Structural and optical properties on thulium-doped LHPG-grown Ta(2)O(5) fibres

Structural, spectroscopic and dielectric properties of thulium-doped laser-heated pedestal Ta(2)O(5) as-grown fibres were studied. Undoped samples grow preferentially with a single crystalline monoclinic structure. The fibre with the lowest thulium content (0.1 at%) also shows predominantly a monoclinic phase and no intra-4f(12) Tm(3+) recombination was observed. For sample with the highest thulium amount (1.0 at%), the appearance of a dominant triclinic phase as well as intraionic optical activation was observed. The dependence of photoluminescence on excitation energy allows identification of different site locations of Tm(3+) ions in the lattice. The absence of recombination between the first and the ground-state multiplets as well as the temperature dependence of the observed transitions was justified by an efficient energy transfer between the Tm(3+) ions. Microwave dielectric properties were investigated using the small perturbation theory. At a frequency of 5 GHz, the undoped material exhibits a dielectric permittivity of 21 and for thulium-doped Ta(2)O(5) samples it decreases to 18 for the highest doping concentration. Nevertheless, the dielectric losses maintain a very low value. (C) 2008 Elsevier Ltd. 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

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

Broadband NIR Emission in Sol-Gel Er(3+)-Activated SiO(2)-Ta(2)O(5) Glass Ceramic Planar and Channel Waveguides for Optical Application

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

Geometries and electronic properties of Ta-n, TanO and TaOn (n=1-3) clusters

Geometries, vibrational frequencies, electron affinities, ionization potentials and dissociation energies of the title clusters in both neutral and positively and negatively charged states were studied by use of density functional theory. For both neutral and charged species, different initial isomers were studied in order to determine the structure with the lowest energy. Vibrational analysis was also performed in order to characterize these isomers. For Ta-2, Ta-Ta metallic bond is strengthened by adding or removing an electron, i.e. the charged species are much more stable than the neutral counterpart. For Ta-3, equilateral triangle with D-3h symmetry has the lowest energy for both neutral and charged species (near equilateral triangle for cation). TaO and its charged species have much larger dissociation energy compared with other tantalum oxides. For Ta2O and TaO2. structure with C-2v symmetry is much more stable than linear chains. For Ta3O, planar structure with doubly bridging oxygen atoms of C-2v, symmetry is the global minimum for both neutral and charged species. While for TaO3, three-dimensional structures are favored for both neutral (C-1 symmetry) and charged species (C-3v symmetry).

(Tables 1, 2) Permafrost borehole characteristics in the Nordic Area during the IPY 2007-2009

This paper provides a snapshot of the permafrost thermal state in the Nordic area obtained during the International Polar Year (IPY) 2007-2009. Several intensive research campaigns were undertaken within a variety of projects in the Nordic countries to obtain this snapshot. We demonstrate for Scandinavia that both lowland permafrost in palsas and peat plateaus, and large areas of permafrost in the mountains are at temperatures close to 0°C, which makes them sensitive to climatic changes. In Svalbard and northeast Greenland, and also in the highest parts of the mountains in the rest of the Nordic area, the permafrost is somewhat colder, but still only a few degrees below the freezing point. The observations presented from the network of boreholes, more than half of which were established during the IPY, provide an important baseline to assess how future predicted climatic changes may affect the permafrost thermal state in the Nordic area. Time series of active-layer thickness and permafrost temperature conditions in the Nordic area, which are generally only 10 years in length, show generally increasing active-layer depths and rising permafrost temperatures.

Lithium borate-strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications

Glass nanocomposites in the system (100 - x)Li2B4O7-xSrBi(2)Ta(2)O(9) (0 less than or equal to x less than or equal to 22.5, in molar ratio) were fabricated via a melt quenching technique followed by controlled heat-treatment. The as-quenched samples were confirmed to be glassy and amorphous by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) techniques, respectively. The phase formation and crystallite size of the heat-treated samples (glass nanocomposites) were monitored by XRD and transmission electron microscopy (TEM). The relative permittivities (epsilon(tau)') of the glass nanocomposites for different compositions were found to lie in between that of the parent host glass (Li2B4O7) and strontium bismuth tantalate (SBT) ceramic in the frequency range 100 Hz-40 MHz at 300 K, whereas the dielectric loss (D) of the glass nanocomposite was less than that of both the parent phases. Among the various dielectric models employed to predict the effective relative permittivity of the glass nanocomposite, the one obtained using the Maxwell's model was in good agreement with the experimentally observed value. Impedance analysis was employed to rationalize the electrical behavior of the glasses and glass nanocomposites. The pyroelectric response of the glasses and glass nanocomposites was monitored as a function of temperature and the pyroelectric coefficient for glass and glass nanocomposite (x = 20) at 300 K were 27 muC m(-2) K-1 and 53 muC m(-2) K-1, respectively. The ferroelectric behavior of these glass nanocomposites was established by P vs. E hysteresis loop studies. The remnant polarization (P-r) of the glass nanocomposite increases with increase in SBT content. The coercive field (E-c) and P-r for the glass nanocomposite (x = 20) were 727 V cm(-1) and 0.527 muC cm(-2), respectively. The optical transmission properties of these glass nanocomposites were found to be composition dependent. The refractive index (n = 1.722), optical polarizability (am = 1.266 6 10 23 cm 3) and third-order nonlinear optical susceptibility (x(3) = 3.046 6 10(-21) cm(3)) of the glass nanocomposite (x = 15) were larger than those of the as-quenched glass. Second harmonic generation (SHG) was observed in transparent glass nanocomposites and the d(eff) for the glass nanocomposite (x = 20) was found to be 0.373 pm V-1.

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

The reaction of [Cp*TaCl(4)], 1 (Cp* = eta(5)-C(5)Me(5)), with [LiBH(4)center dot THF] at -78 degrees C, followed by thermolysis in the presence of excess [BH(3)center dot THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH} ] 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.

Role of pH controlled DNA secondary structures in the reversible dispersion/precipitation and separation of metallic and semiconducting single-walled carbon nanotubes

Single-stranded DNA (ss-DNA) oligomers (dA(20), d(C(3)TA(2))(3)C-3] or dT(20)) are able to disperse single-walled carbon nanotubes (SWNTs) in water at pH 7 through non-covalent wrapping on the nanotube surface. At lower pH, an alteration of the DNA secondary structure leads to precipitation of the SWNTs from the dispersion. The structural change of dA(20) takes place from the single-stranded to the A-motif form at pH 3.5 while in case of d(C(3)TA(2))(3)C-3] the change occurs from the single-stranded to the i-motif form at pH 5. Due to this structural change, the DNA is no longer able to bind the nanotube and hence the SWNT precipitates from its well-dispersed state. However, this could be reversed on restoring the pH to 7, where the DNA again relaxes in the single-stranded form. In this way the dispersion and precipitation process could be repeated over and over again. Variable temperature UV-Vis-NIR and CD spectroscopy studies showed that the DNA-SWNT complexes were thermally stable even at similar to 90 degrees C at pH 7. Broadband NIR laser (1064 nm) irradiation also demonstrated the stability of the DNA-SWNT complex against local heating introduced through excitation of the carbon nanotubes. Electrophoretic mobility shift assay confirmed the formation of a stable DNA-SWNT complex at pH 7 and also the generation of DNA secondary structures (A/i-motif) upon acidification. The interactions of ss-DNA with SWNTs cause debundling of the nanotubes from its assembly. Selective affinity of the semiconducting SWNTs towards DNA than the metallic ones enables separation of the two as evident from spectroscopic as well as electrical conductivity studies.

不同贮藏条件下果实角质层成分及其与耐贮性关系研究

角质层是果实抵御外界环境胁迫的一个屏障，既能调节果实自身的生理活动，也能增加对病原菌入侵的抵抗力，在果实贮藏保鲜中具有重要的作用。本文利用傅里叶变换红外光谱检测（Fourier-transform-infrared-spectroscopy）法，重点研究了不同贮藏条件下果实角质层和果肉细胞壁成分变化，及对果实品质和贮藏性的影响，为进一步阐明角质层在果实贮藏保鲜中的作用提供依据。研究内容包括：（1）壶瓶枣果实在冷藏和气调下软化率、品质、角质层和果肉细胞壁成分变化；（2）即时冷藏和延迟冷藏下，桃果实好果率、品质、角质层和果肉细胞壁成分变化；（3）采前喷施氯化钙或油菜素内酯对甜樱桃单果重、品质、果肉细胞壁结构以及耐贮性的影响。 试验结果表明：（1）与冷藏（-1±1 ºC）相比，气调贮藏（10% O2 + 0% CO2， -1±1 ºC）能够显著降低壶瓶枣软化率，更好地保持果实的硬度、可溶性固形物（SSC）和可滴定酸（TA）含量以及较高含量的果肉细胞壁物质和较低含量的角质层物质。（2）与延迟冷藏（25 ºC，48 h后转入0 ºC）相比，即时冷藏使“八月脆”桃果实能保持较高的果实硬度和好果率，显著减慢TA含量下降，能保持较高含量的果肉细胞壁物质和角质层物质，但对SSC和Vc含量没有显著的影响。（3）与对照相比，采前喷施CaCl2（1%，m/v）能够增加“红灯”（6.94%）的单果重，对甜樱桃果实的品质指标（硬度、SSC、TA）和细胞壁结构没有明显的影响。（4）与对照相比，采前喷施0.15 mg•L-1油菜素内酯能增加“红灯”（3.68%）和“大紫”（8.61%）的单果重，降低“红灯”果实的自然腐烂率，并不影响果实的品质指标（硬度、SSC、TA）。 这些研究结果说明：（1）与冷藏（-1±1 ºC）相比，气调贮藏（10% O2 + 0% CO2， -1±1 ºC）更利于壶瓶枣果实贮藏保鲜；（2）与延迟冷藏（25 ºC，48 h后转入0 ºC）相比，即时冷藏（0 ºC）更利于“八月脆”桃果实贮藏保鲜；（3）气调贮藏和即时冷藏通过调节果实角质层和细胞壁代谢等途径发挥作用。气调贮藏会降低壶瓶枣果实角质层物质含量，增强其透气性，减少壶瓶枣酒软发生；但即时冷藏会延缓“八月脆”桃果实角质层降解，维持角质层物质较高的含量以及结构完整性，以充分发挥角质层的保护作用，减缓果实的软化进程，维持果实硬度和品质；（4）采前适当浓度的钙或油菜素内酯处理对增加甜樱桃单果重，降低自然腐烂率有一定的作用，但在不同品种中的作用效果有差异。

Ferroelectricity in epitaxial pulsed laser deposited bismuth-layered perovskite thin films of different crystallographic orientations

Epitaxial thin films Of various bismuth-layered perovskites SrBi(2)Ta(2)O(9), Bi(4)Ti(3)O(12), BaBi(4)Ti(4)O(15), and Ba(2)Bi(4)Ti(5)O(18) were deposited by pulsed laser deposition onto epitaxial conducting LaNiO(3) or SrRuO(3) electrodes on single crystalline SrTiO(3) substrates with different crystallographic orientations or on top of epitaxial buffer layers on (100) silicon. The conductive perovskite electrodes and the epitaxial ferroelectric films are strongly influenced by the nature of the substrate, and bismuth-layered perovskite ferroelectric films with mixed (100), (110)- and (001)-orientations as well as with uniform (001)-, (116)- and (103)- orientations have been obtained. Structure and morphology investigations performed by X-ray diffraction analysis, scanning probe microscopy, and transmission electron microscopy reveal the different epitaxial relationships between films and substrates. A clear correlation of the crystallographic orientation of the epitaxial films with their ferroelectric properties is illustrated by macroscopic and microscopic measurements of epitaxial bismuth-layered perovskite thin films of different crystallographic orientations.

Efeito da proteína anticongelante tipo I (AFP I) na criopreservação de embriões e blastómeros de teleósteos

Dissertação de mest., Biologia Marinha, Faculdade de Ciências do Mar e do Ambiente, Universidade do Algarve, 2007

Optical properties of organic superconductor K-(BETS)2FeBr4 /

/c-(BETS)2FeBr4 is the first antiferromagnetic organic superconductor with successive antiferromagnetic and superconducting transitions at Ta^=2.5K and Tc=l.lK respectively at ambient pressure. Polarized reflectance measurements were performed on three single crystalsamples of this material using a Briiker IFS66V/S Interferometer, and a Bolometer detector or an MCT detector, at seven temperatures between 4K and 300K, in both the far-infrared and mid-infrared frequency range. After the reflectance results were obtained, the Kramers-Kronig dispersion relation was apphed to determine the optical conductivity of /c-(BETS)2FeBr4 at these seven temperatures. Additionally, the optical conductivity spectra were fitted with a Drude/Lorentz Oscillator model in order to study the evolution of the optical conductivity with temperature along the a-axis and c-axis. The resistivities calculated from the Drude model parameters along the a-axis and c-axis agreed reasonably with previous transport measurements.

Fiabilité et changement minimal détectable de mesures obtenues à partir d'images enregistrées par ultrasonographie afin de caractériser l'intégrité du tendon d'Achille

Problématique : La quantification de l’intégrité du tendon d’Achille (TA) représente un défi en réadaptation. L’adoption de mesures quantitatives du TA, extraites à partir d’une image ultrasonographique (QUS), pourrait remédier à cette lacune. Objectifs : 1) Évaluer la fiabilité test-retest et la précision de mesures QUS du TA; 2) Déterminer le meilleur protocole de collecte de mesures QUS à employer en pratique clinique. Méthodologie : Un total de 23 TAs présentant des symptômes d’une tendinopathie achilléenne et 63 TAs asymptomatiques ont été évalués. Pour chaque TA, 8 images ont été enregistrées (2 visites * 2 évaluatrices * 2 images). Différents types de mesures QUS ont été prises : géométriques (épaisseur, largeur, aire), dérivées d’un histogramme des niveaux de gris et dérivées d’une matrice de co-occurrence. Une étude de généralisabilité a quantifié la fiabilité et la précision de chaque mesure QUS et une étude de décision a fait ressortir les meilleurs protocoles de prise de mesures. Résultats : Les mesures géométriques ont démontré une excellente fiabilité et précision. Les mesures dérivées de l’histogramme des niveaux de gris ont démontré une fiabilité et précision médiocres. Les mesures dérivées d’une matrice de co-occurrence ont démontré une fiabilité modérée à excellente et une précision variable. En pratique clinique, il est recommandé de moyenner les résultats de trois images collectées par un évaluateur lors d’une visite. Conclusion : L’utilisation des mesures QUS géométriques permet de quantifier l’intégrité du TA (clinique et recherche). Davantage d’études sur les mesures QUS dérivées d’une matrice de co-occurrence s’avèrent nécessaires.