Time dependence and energy-transfer mechanisms in Tm3+Ho3+ and Tm3+-Ho3+ co-doped alkali niobium tellurite glasses sensitized by Yb3+

Glass samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb3+-5% Tm3+ and 5% Yb3+-5% Tm3+-0.5% Ho3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb3+ F-2(5/2) excited state. A good fit for the luminescence time evolution was obtained with the Yokota-Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb-5% Tm. 5% Yb-0.5% Ho and 5% Yb-5% Tm-0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from (1)G(4) and F-3(2) Tm3+ energy levels in all samples. The S-5(2) Ho3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

A comparison of charge-transfer mechanisms at rotated disk electrode for biomimetic binuclear and tetranuclear oxo-manganese complex in aqueous solution

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Ligand-rare-earth ion energy transfer in coordination compounds. A theoretical approach

A theoretical approach to the energy transfer process that occurs between a ligand and a rare-earth ion in luminescent complexes is presented. A discussion on the energy transfer mechanisms involved and on the associated selection rules is made. Numerical estimates are also presented.

Respiratory heat loss in the sheep: a comprehensive model

A model is presented for the respiratory heat loss in sheep, considering both the sensible heat lost by convection (C-R) and the latent heat eliminated by evaporation (E-R). A practical method is described for the estimation of the tidal volume as a function of the respiratory rate. Equations for C-R and E-R are developed and the relative importance of both heat transfer mechanisms is discussed. At air temperatures up to 30 degreesC sheep have the least respiratory heat loss at air vapour pressures above 1.6 kPa. At an ambient temperature of 40 degreesC respiratory loss of sensible heat can be nil; for higher temperatures the transfer by convection is negative and thus heat is gained. Convection is a mechanism of minor importance for the respiratory heat transfer in sheep at environmental temperatures above 30 degreesC. These observations show the importance of respiratory latent heat loss for thermoregulation of sheep in hot climates.

Desenvolvimento de um eletrodo modificado com monocamadas auto-organizadas e sua utilização como biossesor

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise teórica e simulação computacional de um sistema de resfriamento líquido de processadores de computadores pessoais

This paper aims to study the thermal aspects involved in a liquid cooling system for processors, analyzing their competitiveness and efficiency across the fins and fan system usually used by personal computers, because electronic components become more potent and consequently current methods of cooling are becoming ineffective. The liquid cooling system and air cooling system have different heat transfer mechanisms that involve mainly convection and conduction heat transfer modes, and, furthermore, requires an analysis of fluid dynamics, which can evaluate the losses involved in the closed system, consisting in an exchanger heat pipe and water blocks in liquid cooling system or heat sink and turbo-axial fan in the air cooling system

EStudo fundamental da interação de nanopartículas metálicas com íons terras raras em vidros e vitrocerâmicas para aplicações na região do infravermelho

Pós-graduação em Química - IQ

Cell death evaluation in benzo[a]pyrene-transformed human breast epithelial cells after microcell-mediated transfer of chromosomes 11 and 17

The incidence of apoptosis and nuclear instability, including the incidence of catastrophic death, were investigated in benzo[a]pyrene (BP)-transformed human breast epithelial cells (BP1-E cell line) after microcell-mediated transfer of chromosomes 11 and 17. Since the introduction of normal chromosomes 11 and 17 into tumorigenic human breast BP1-E cells reverts some of these cells' characteristics (especially those affected by microsatellite instabilities and loss of heterozygosity) those of parental non-transformed MCF-10F cells, it was expected that the cell death rates would also be affected by this treatment. The transfer of the mentioned chromosomes, especially chromosome 17, to tumorigenic BP1-E cells increased the apoptotic ratios and decreased the nuclear instability ratios, thus showing that the microsatellite instability and loss of heterozygosity induced by BP in these chromosomes of MCF-10F cells affect the control of cell death mechanisms. (C) 2003 Elsevier B.V. All rights reserved.

Excitation mechanisms and effects of dopant concentration in Gd2O2S : Tb3+ phosphor

Gadolinium oxysulfide powders doped with different Tb3+ concentrations were prepared from sulfur vaporization on rare earths' basic carbonate precursors. Single-phase Gd2O2S samples were obtained, with Tb3+ doping up to 9 at%. The study of the excitation mechanisms revealed that the Tb3+ emission might occur after the direct Tb3+ excitation either by energy transfer from Gd3+ or from the phosphor host. The characteristic terbium emission lines were observed, resulting from the radiative decay from D-5(3) or D-5(4), to F-7(j) levels. The cross-relaxation phenomenon was observed and its effects on the materials emission color were discussed based on the CIE diagram. By using time-resolved spectroscopy, D-5(3) -> F-7(J) and D-5(4) -> F-7(J) transitions were separated. (c) 2007 Elsevier B.V. All rights reserved.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Spectroscopic properties and upconversion mechanisms in Er3+-doped fluoroindate glasses

Fluorindate glasses containing 1,2,3,4 ErF3 mol % were prepared in a dry box under argon atmosphere. Absorption, Stokes luminescence (under visible and infrared excitation), the dependence of 4S3/2, 4I11/2, and 4I13/2 lifetimes with Er concentration, and upconversion under Ti-saphire laser excitation at λ=790 nm were measured, mostly at T=77 and 300 K. The upconversion results in a strong green emission and weaker blue and red emissions whose intensity obeys a power-law behavior I∼Pn, where P is the infrared excitation power and n=1.6, 2.1, and 2.9 for the red, green, and blue emissions, respectively. The red emission exponent n=1.5 can be explained by a cross relaxation process. The green and blue emissions are due to excited state absorption (ESA) and energy transfer (ET) processes that predict a factor n=2 and n=3 for the green and blue emissions, respectively. From transient measurements we concluded that for lightly doped samples the green upconverted emission is originated due to both processes ESA and ET. However, for heavily doped samples ET is the dominant process.

Optical properties and energy-transfer frequency upconversion of Yb 3+-sensitized Ho3+- And Tb3+-doped lead-cadmium-germanate glass and glass ceramic

In this report we investigate the optical properties and energy-transfer upconversion luminescence of Ho3+- and Tb3+/Yb 3+-codoped PbGeO3-PbF2-CdF2 glass-ceramic under infrared excitation. In Ho3+/Yb 3+-codoped sample, green(545 nm), red(652 nm), and near-infrared(754 nm) upconversion luminescence corresponding to the 4S 2(5F4) → 5I8, 5F5 → 5I8, and 4S2(5F4) → 5I 7, respectively, was readly observed. Blue(490 nm) signals assigned to the 5F2,3 → 5I8 transition was also detected. In the Tb3+/Yb3+ system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the 5D3(5G6) → 7FJ(J=6,5,4) and 5D4→ 7FJ(J=6,5,4,3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicate that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed.

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism

Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, as for conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerable interest. Here we provide evidence for ferroelectricity, accompanied by antiferromagnetic spin order, in a two-dimensional organic charge-transfer salt, thus representing a new class of multiferroics. We propose a charge-order-driven mechanism leading to electronic ferroelectricity in this material. Quite unexpectedly for electronic ferroelectrics, dipolar and spin order arise nearly simultaneously. This can be ascribed to the loss of spin frustration induced by the ferroelectric ordering. Hence, here the spin order is driven by the ferroelectricity, in marked contrast to the spin-driven ferroelectricity in helical magnets. © 2012 Macmillan Publishers Limited. All rights reserved.