cations are slightly distorted tetra-hedra (m symmetry for MnO(4) and SiO(4)), which are linked by corner-sharing to each other. The vertices of the tetra-hedra point to the same direction perpendicular to the distorted hexa-gonal close-packed (hcp) array of O atoms within which half of the tetra-hedral voids are occupied by cations. In comparison with the previous refinement from powder X-ray data [Dominko et al. (2006 ▶). Electrochem. Commun.8, 217-222], the present reinvestigation from single-crystal X-ray data allows a more precise determination of the distribution of the Li(+) and Mn(2+) cations, giving a perfectly site-ordered structure model for both Li(+) and Mn(2+).

Combinatorial synthesis of phosphors using arc-imaging furnace.

We have applied a novel 'melt synthesis technique' rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10-60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1-5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10-60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions.