New phosphinate ligand synthesis and its effect on optical properties of the europium beta-diketonate complex

The synthesis and characterization of a new organic ligand monooctyldiphenylphosphinate (L) is described, as well as a new Eu(3+) diketonate complex [Eu(tta)(3)(L)(2)] (tta = thenoyltrifluoracetone). The ligand (L) was formed by substitution reaction (80% yield) and characterized by uni- and bidimensional (1)H, (13)C and (31)P NMR experiments, to confirm its molecular structure. The coordination of (L) to Eu(3+) in the complex [Eu(tta)(3)(L)(2)] was confirmed by FT-IR spectra. The emission spectra present the same profile when excited in Eu(3+) or in the ligands, suggesting an energy transfer from ligands to Eu(3+) ions. The emission spectra of the precursor [Eu(tta)(3)(H(2)O)(2)], and [Eu(tta)(3)(L(2))] present bands arising from f-f intra-configurational transitions. The only (5)D(0)-(7)F(0) transition shows the presence of at least one site without symmetry center. The FWHM of such transition is 7 cm(-1) and 57 cm(-1) for [Eu(tta)(3)(H(2)O)(2)] and [Eu(tta)(3)(L)(2)] complexes, respectively. This widening is provided by the presence of large groups around Eu(3+) ion. The calculated intensity parameters Omega(2) and Omega(4) show that the interaction features between center-ion and ligand are different; the small value of Omega(4) is related to long range effects of alkyl chain. The Langmuir isotherms of this ligand and complex have been investigated although their hydrolysis in water subphase does not allow stable monolayers. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Catálise estereoespecífica de estireno por titanocenos alquil-substituídos do tipo (RCp)2TiCl2

Uma série de sete complexos alquil substituídos do tipo (RCp)2TiCl2 (R= H, etila, n-propila, iso-propila, n-butila, iso-amila, ciclo-hexila) foi preparada juntamente com o ainda inédito contendo R= sec-butila, e o efeito do substituinte na polimerização do estireno foi investigada à temperaturas de polimerização de 0 e 50 ºC. Foi encontrado que R = n-butila maximiza a produção de poliestireno sindiotático. Ligantes alquilas com R = RCH2- são superiores aos R = RR CH- e ao precursor Cp2TiCl2 na produção de poliestireno sindiotático de alto peso molecular.

Influência da energia de soldagem em uniões de lâminas finas através de laser pulsado de Nd:YAG

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Obtenção in situ do compósito alfa-SiAlON-SiC

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

Photoluminescence in ZrO2 doped with Y and La

O objetivo deste trabalho é descrever a síntese e a caracterização óptica de uma solução sólida de óxido de zircônio contendo ítrio e lantânio. Foram misturados citrato de zircônio, nitrato de ítrio e nitrato de lantânio nas proporções 94 mol% ZrO2-6 mol% Y2O3 e 92 mol% ZrO2-6 mol % Y2O3-2 mol % La2O3. A análise de espectroscopia de absorção no infravermelho com tranformada de Fourier mostra material orgânico em decomposição e a análise térmica mostra a transformação de fases da zircônia tetragonal para monoclínica, a perda de água e a desidroxilação do zircônio. A análise por difração de raios X mostra formação de fases homogênea de ZrO2-Y2O3-La2O3 demonstrando que a adição de lantânio não provoca formação de fases, promovendo uma solução sólida baseada em zircônia cúbica. Os espectros de fotoluminescência mostram bandas de absorção em 562 nm e 572 nm (350 ºC) e bandas de absorção específicas em 543 nm, 561 nm, 614 nm e 641 nm (900 ºC). O efeito fotoluminescente a baixas temperaturas é causado por defeitos como (Y Zr,Y O)', (2Y Zr,V O)'' e V O. As emissões em 614 nm e 641 nm são causadas pela transição O-2p -> Zr-4d. Uma emissão em 543 nm pode ser atribuída a centros LaO8 com transição O-2p -> La-5d.

Luminescent properties of some rare earth phosphates

Luminescent properties of scandium and yttrium phosphates are discussed and mechanisms involving their emissions proposed.

Pulpal temperature increases with Er : YAG laser and high-speed handpieces

Statement of problem. During tooth preparation, both high-speed handpieces and lasers generate heat, which, if not controlled, can cause pulpal necrosis.Purpose. The aim of this study was to compare temperature increases produced by a high-speed dental handpiece with those produced by a relatively new instrument, the Er:YAG (erbium: yttrium-aluminum-garnet) laser.Material and methods. Thirty bovine mandibular incisors were reduced to an enamel/dentin thickness of 2.5 mm. Class V preparations were completed to a depth of 2.0 mm, measured with a caliper or by a mark oil the burs. A thermocouple was placed inside the pulp chamber to determine temperature increases (degreesC). Analysis was performed on the following groups (n = 10): Group 1, high-speed handpiece without water cooling, Group 11, high-speed handpiece with water cooling (30 mL/min), and Group III, the noncontact Er:YAG laser (2.94 mum at 350 mJ/10 Hz) with water cooling (4.5 mL/min). The temperature increases were recorded by a computer linked to the thermocouples. The data were analyzed using the Kruskal-Wallis test. The Dunn multiple comparison test was used as post hoc test (alpha = .05).Results. The average temperature rises were: 11.64degreesC (+/-4.35) for Group 1, 0.96degreesC (+/-0.71) for Group 11, and 2.69degreesC (+/-1.12) for Group III. There were no statistical differences between Groups 11 and III, both 11 and III differed from Group I significantly (P = .000 and P = .002, respectively).Conclusion. The preparations made with the high-speed and the laser instrument generated similar heat increases under water cooling. Water cooling was essential to avoid destructive temperature increases when using both the high-speed handpiece and laser.

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.

Phosphate functionalization of spongiolite surface

Spongiolite from Mato Grosso do Sul (Brazil), natural inorganic composite constituted of silica needles, was treated with concentrated phosphoric acid at high temperatures. Superficial coating of the needles was proved to be constituted of silicon diphosphate, a compound offering six-coordinated silicon sites. Owing to the affinity of three charged ions to phosphate groups, this coating acts as specific adsorbent for the rare earth elements which prefer octahedral coordination (starting from samarium, yttrium included). The uptake of lanthanum and neodymium are significantly lower due to different coordination tendencies. Lanthanide fixation upon silica with PO4 groups anchored on its surface may be useful in the manufacturing of special phosphate-silicate glasses. (C) 2003 Elsevier B.V. All rights reserved.

NEAR-RESONANT SCATTERING FROM NONSYMMETRIC DIMERS - APPLICATIONS TO SUBSTITUTED POLYANILINES

In this work we show that, beyond the prediction of the random dimer model [Wu and Phillips, Phys. Rev. Lett. 66, 1366 (1991)], it is possible to have near resonant scattering from nonsymmetric dimers. It is shown by direct density of states calculations as well as by a procedure similar to the random dimer model that protonated chains of alkyl-substituted polyanilines support extended electronic states at the Fermi energy when a disordered distribution of symmetric or asymmetric bipolarons is present. An extension of the random dimer model to include resonant scattering by nonsymmetric dimers is proposed.

Estudo comparativo entre alguns benzalpiruvatos-fenil substituído de lantanídeos e ítrio no estado sólido.

In the present work, the thermal decomposition step of some lanthanides and yttrium compounds involving different ligand phenyl-substituted derivatives of benzylidenepyruvate was appraised by thermogravimetry (TG). A correlation about the metal ions content was made by comparison of the results obtained by TG and EDTA complexometry.

A comparative analysis of the chemical nature of defensive secretions of Gonyleptidae (Arachnida : Opiliones : Laniatores)

The arachnids of the order Opiliones (harvestmen) produce substances used in defense. In the present paper, we analyzed 22 species of Gonyleptidae to explore the use of defensive substances in taxonomy and evolutionary biology. Thirty-seven different compounds were detected, 18 of which were preliminarily identified. These compounds were mapped onto a phylogenetic tree showing the relationships within the Gonyleptidae. Data from Cosmetidae were used as an outgroup. Five ketones and six alkyl phenols were reported for the first time in harvestmen. (c) 2005 Elsevier Ltd. All rights reserved.

Carboxylic acids of marine evaporitic oils from Sergipe-Alagoas Basin, Brazil

A. suite of 10 different marine evaporitic oil samples from Sergipe-Alagoas Basin, Brazil was studied for its biomarker content, in particular its acidic constituents. The oils showed different molecular distributions and relative abundances of n-alkanoic, isoprenoid and hopanoic acids. The observed differences were assigned to the incorporation of immature organic matter in the oils and fractionation along the migration pathway. The diagenetic precursor functionality (alcohol/ether or acid) was proposed based on the comparison of the relative abundances of the neutral and acidic biomarkers (hopanoids, isoprenoids, alkyl-steranes, monoaromatic alkyl-steroids). In the acidic fraction, 3 series of steroid-alkanoic acids and monoaromatic steroid-alkanoic acids (steroid-methanoic, ethanoic and propanoic acids and monoaromatic steroid-methanoic, ethanoic and propanoic acids) were detected, while in the neutral fraction only 2 series of each corresponding class could be observed (methyl and ethyl-steranes and monoaromatic methyl and ethyl-steroids). These carbon shifts suggest that decarboxylation is an important process in the formation of the alkyrsteranes and monoaromatic alkyl-steroids, and we infer that carboxylic acids are the diagenetic precursors of these classes of compounds. When alcohol or ether are the diagenetic precursors (isoprenoids and hopanoids), no significant differences in the molecular distributions between neutral and acidic fractions were observed. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

alpha-SiAlON ceramics with elongated grain morphology using an alternative sintering additive

In this work, the use of a natural yttrium oxide and rare earth oxide solid solution (CRE2O3) as stabilizers of the alpha-Si3N4 phase to form alpha-SiAlON has been investigated. This oxide mix is produced at FAENQUIL-DEMAR, at a cost of only 20% of pure commercial Y2O3. Two alpha-SiAlONs using pure Y2O3 or CRE2O3 have been prepared, using mixes of 20% by volume of a molar fraction of 9:1 of AlN to Y2O3 or AlN to CRE2O3, respectively, with 80% alpha-Si3N4. Samples were gas pressure-sintered at 1900 degreesC, under 1.5 MPa of N-2 for 60 min. Both compositions yielded alpha-SiAlON ceramics with high relative densities (98% t.d.), hardness of 18 GPa and fracture toughness of 5 Mpa m(1/2), with homogeneous microstructures composed of elongated alpha-SiAlON grains with aspect ratios of 5. It is concluded that the mixed rare earth concentrate (CRE2O3) can be used to produce alpha-SiAlON ceramics with similar microstructures and mechanical properties of alpha-SiAlON ceramics fabricated using pure Y2O3, but with the advantage of its lower production cost. (C) 2004 Elsevier B.V All rights reserved.

Ceramic Primer Heat-Treatment Effect on Resin Cement/Y-TZP Bond Strength

The purpose of this study was to evaluate the effect of different heat-treatment strategies for a ceramic primer on the shear bond strength of a 10-methacryloyloxydecyl-dihydrogen-phosphate (MDP)-based resin cement to a yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic. Specimens measuring 4.5 x 3.5 x 4.5 mm(3) were produced from Y-TZP presintered cubes and embedded in polymethyl methacrylate (PMMA). Following finishing, the specimens were cleaned using an ultrasound device and distilled water and randomly divided into 10 experimental groups (n=14) according to the heat treatment of the ceramic primer and aging condition. The strategies used for the experimental groups were: GC (control), without primer; G20, primer application at ambient temperature (20 degrees C); G45, primer application + heat treatment at 45 degrees C; G79, primer application + heat treatment at 79 degrees C; and G100, primer application + heat treatment at 100 degrees C. The specimens from the aging groups were submitted to thermal cycling (6000 cycles, 5 degrees C/55 degrees C, 30 seconds per bath) after 24 hours. A cylinder of MDP-based resin cement (2.4 mm in diameter) was constructed on the ceramic surface of the specimens of each experimental group and stored for 24 hours at 37 degrees C. The specimens were submitted to a shear bond strength test (n=14). Thermal gravimetric analysis was performed on the ceramic primer. The data obtained were statistically analyzed by two-way analysis of variance and the Tukey test (alpha=0.05). The experimental group G79 without aging (7.23 +/- 2.87 MPa) presented a significantly higher mean than the other experimental groups without aging (GC: 2.81 +/- 1.5 MPa; G20: 3.38 +/- 2.21 MPa; G100: 3.96 +/- 1.57 MPa), showing no difference from G45 only (G45: 6 +/- 3.63 MPa). All specimens of the aging groups debonded during thermocycling and were considered to present zero bond strength for the statistical analyses. In conclusion, heat treatment of the metal/zirconia primer improved bond strength under the initial condition but did not promote stable bonding under the aging condition.