Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.

Efficient UV-visible upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate vitroceramic

Cooperative energy-transfer upconversion luminescence in Tb 3+/Yb 3+-codoped PbGeO 3-PbF 2-CdF 2 vitroceramic and its precursor glass under resonant and off-resonance infrared excitation, is investigated. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm, identified as due to the 5D 3( 5G 6 → 7F J(J=6,5,4) and 5D 4 → 7F J(J=6,5,4,3) transitions, respectively, were readily observed. The results indicate that cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The comparison of the upconversion process in a vitroceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.

Upconversion ultraviolet random lasing in Nd 3+ doped fluoroindate glass powder

An upconversion random laser (RL) operating in the ultraviolet is reported for Nd 3+ doped fluoroindate glass powder pumped at 575 nm. The RL is obtained by the resonant excitation of the Nd 3+ state 2G 7/2 followed by energy transfer among two excited ions such that one ion in the pair decays to a lower energy state and the other is promoted to state 4D 7/2 from where it decays emitting light at 381 nm. The RL threshold of 30 kW/cm 2 was determined by monitoring the photoluminescence intensity as a function of the pump laser intensity. The RL pulses have time duration of 29 ns that is 50 times smaller than the decay time of the upconversion signal when the sample is pumped with intensities below the RL laser threshold. © 2011 Optical Society of America.

State Dependent Riccati Equation (SDRE) control method applied in cancellation of a parametric resonance in a magnetically levitated body

Here, a simplified dynamical model of a magnetically levitated body is considered. The origin of an inertial Cartesian reference frame is set at the pivot point of the pendulum on the levitated body in its static equilibrium state (ie, the gap between the magnet on the base and the magnet on the body, in this state). The governing equations of motion has been derived and the characteristic feature of the strategy is the exploitation of the nonlinear effect of the inertial force associated, with the motion of a pendulum-type vibration absorber driven, by an appropriate control torque [4]. In the present paper, we analyzed the nonlinear dynamics of problem, discussed the energy transfer between the main system and the pendulum in time, and developed State Dependent Riccati Equation (SDRE) control design to reducing the unstable oscillatory movement of the magnetically levitated body to a stable fixed point. The simulations results showed the effectiveness of the (SDRE) control design. Copyright © 2011 by ASME.

On nonlinear dynamics in a free fluid surface of a tank excited by a non-ideal power source

We investigate the nonlinear oscillations in a free surface of a fluid in a cylinder tank excited by non-ideal power source, an electric motor with limited power supply. We study the possibility of parametric resonance in this system, showing that the excitation mechanism can generate chaotic response. Additionally, the dynamics of parametrically excited surface waves in the tank can reveal new characteristics of the system. The fluid-dynamic system is modeled in such way as to obtain a nonlinear differential equation system. Numerical experiments are carried out to find the regions of chaotic solutions. Simulation results are presented as phase-portrait diagrams characterizing the resonant vibrations of free fluid surface and the existence of several types of regular and chaotic attractors. We also describe the energy transfer in the interaction process between the hydrodynamic system and the electric motor. Copyright © 2011 by ASME.

Purification, characterization, and specificity determination of a new serine protease secreted by penicillium waksmanii

The purpose of this work was to purify a protease from Penicillium waksmanii and to determine its biochemical characteristics and specificity. The extracellular protease isolated that was produced by P. waksmanii is a serine protease that is essential for the reproduction and growth of the fungus. The protease isolated showed 32 kDa, and has optimal activity at pH 8.0 and 35 C towards the substrate Abz-KLRSSKQ-EDDnp. The protease is active in the presence of CaCl2, KCl, and BaCl, and partially inhibited by CuCl2, CoCl2 and totally inhibited by AlCl3 and LiCl. In the presence of 1 M urea, the protease remains 50 % active. The activity of the protease increases 60 % when it is exposed to 0.4 % nonionic surfactant-Triton X-100 and loses 10 % activity in the presence of 0.4 % Tween-80. Using fluorescence resonance energy transfer analysis, the protease showed the most specificity for the peptide Abz-KIRSSKQ-EDDnp with k cat/K m of 10,666 mM-1 s-1, followed by the peptide Abz-GLRSSKQ-EDDnp with a k cat/K m of 7,500 mM -1 s-1. Basic and acidic side chain-containing amino acids performed best at subsite S1. Subsites S2, S3, S′ 2, and S′ 1, S ′ 3 showed a preference for binding for amino acids with hydrophobic and basic amino acid side chain, respectively. High values of k cat/K m were observed for the subsites S2, S3, and S′ 2. The sequence of the N-terminus (ANVVQSNVPSWGLARLSSKKTGTTDYTYD) showed high similarity to the fungi Penicillium citrinum and Penicillium chrysogenum, with 89 % of identity at the amino acid level. © 2012 Springer Science+Business Media New York.

Strongly luminescent, highly ionic europium in a lanthanum diphenylphosphinate matrix

A series of insoluble, chemically inert and thermally stable compounds La1-xEux(DPP)3 (x = 0.50, 0.20, 0.10, and 0.050; DPP = diphenylphosphinate) was synthesized and characterized by elemental and thermogravimetric analysis, FT Infrared spectroscopy and X-ray powder diffraction. Luminescence spectroscopy at both 77 and 298 K showed changes in the intensity of the hypersensitive transition 5D 0 → 7F2 of Eu3+ which are dependent of the excitation wavelength, suggesting that the europium occupies two different sites in the compounds. The large quantum efficiency and quantum yield, as well as the long radiative lifetime of the 5D0 Eu3+ level of the series of compounds, which are desirable qualities for light-conversion molecular devices, are discussed in terms of the interactions and the energy transfer process between the ligands and the metal ion. © 2012 Elsevier B.V. All rights reserved.

First crystal structures of lanthanide-hydrocinnamate complexes: Hydrothermal synthesis and photophysical studies

Five new lanthanide(III) complexes of hydrocinnamic acid (Hcin), [Ln(cin)3(H2O)3]·3Hcin (Ln = Tb(III) (1), Dy(III) (2), Er(III) (3), Eu(III) (4) and Gd(III) (5)) have been synthesized and characterized. The X-ray structures of 1-5 reveal that all compounds are isostructural and that each lanthanide ion is nine-coordinated by oxygen atoms in an overall distorted tricapped trigonal-prismatic geometry. Six oxygen atoms are provided by carboxylate moieties, and the other three by water molecules. The supramolecular architectures of 1-5 show the presence of uncoordinated hydrocinnamic acid molecules which induce the formation of numerous hydrogen bonds. The photophysical properties of these complexes in the solid state at room temperature were studied using diffuse reflectance (DR), fluorescence excitation and emission spectra. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer, indicating that cin- ligands can act as intramolecular energy donors for Tb(III), Dy(III) and Eu(III) ions. © 2012 Elsevier B.V.

Upconversion luminescence in Er3+ doped Ga10Ge 25S65 glass and glass-ceramic excited in the near-infrared

The infrared-to-visible frequency upconversion was investigated in Er 3+-doped Ga10Ge25S65 glass and in the transparent glass-ceramic obtained by heat-treatment of the glass above its glass-transition temperature. Continuous-wave and pulsed lasers operating at 980 nm and 1480 nm were used as excitation sources. The green (2H 11/2 → 4I15/2; 4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) photoluminescence (PL) signals due to the Er3+ ions were characterized. The PL decay times were influenced by energy transfer among Er3+ ions, by cross-relaxation processes and by energy transfer from the Er3+ ions to the host material. The PL from the Er3+ ions hosted in the crystalline phase was distinguished only when the glass-ceramic was excited by the 1480 nm pulsed laser. The excitation pathways responsible for the green and red PL bands are discussed to explain the differences between the spectra observed under continuous-wave and pulsed excitation. © 2013 American Institute of Physics.

Synthesis, crystal structure and photoluminescence of a binuclear complex of europium(III) containing 3,5-dicarboxypyrazolate and succinate

The new europium binuclear complex [Eu2(dcpz) 2(suc)(H2O)8]·(H2O) 1.5 (dcpz = 3,5-dicarboxypyrazolate and suc = succinate) has been synthesized and structurally characterized by single crystal X-ray diffraction methods. The binuclear complex crystallizes in the triclinic space group P1̄ and consists of two lanthanide ions linked by two different bridging organic ligands. 3D supramolecular framework is constructed by hydrogen bonds. The compound shows strong red emission under UV excitation at room temperature associated to IL transitions indicating a ligand to metal energy transfer mechanism since the triplet energy level lies higher than that of europium 5D0 level. Magnetic susceptibility studies showed weak temperature dependence characteristic of the Van Vleck paramagnetism. © 2013 Elsevier Ltd. All rights reserved.

Enhanced optical properties of germanate and tellurite glasses containing metal or semiconductor nanoparticles

Germanium- and tellurium-based glasses have been largely studied due to their recognized potential for photonics. In this paper, we review our recent studies that include the investigation of the Stokes and anti-Stokes photoluminescence (PL) in different glass systems containing metallic and semiconductor nanoparticles (NPs). In the case of the samples with metallic NPs, the enhanced PL was attributed to the increased local field on the rare-earth ions located in the proximity of the NPs and/or the energy transfer from the metallic NPs to the rare-earth ions. For the glasses containing silicon NPs, the PL enhancement was mainly due to the energy transfer from the NPs to the Er3+ ions. The nonlinear (NL) optical properties of PbO-GeO 2 films containing gold NPs were also investigated. The experiments in the pico- and subpicosecond regimes revealed enhanced values of the NL refractive indices and large NL absorption coefficients in comparison with the films without gold NPs. The reported experiments demonstrate that germanate and tellurite glasses, having appropriate rare-earth ions doping and NPs concentration, are strong candidates for PL-based devices, all-optical switches, and optical limiting. © 2013 Cid Bartolomeu de Araujo et al.

Luminescent properties of hybrid materials prepared by the polymeric precursor method

Rare earth complexes (RE) can be incorporated in silica matrixes, originating organic/inorganic hybrid materials with good thermal stability and high rare earth emission lines. In this work, the hybrid material was obtained by the polymeric precursor method and ultrasonic dispersed with spherical silica particles prepared by the Stöber Method. The Raman spectra indicated that the Eu3+ ions are involved in a polymeric structure formed as consequence of the chelation and polyesterification reactions of this ion with citric acid and ethylene glycol. After the ultrasonic stirring, 2-hydroxynicotinic ligand will also compose this polymeric rigid structure. The TGA/DTA analysis showed that this polymeric material was thermal decomposed at 300 °C. Moreover, this process allows the chelating process of the 2-hydroxynicotinic acid ligand to the Eu3+ ions. The 29Si NMR showed that the ultrasonic dispersion of the reactants was not able to promote the functionalization of the silica particles with the 2-hydroxynicotinic acid ligand. Moreover, heat treatment promotes the [Eu(HnicO2)3] complex particles incorporation into silica pores. At this temperature, the TGA curve showed that only the thermal degradation of ethylene glycol and citric acid used during the experimental procedure occurs. The silica and hybrid materials are composed by spherical and aggregated particles with particle size of approximately 450 nm, which can be influenced by the heat treatment. These materials also present an absorption band located at 337 nm. The photoluminescent study showed that when the hybrid samples were excited at 337 nm wavelength, the ligand absorbs the excitation light. Part of this energy is transferred to the Eu3+ ion, which main emission, 5D0→ 7F2, is observed in the emission spectrum at 612 nm. As the heating temperature increases to 300 C, the energy transfer is more favorable. The lifetime values showed that the Eu3+ emission is enhanced due to the energy transfer process in the powders. © 2013 Elsevier B.V. All rights reserved.

Tunable plasmon resonance modes on gold nanoparticles in Er 3 +-doped germanium-tellurite glass

Relative to the Er3 +:gold-nanoparticle (Er3 +:Au-NP) axis, the polarization of the gold nanoparticle can be longitudinal (electric dipole parallel to the Er3 +:Au-NP axis) or transverse (electric dipole perpendicular to the Er3 +:Au-NP axis). For longitudinal polarization, the plasmon resonance modes of gold nanoparticles embedded in Er3 +-doped germanium-tellurite glass are activated using laser lines at 808 and 488 nm in resonance with radiative transitions of Er3 + ions. The gold nanoparticles were grown within the host glass by thermal annealing over various lengths of time, achieving diameters lower than 1.6 nm. The resonance wavelengths, determined theoretically and experimentally, are 770 and 800 nm. The absorption wavelength of nanoparticles was determined by using the Frohlich condition. Gold nanoparticles provide tunable emission resulting in a large enhancement for the 2H11/2 → 4I13/2 (emission at 805 nm) and 4S 3/2 → 4I13/2 (emission at 840 nm) electronic transitions of Er3 + ions; this is associated with the quantum yield of the energy transfer process. The excitation pathways, up-conversion and luminescence spectra of Er3 + ions are described through simplified energy level diagrams. We observed that up-conversion is favored by the excited-state absorption due to the presence of the gold nanoparticles coupled with the Er3 + ions within the glass matrix. © 2013 Elsevier B.V.

Synthesis, structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

Estudo da interação entre flavonóides e a albumina do soro humano

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)