Diplomatic Spin: EU3+3 talks on Iran���s nuclear file. CEPS Commentary, 21 November 2014

The Joint Plan of Action agreed upon with Iran on 24 November 2013 gave negotiators one year to forge a comprehensive agreement that restricts the country���s ability to militarise its nuclear programme. That deadline will lapse in the next few days and diplomats involved in the talks have been trying to rein in expectations that a deal will be struck on time. Satisfying domestic constituencies in Iran and the US is what makes the politics of dealing with the nuclear file so much harder than the physics of slowing down the nuclear programme. Any future deal will have to stand on its own merits, enabling Iran and the EU3+3 to cooperate on the other geopolitical challenges they face. Both parties should therefore balance their demands with what they can realistically offer and make concessions to reach a compromise. The author of this CEPS Commentary argues that if no deal is reached on November 24th, then diplomacy should be allowed to keep on spinning for a few more months.

Poli-l��quidos i��nicos e complexos sol��veis de Eu3+ e Tb3+ : bioimageamento celular seletivo

Disserta����o (mestrado)���Universidade de Bras��lia, Instituto de Qu��mica, Programa de P��s-Gradua����o em Qu��mica, 2015.

X-ray photoelectron spectroscopy of superconducting RuSr2Eu1.5Ce0.5Cu2O10 and nonsuperconducting RuSr2EuCeCu2O10

We report x-ray photoelectron spectroscopic investigation of RuSr2Eu1.5Ce0.5Cu2O10 with ferromagnetic T-C similar to 100 K and a superconducting transition temperature of similar to 30 K compared with RuSr2EuCeCu2O10, which is a ferromagnetic (T-C similar to 150 K) insulator. Our results show that the rare earths, Eu and Ce, are in 3+ and 4+ states, respectively. Comparing the Ru core level spectra from these compounds to those from two Ru reference oxides, we also show that Ru in these ruthenocuprates is always in 5+ state, suggesting that the doped holes in the superconducting compound arising from the substitution of Ce4+ by Eu3+ are primarily in the Cu-O plane, in close analogy to all other doped high-T-C cuprates. Analysis of Cu 2p spectra in terms of a configuration interaction model provides a quantitative description of the gross electronic structures of these ruthenocuprates.

Lanthanide Luminescent Coordination Polymer Constructed from Unsymmetrical Dinuclear Building Blocks Based on 4-((1H-Benzod]imidazol-1-yl)methyl)benzoic Acid

Lanthanide coordination polymers of the general formula Ln(2)(L)(5)(NO3)(H2O)(4)](n) (Ln = Eu (1), Tb (2), Gd (3)) supported by a novel aromatic carboxylate ligand 4-((1H-benzod]imidazol-1-yl)methyl)benzoic acid (HL) have been synthesized, characterized, and their photoluminescence behavior is examined. The powder X-ray diffraction patterns of complexes 1-3 showed that 1-3 are isostructural; thus, 1 has been chosen as an example to discuss in detail about the molecular structure by single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1D) helical chain-like coordination polymer consisting of unique unsymmetrical dinuclear lanthanide building blocks. The 1D chains are further linked by the significant intermolecular hydrogen-bonding interactions to form a two-dimensional supramolecular network. The Tb3+ complex exhibits bright green luminescence efficiency in the solid state with a quantum yield of 15%. On the other hand, poor luminescence efficiency has been noted for Eu3+-benzoate complex.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40<x<75) by the addition of ammonium carbonate. During calcination, CeO2.xH(2)O dehydroxylation is followed by the reaction with SrCO3 to form Sr2CeO4 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Combustion synthesis approach for spectral tuning of Eu doped CaAl2O4 phosphors

Despite being a particularly good emitter, use of divalent Eu has been seriously limited. This is because severe reducing environments or special hosts are needed during synthesis of divalent Eu containing phosphors. In this work we stabilize Eu in its 2+ state (in CaAl2O4) using an open-air solution combustion reaction. The impact of fuel (F) to oxidizer (O) molar ratios (F/O = 0.5-2.0) on luminescence properties is explored. Chromaticity of Eu:CaAl2O4 depends sensitively on the F/O ratio. In general, higher F/O inhibits Eu3+ and promotes Eu2+ formation, which in turn improves the quality of the blue phosphor. EPR spectra show inhomogeneous broadening effects with the increase in F/O ratio, which suggests that disorder creation is promoted when F/O is increase. This is also confirmed by an increase in emission line width in PL spectra, when F/O is increased. (C) 2013 Elsevier B.V. All rights reserved.

Novel spherical hierarchical structures of GdOOH and Eu:GdOOH: rapid microwave-assisted synthesis through self-assembly, thermal conversion to oxides, and optical studies

We report a novel, rapid, and low-temperature method for the synthesis of undoped and Eu-doped GdOOH spherical hierarchical structures, without using any structure-directing agents, through the microwave irradiation route. The as-prepared product consists of nearly monodisperse microspheres measuring about 1.3 mu m in diameter. Electron microscopy reveals that each microsphere is an assembly of two-dimensional nanoflakes (about 30 nm thin) which, in turn, result from the assembly of crystallites measuring about 9 nm in diameter. Thus, a three-level hierarchy can be seen in the formation of the GdOOH microspheres: from nanoparticles to 2D nanoflakes to 3D spherical structures. When doped with Eu3+ ions, the GdOOH microspheres show a strong red emission, making them promising candidates as phosphors. Finally, thermal conversion at modest temperatures leads to the formation of corresponding oxide structures with enhanced luminescence, while retaining the spherical morphology of their oxyhydroxide precursor.

Gd1.96-xYxEu0.04O3 (x=0.0, 0.49, 0.98, 1.47, 1.96 mol%) nanophosphors: Propellant combustion synthesis, structural and luminescence studies

Gd1.96-xYxEu0.04O3 (x = 0.0, 0.49, 0.98, 1.47, 1.96 mol%) nanophosphors were synthesized by propellant combustion method at low temperature (400 degrees C). The powder X-ray diffraction patterns of as formed Gd1.96Eu0.04O3 showed monoclinic phase, however with the addition of yttria it transforms from monoclinic to pure cubic phase. The porous nature increases with increase of yttria content. The particle size was estimated from Scherrer's and W-H plots which was found to be in the range 30-40 nm. These results were in well agreement with transmission electron microscopy studies. The optical band gap energies estimated were found to be in the range 5.32-5.49 eV. PL emission was recorded under 305 nm excitation show an intense emission peak at 611 nm along with other emission peaks at 582, 641 nm. These emission peaks were attributed to the transition of D-5(0) ���> F-7(J) (J = 0, 1, 2, 3) of Eu3+ ions. It was observed that PL intensity increases with increase of Y content up to x = 0.98 and thereafter intensity decreases. CIE color co-ordinates indicates that at x = 1.47 an intense red bright color can be achieved, which could find a promising application in flat panel displays. The cubic and monoclinic phases show different thermoluminescence glow peak values measured under identical conditions. The response of the cubic phase to the applied dose showed good linearity, negligible fading, and simple glow curve structure than monoclinic phase indicating that suitability of this phosphor in dosimetric applications. (C) 2014 Elsevier B.V. All rights reserved.

Luminescence studies and EPR investigation of derived Eu doped ZnO

ZnO:Eu (0.1 mol%) nanopowders have been synthesized by auto ignition based low temperature solution combustion method. Powder X-ray diffraction (PXRD) patterns confirm the nanosized particles which exhibit hexagonal wurtzite structure. The crystallite size estimated from Scherrer's formula was found to be in the range 35-39 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal particles are agglomerated with quasi-hexagonal morphology. A blue shift of absorption edge with increase in band gap is observed for Eu doped ZnO samples. Upon 254 nm excitation, ZnO:Eu nanopowders show peaks in regions blue (420-484 nm), green (528 nm) and red (600 nm) which corresponds to both Eu2+ and Eu3+ ions. The electron paramagnetic resonance (EPR) spectrum exhibits a broad resonance signal at g= 4.195 which is attributed to Eu2+ ions. Further, EPR and thermo-luminescence (TL) studies reveal presence of native defects in this phosphor. Using TL glow peaks the trap parameters have been evaluated and discussed. (C) 2014 Elsevier B.V. All rights reserved.

Rapid, microwave-assisted synthesis of Gd2O3 and Eu:Gd2O3 nanocrystals: characterization, magnetic, optical and biological studies

Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.

Tuning Photoluminescence Response by Electric Field in Electrically Soft Ferroelectrics

We show that an electrically soft ferroelectric host can be used to tune the photoluminescence (PL) response of rare-earth emitter ions by external electric field. The proof of this concept is demonstrated by changing the PL response of the Eu3+ ion by electric field on a model system Eu-doped 0.94(Na1/2Bi1/2TiO3)-0.06(BaTiO3). We also show that new channels of radiative transitions, forbidden otherwise, open up due to positional disorder in the system, which can as well be tuned by electric field.

Micromodification of element distribution in glass using femtosecond laser irradiation

We report micromodification of Eu element distribution in a silicate glass with femtosecond laser irradiation. Elemental analysis shows that the content of Eu decreased at the focal point and increased in a ring-shaped region around the focal point, which indicates migration of Eu ions has been induced by the femtosecond laser irradiation. Confocal fluorescence spectra demonstrate that the fluorescence intensity of Eu3+ ions increased by 20% in the laser-induced, Eu-enriched, ring-shaped region compared with that for nonirradiated glass. The mechanism for the laser induced change in fluorescence properties of Eu3+ has been investigated. (C) 2009 Optical Society of America

Tuning the Eu luminescence in glass materials synthesized in air by adjusting glass compositions

The doped Eu3+ ions can be partly reduced to Eu2+ in a series of MO-B2O3: Eu (M=Ba, Sr, Ca) glasses synthesized in air atmosphere, but not in the 12CaO-7Al(2)O(3): Eu glass. The different redox-behavior of Eu ions in these two glass systems is attributed to the different host optical basicity. It is found that a lower valence state of Eu2+ is more favorable in acidic glasses, which have lower optical basicities. A notion of the critical value of optical basicity is introduced empirically, which can be used as a guide for the selection of glass composition suitable to incorporate Eu2+ for luminescence. (C) 2006 Elsevier B.V. All rights reserved.

Investigations on valence-change behaviors of europium ions in Eu-doped aluminate and silicate phosphors

Compounds of Sr3Al2O6: Eu, Sr4Al14O25: Eu, and BaZnSiO4: Eu were synthesized by high-temperature solid state reactions. The doping Eu3+ ions were partially reduced to Eu2+ in Sr4Al14O25: Eu and BaZnSiO4: Eu prepared in an oxidizing atmosphere, N-2 + O-2. However, such an abnormal reduction process could not be performed in Sr3Al2O6: Eu, which was also prepared in an atmosphere of N-2 + O-2. Moreover, even though Sr3Al2O6: Eu was synthesized in a reducing condition CO, only part of the Eu3+ ions was reduced to Eu2+. The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu3+ to Eu2+.

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