Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelandia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO(3), 100 mg of sample), and that for the Niquelandia samples also by Parr bomb treatment (5 days at 200 degrees C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelandia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.

Optical properties of red, green and blue emitting rare earth benzenetricarboxylate compounds

Red, blue and green emitting rare earth compounds (RE(3+) = Eu(3+), Gd(3+) and Tb(3+)) containing the benzenetricarboxylate ligands (BTC) [hemimellitic (EMA), trimellitic (TLA) and trimesic (TMA)] were synthesized and characterized by elemental analysis, complexometric titration, X-ray diffraction patterns, thermogravimetric analysis and infrared spectroscopy. The complexes presented the following formula: [RE(EMA)(H(2)O)(2)], [RE(TLA)(H(2)O)(4)] and [RE(TMA)(H(2)O)(G)], except for Tb-TMA compound, which was obtained only as anhydrous. Phosphorescence data of Gd(3+)-(BTC) complexes showed that the triplet states (T) of the BTC(3-) anions have energy higher than the main emitting states of the Eu(3+) ((5)D(0)) and Tb(3+) ((5)D(4)), indicating that BTC ligands can act as intramolecular energy donors for these metal ions. The high values of experimental intensity parameters (Omega(2)) of Eu(3+)-(BTC) complexes indicate that the europium ion is in a highly polarizable chemical environment. Based on the luminescence spectra, the energy transfer from the T state of BTC ligands to the excited (5)D(0) and (5)D(4) levels of the Eu(3+) and Tb(3+) ions is discussed. The emission quantum efficiencies (eta) of the (5)D(0) emitting level of the Eu(3+) ion have been also determined. In the case of the Tb(3+) ion, the photoluminescence data show the high emission intensity of the characteristic transitions (5)D(4) -> (7)F(J) (J=0-6), indicating that the BTC ligands are good sensitizers. The RE(3+)-(BTC) complexes act as efficient light conversion molecular devices (LCMDs) and can be used as tricolor luminescent materials. (C) 2009 Elsevier B.V. All rights reserved.

Electroluminescent devices based on rare-earth tetrakis beta-diketonate complexes

In this paper the synthesis, photo luminescence and electroluminescence investigation of the novel tetrakis beta-diketonate of rare-earth complexes such as M[Eu(dbM)(4)] and M[Tb(acac)(4)] with a variety of cationic ligands, M=Li(+), Na(+) and K(+) have been investigated. The emission spectra of the Eu(3+) and Tb(3+) complexes displayed characteristic narrow bands arising from intraconfigurational transitions of trivalent rare-earth ions and exhibited red color emission for the Eu(3+) ion ((5)D(0) -> F(J), J=0-6) and green for the Tb(3+) ion ((5)D(4) -> (7)F(J), J = 6-0). The lack of the broaden emission bands arising from the ligands suggests the efficient intramolecular energy transfer from the dbm and acac ligands to Eu(3+) and Tb(3+) ions, respectively. In accordance to the expected, the values of PL quantum efficiency (eta) of the emitting (5)D(0) state of the tetrakis(beta-diketonate) complexes of Eu(3+) were higher compared with those tris-complexes. Therefore, organic electroluminescent (EL) devices were fabricated with the structure as follows: indium tin oxide (ITO)/hole transport layer (HTL) NPB or MTCD/emitter layer M[RE(beta-diketonate)(4)] complexes)/Aluminum (Al). All the films were deposited by thermal evaporation carried out in a high vacuum environment system. The OLED light emission was independent of driving voltage, indicating that the combination of charge carriers generates excitons within the M[RE(beta-diketonate)(4)] layers, and the energy is efficiently transferred to RE(3+) ion. As a best result, a pure red and green electroluminescent emission was observed from the Eu(3+) and Tb(3+) devices, confirmed by (X,Y) color coordinates. (C) 2008 Elsevier B.V. All rights reserved.

Stochastic discount factor bounds and rare events: a review

We aim to provide a review of the stochastic discount factor bounds usually applied to diagnose asset pricing models. In particular, we mainly discuss the bounds used to analyze the disaster model of Barro (2006). Our attention is focused in this disaster model since the stochastic discount factor bounds that are applied to study the performance of disaster models usually consider the approach of Barro (2006). We first present the entropy bounds that provide a diagnosis of the analyzed disaster model which are the methods of Almeida and Garcia (2012, 2016); Ghosh et al. (2016). Then, we discuss how their results according to the disaster model are related to each other and also present the findings of other methodologies that are similar to these bounds but provide different evidence about the performance of the framework developed by Barro (2006).

Oral foreign body granuloma: unusual presentation of a rare adverse reaction to permanent injectable cosmetic filler

COSTA MIGUEL, M. C.; NONAKA, C. F. W.; GERMANO, A. R.; SOUZA, L. B.; SOUZA, L. B. Oral foreign body granuloma: unusual presentation of a rare adverse reaction to permanent injectable cosmetic filler. International journal of oral and maxillofacial surgery, v. 38, p. 385-387, 2009.

Nuclear-follower foraging associations among Characiformes fishes and Potamotrygonidae rays in clean waters environments of Teles Pires and Xingu rivers basins, Midwest Brazil

Por meio de observações sub e supra-aquáticas foram registradas associações alimentares do tipo nuclear-seguidor entre três espécies de peixes characiformes - Chalceus epakros, Hemiodus semitaeniatus e Hemiodus unimaculatus - e uma espécie de raia de água doce - Potamotrygon orbignyi - nas bacias dos rios Teles Pires e Xingu, no Centro-Oeste do Brasil. Os peixes teleósteos foram observados seguindo as raias quando estas revolviam o substrato à procura de invertebrados, formando discretas nuvens de sedimento. Essas situações atraíram os peixes que se aproximaram das raias para se alimentar de pequenas presas e outros tipos de alimentos expostos desta forma. Esse é um típico exemplo de relação comensal onde um participante é beneficiado enquanto o outro não é prejudicado e representa o segundo registro na literatura de associação alimentar do tipo nuclear-seguidor entre raias potamotrigonídeas e peixes teleósteos, demonstrando o potencial de estudos naturalísticos para a descoberta de novas interações envolvendo espécies de peixes de água doce.

Processos carioevolutivos na ordem tetraodontiformes: uma visão através de suas diferentes linhagens

Given the great diversity of fishes, the Order Tetraodontiformes stands to show genetic and morphological characteristics enough singular. The fishes of this order have a compact DNA which favors molecular studies, as well as comparisons with more basal species. Model of genome evolution, there are still many gaps in knowledge about their chromosomal patterns and how evolutionary rearrangements influence the marked variation in DNA content of this order. In view of this, we present cytogenetic analyzes of the species Acanthostracion quadricornis (Ostraciidae), A. polygonius (Ostraciidae) Melichthys niger (Balistidae) Cantherhines macrocerus (Monacanthidae) and C. pullus (Monacanthidae), Lagocephalus laevigatus, Colomesus psittacus and Canthigaster figueiredoi (Tetraodontidae), to contribute with cytogenetic data for this group. The analysis was performed by C-banding, Ag-RONs, coloring with base-specific fluorochromes DAPI-CMA3, restriction enzymes AluI, EcoRI, TaqI, PstI and HinfI and in situ hybridization with probes for ribosomal DNA 18S and 5S. The heterochromatic ultrastructure of A. quadricornis and A. polygonius revealed a outstanding heterochromatin content, which may indicate that the accumulation or loss of extensive heterochromatin content could be responsible for large variations in genomic content displayed in different Tetraodontiformes families. The species Cantherhines macrocerus, C. pullus (Monacanthidae) and Melichthys niger (Balistidae) shows a huge karyotypic similarity both numerically and structural. L. laevigatus showed similar cytogenetic features (2n = 44 and single RONs) to the species of the genus Takifugu, which reinforces the idea of their phylogenetic relationships. C. psittacus presented the highest diploid number described for the family (2n = 56) and large amount of HC, features that related with its sister family Diodontidae. Cytogenetic analysis in C. figueiredoi revealed heterochromatic polymorphisms, RONs multiple and Bs chromosomes. These events are rare in marine fishes, and are possibly associated with the strong restructuring and genomic reduction that this family has been suffered. These features, plus the morphological and molecular data suggests that these species share the same ancestral branch, with a possible monophyletic origin. In this study, new contributions to the knowledge of evolutionary patterns facing by Tetraodontiformes are provided and discussed under cytotaxonomyc, genomic and evolutionary perspectives.

Comparative evaluation of the susceptibility of cultivated fishes to the natural infection with myxosporean parasites and tissue changes in the host

O objetivo deste estudo foi avaliar a susceptibilidade de 4 importantes peixes cultivados a parasitos esporozoários. Os peixes foram coletados bimestralmente de um tanque de cultivo, durante 1 ano. Myxobolus colossomatis e Henneguya piaractus foram encontrados nos órgãos internos e brânquias, respectivamente. A incidência de ambos os parasitos foi de 97,3% em pacu (Piaractus mesopotamicus), 33,3% no híbrido tambacu (Piaractus mesopotamicus x Colossoma macropomum), 5,6% em tambaqui (Colossoma macropomum) e 0% em carpa (Cyprinus carpio). Pacu foi o peixe mais susceptível, encontrando-se parasitado 79,2% nas brânquias, 66,7% nos rins e 50% no baço. A análise histopatológica das brânquias mostrou hemorragias, reação inflamatória com células mononucleares, fibroblastos e hiperplasia das células basais e mucosas.

Association of ABO gene mutations resulting in a rare B subgroup

Background and Objectives B subgroups are rare and the genetic analysis reported to date has been limited.Materials and Methods Serological and molecular investigations were performed in blood from a B-subgroup donor.Results Red cells did not react with anti-B and anti-AB reagents. However, cells absorbed anti-B. Red cells presented positive reactions with anti-H, and saliva secreted H substance. The molecular study demonstrated a B allele with the substitutions 467C>T, 646T>A, 681G>A, 771C>T, 796C>A, 803G>C, 829G>A and an 0 allele with the sequence of 002.Conclusions It is probable that the presence in exon 7 of some of the 002 substitutions could have weakened the enzymatic activity of the encoded B transferase.

Rare earth centers properties and electron trapping in SnO2 thin films produced by sol-gel route

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dielectric response features and oxygen migration on rare earth modified lead titanate ferroelectric ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)