Thermoluminescence, structural and magnetic properties of a Li(2)O-B(2)O(3)-Al(2)O(3) glass system doped with LiF and TiO(2)

A Li(2)O-B(2)O(3)-Al(2)O(3) glass system, un-doped and doped with LiF, and/or TiO(2) was synthesized by the fusion method and its physical properties were investigated by thermoluminescence (TL), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), atomic force microscopy (AFM) and differential thermal analysis (DTA). The samples were subjected to gamma-rays from a colbalt-60 ((60)Co) source. These techniques provided evidence of LiF and LiF doped with Ti crystal formation in the glass system. A TL glow peak at about 433 K was sensitive to (60)Co gamma-rays and showed good linearity with doses and consequently could be used to quantify radiation doses. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Effect of Eu(2)O(3) doping on Ta(2)O(5) crystal growth by the laser-heated pedestal technique

High energy band gap hosts doped with lanthanide ions are suitable for optical devices applications To study the potential of Ta(2)O(5) as a host compound pure and Eu(2)O(3)-doped Ta(2)O(5) crystal fibers were grown by the laser-heated pedestal growth technique in diameters ranging from 250 to 2600 pm and in lengths of up to 50 mm The axial temperature gradient at the solid/liquid interface of pure Ta(2)O(5) fibers revealed a critical diameter of 2200 gm above which the fiber cracks X-ray diffraction measurements of the pure Ta(2)O(5) single crystals showed a monoclinic symmetry and a growth direction of [1 (1) over bar 0] An analysis of the pulling rate as a function of the fiber diameter for Eu(2)O(3)-doped Ta(2)O(5) fibers indicated a well defined region in which constitutional supercooling is absent Photoluminescence measurements of pure Ta(2)O(5) crystals using excitation above the band gap (3 8 eV) were dominated by a broad unstructured green band that peaked at 500 nm Three Eu(3+)-related optical centers were identified in the doped samples with nominal concentrations exceeding 1 mol% Two of these centers were consistent with the ion in the monoclinic phase with different oxygen coordinations The third one was visible in the presence of the triclinic phase (C) 2010 Elsevier B V All rights reserved

Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Spectroscopic Investigation on the Formation of a Dinuclear Me(2)SO-Ru(2)-Mercaptopyridine Bridged Complex: [Ru(2)Cl(3)(mu-pyS)(mu-dmso)(dmso)(4)]center dot 2H(2)O

A dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine (2-pyridinethiol or 2-pyridyl mercaptan) and a methyl sulfoxide (dmso) have been characterized by X-ray crystallography. The reported compound with formula [Ru(2)Cl(3) (mu-pyS)(mu-dmso)(dmso)(4)] center dot 2H(2)O, [C(15)H(36)Cl(3)NO(7)S(6)Ru(2)] (P2/c, a = 13.8175(2) angstrom, b = 10.5608(2) angstrom, c = 21.3544 (3) angstrom, beta = 106.090(1)degrees, V = 2,994.05(8) angstrom(3), Z = 4) represents a seven-membered ring system with both rutheniums in an octahedral geometry. All the hydrogen bonds (C-H-Cl) and the van der Waals contacts give rise to three-dimensional network in the structure and add stability to the dinuclear compound. To our knowledge, this is the first time that the formation of a dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine and dmso have been reported. The study also provided valuable insight into bioinorganic chemistry as continuing efforts are being made to develop metal-based cancer chemotherapeutics. A major feature of this paper is the resolution of a double bridged ruthenium structure which contributes to a better understanding of ruthenium reactivity.

Structural role of fluoride in the ion-conducting glass system B(2)O(3)-PbO-LiF studied by single- and double-resonance NMR

The local structure of an ion-conducting glass with nominal composition 50B(2)O(3)-10PbO-40LiF has been investigated by complementary (7)Li, (11)B, (19)F, and (207)Pb single- and double-resonance experiments. The results give insight into the structural role of the lithium fluoride additive in borate glasses: (1) LiF is seen to actively participate in the network transformation process contributing to the conversion of three- into four-coordinate boron units, as shown by (11)B single-resonance as well as by (11)B{(19)F} and (19)F{(11)B} double-resonance experiments. (2) (19)F signal quantification experiments suggest substantial fluoride loss, presumably caused by formation of volatile BF(3). A part of the fluoride remains in the dopant role, possibly in the form of small LiF-like cluster domains, which serve as a mobile ion supply. (3) The extent of lithium-fluorine and lead-fluorine interactions has been characterized by (7)Li{(19)F} and (207)Pb{(19)F} REDOR and SEDOR experiments. On the basis of these results, a quantitative structural description of this system has been developed.

On the use of 2,1,3-benzothiadiazole derivatives as selective live cell fluorescence imaging probes

Newly designed 2,1,3-benzothiadiazole-containing fluorescent probes with four excited state intramolecular proton transfer (ESIPT) sites were successfully tested in live cell-imaging assays using a confluent monolayer of human stem-cells (tissue). All tested dyes were compared with the commercially available DAPI and gave far better results. (c) 2010 Elsevier Ltd. All rights reserved.

Thermoluminescence and synchrotron radiation studies on the persistent luminescence of BaAl(2)O(4)/Eu(2+),Dy(3+)

The persistent luminescence materials, barium aluminates doped with Eu(2+) and Dy(3+) (BaAl(2)O(4): Eu(2+),Dy(3+)), were prepared with the combustion synthesis at temperatures between 400 and 600 degrees C as well as with the solid state reaction at 1500 degrees C. The concentrations of Eu(2+)/Dy(3+) (in mol% of the Ba amount) ranged from 0.1/0.1 to 1.0/3.0. The electronic and defect energy level structures were studied with thermoluminescence (TL) and synchrotron radiation (SR) spectroscopies: UV-VUV excitation and emission, as well as with X-ray absorption near-edge structure (XANES) methods. Theoretical calculations using the density functional theory (DFT) were carried out in order to compare with the experimental data. (C) 2010 Elsevier Inc. All rights reserved.

Optical energy storage properties of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr(2)MgSi(2)O(7):Eu(2+),R(3+) material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 A degrees C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R(3+) co-dopants.

Persistent luminescence of Eu(2+) and Dy(3+) doped barium aluminate (BaAl(2)O(4):Eu(2+),Dy(3+)) materials

Polycrystalline Eu(2+) and Dy(3+) doped barium aluminate materials, BaAl(2)O(4):Eu(2+),Dy(3+), were prepared with solid state reactions at temperatures between 700 and 1500 degrees C. The influence of the thermal treatments on the stability, homogeneity and structure as well as to the UV-excited and persistent luminescence of the materials was investigated by X-ray powder diffraction, SEM imaging and infrared spectroscopies as well as by steady state luminescence spectroscopy and persistent luminescence decay curves, respectively. The IR spectra of the materials prepared at 250, 700, and 1500 degrees C follow the formation of BaAl(2)O(4) composition whereas the X-ray powder diffraction of compounds revealed how the hexagonal structure was obtained. The morphology of the materials at high temperatures indicated important aggregation due to sintering. The luminescence decay of the quite narrow Eu(2+) band at ca. 500 nm shows the presence of persistent luminescence after UV irradiation. The dopant (Eu(2+)) and co-clopant (Dy(3+)) concentrations affect the crystallinity and luminescence properties of the materials. (C) 2009 Elsevier B.V. All rights reserved.

Group 11 (Cu, Ag, Au) promotion of 15%Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts

Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts promoted with different quantities of Group 11 metals (Cu, Ag, Au) were characterized and tested. The presence of relatively small quantities of such metals enhanced Co reducibility and, in the cases of Ag and Au, improved the surface Co metal active site densities. EXAFS experiments with the most loaded catalyst samples show that only Co-Co and Me-Me (Me = Cu, Ag and Au) coordination could be observed. This suggests that the greater fraction of the metals form different phases. However, the reduction promoting effect of the Group 11 metal is severely hampered once the catalyst receives a mild passivation treatment following primary reduction. An explanation in terms of promoter segregation during primary reduction is proposed. At lower promoter levels (0.83%Ag and 1.51%Au) and higher Ag levels (2.76%), significant gains in Co active site densities were achieved resulting in improved CO conversion levels relative to the unpromoted catalyst. Moreover, slight decreases in light product (e.g., CH(4)) selectivity and slight increases in C(5)+ selectivity were achieved. At high Au loading (5.05%), however, too much Au was loaded which, although significantly increasing the fraction of Co reduced, blocked Co surface sites and resulted in decreased Co conversion rates. While Cu facilitated Co reduction, the increased fraction of reduced Co did not translate to improved active site densities. It appears that a fraction of Cu tended to cover the rim of Co clusters, resulting in decreases in CO conversion rates and detrimental increases in light product selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Biolabeling with nanoparticles based on Y(2)O(3):Nd(3+) and luminescence detection in the near-infrared

Neodymium based fluorescence presents several advantages in comparison to conventional rare earth or enzyme-substrate based fluorescence emitting sources (e.g.Tb, HRP). Based on this fact we have herein explored a Nd-based fluoroimmunoassay. We efficiently detected the presence of an oxidized low-density lipoprotein (oxLDL) in human plasma a well-known marker for cardiovascular diseases, which causes around 30% of deaths worldwide. Conventional fluoroimmunoassay uses time-resolved luminescence techniques, with detection in the visible range, to eliminate the fluorescence background from the biological specimens. By using an immunoassay based on functionalized Y(2)O(3):Nd(3+) nanoparticles, where the excitation and emission processes in the Nd(3+) ion occur in the near-infrared (NIR) region, we have succeeded in eliminating the interferences from the biological fluorescence background, avoiding the use of time-resolved techniques. This yields higher emission intensity from the Nd(3+)-nanolabels and efficient detection of anti-oxidized low-density lipoproteins (anti-oxLDL) by Y(2)O(3):Nd(3+)-antibody-antigen conjugation, leading to a novel biolabeling method. (C) 2010 Elsevier B.V. All rights reserved.

Development of secondary palate requires strict regulation of ECM remodeling: sequential distribution of RECK, MMP-2, MMP-3, and MMP-9

We have evaluated RECK (reversion-inducing-cysteine-rich protein with Kazal motifs), MMP-2 (matrix metalloproteinase-2), MMP-3, and MMP-9 involvement during palate development in mice by using various techniques. Immunohistochemical features revealed the distribution of RECK, MMP-2, and MMP-3 in the mesenchymal tissue and in the midline epithelial seam at embryonic day 13 (E13), MMPs-2, -3, and -9 being particularly expressed at E14 and E14.5. In contrast, RECK was weakly immunostained at these times. Involvement of MMPs was validated by measuring not only their protein expression, but also their activity (zymograms). In situ hybridization signal (ISH) for RECK transcript was distributed in mesenchymal and epithelial regions within palatal shelves at all periods evaluated. Importantly, the results from ISH analysis were in accord with those obtained by real-time polymerase chain reaction. The expression of RECK was found to be temporally regulated, which suggested possible roles in palatal ontogeny. Taken together, our results clearly show that remodeling of the extracellular matrix is finely modulated during secondary palate development and occurs in a sequential manner.

Production of hydrogen via steam reforming of biofuels on Ni/CeO(2)-Al(2)O(3) catalysts promoted by noble metals

The catalytic activity of Ni/CeO(2)-Al(2)O(3) catalysts modified with noble metals (Pt, Ir, Pd and Ru) was investigated for the steam reform of ethanol and glycerol. The catalysts were characterized by the following techniques: Energy-dispersive X-ray, BET, X-ray diffraction, temperature-programmed reduction, UV-vis diffuse reflectance spectroscopy and X-ray absorption near edge structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of CeO(2) dispersed on alumina. The promoting effect of noble metals included a decrease in the reduction temperatures of NiO species interacting with the support, due to the hydrogen spillover effect. It was seen that the addition of noble metal stabilized the Ni sites in the reduced state along the reforming reaction, increasing the ethanol and glycerol conversions and decreasing the coke formation. The higher catalytic performance for the ethanol steam reforming at 600 degrees C and glycerol steam reforming was obtained for the NiPd and NiPt catalysts, respectively, which presented an effluent gaseous mixture with the highest H(2) yield with reasonably low amounts of CO. (c) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Effect of the Y(2)O(3)-ZrO(2) support composition on nickel catalyst evaluated in dry reforming of methane

Nickel catalysts with a load of 5 wt.% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4 mol%, 8 mol% and 12 mol% of Y(2)O(3), were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and electronic paramagnetic resonance (EPR) and tested as catalysts for carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of a Y(2)O(3)-ZrO(2) solid solution. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the composition of the support. Catalytic tests were conducted at 800 degrees C for 6 h, and the composition of the gaseous products and the catalytic conversion rate depended on the composition of the Y(2)O(3)-ZrO(2) solid solution and its influence on the supported NiO species. A direct relation was observed between the variation in the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2008 Elsevier B.V. All rights reserved.

Co catalysts supported on SiO(2) and gamma-Al(2)O(3) applied to ethanol steam reforming: Effect of the solvent used in the catalyst preparation method

Cobalt catalysts were prepared on supports of SiO(2) and gamma-Al(2)O(3) by the impregnation method, using a solution of Co precursor in methanol. The samples were characterized by XRD, TPR, and Raman spectroscopy and tested in ethanol steam reforming. According to the XRD results, impregnation with the methanolic solution led to smaller metal crystallites than with aqueous solution, on the SiO(2) support. On gamma-Al(2)O(3), all the samples exhibited small crystallites, with either solvent, due to a higher Co-support interaction that inhibits the reduction of Co species. The TPR results were consistent with XRD results and the samples supported on gamma-Al(2)O(3) showed a lower degree of reduction. In the steam reforming of ethanol, catalysts supported on SiO(2) and prepared with the methanolic solution showed the best H(2), CO(2) and CO selectivity. Those supported on gamma-Al(2)O(3) showed lower H(2) selectivity. (C) 2011 Elsevier Ltd. All rights reserved.