Reduction from Eu3+ to Eu2+ in BaAl2O4 : Eu phosphor prepared in an oxidizing atmosphere and luminescent properties of BaAl2O4 : Eu

A reduction phenomenon of Eu3+ -> Eu2+ was observed for the first time when Eu3+ ions were doped into an AlO4-tetrahedron-containing compound BaAl2O4 in an oxidizing atmosphere of air by high-temperature solid-state reaction. X-ray powder diffraction patterns and photoluminescent spectra are used to confirm the compound structure and detect the simultaneous existence of both divalent and trivalent europium ions, respectively. The abnormal Eu3+ -> Eu2+ reduction is explained by a charge compensation model. Spectroscopic properties of BaAl2O4:Eu are discussed and Eu2+ emission spectrum shows consistence with the results reported by Katsumata et a]. [J. Cryst. Growth 198/199 (1999) 869.] and Lin et al. [Mater. Chem. Phys. 70 (2001) 156.].

Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propylthiethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by H-1 NMR IR and MS, The monomer acts as a ligand for Tb3+ ion and as a sol-gel precursor. Band emission front Tb3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the D-5(4) level of Tb3+ ion falls in the exciting range to sensitize Tb3+ ion fluorescence.

Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

Preparation of rare earth ion induced conformation-specific anti-calmodulin monoclonal antibody

Monoclonal antibody technique was employed to detect the conformational change of calmodulin induced by metal ions. Bovine calmodulin was firstly modified by 2,4-dinitrofluorobenzene to improve its immunogenicity, then, the derived protein was saturated with trivalent europium ions and injected to Balb/c mice as antigen. After four times of immunization, a corresponding antibody was detected and its titer in serum was determined as 1 : 12 000. By fusing of the spleen cells with hybridoma cells, a europium induced conformation-specific anti-calmodulin monoclonal antibody cell strain named as 2C3 was produced successfully. The molecular recognition ability of antibody to apocalmodulin and holocalmodulin showed a significant difference, indicating that this antibody could be applied to the studies of different effects of metal ions on the conformational change of calmodulin and its interaction with target molecules.

Ce3+ -> Eu2+ energy transfer in BaLiF3 phosphor

Photoluminescence characteristics and the energy transfer between Ce3+ and Eu2+ in BaLiF3 host lattice have been investigated. A series of concentrations of Ce3+ ion with a fixed Eu2+ concentration in doubly doped BaLiF3:Ce3+,Eu2+ have been studied. According to the defects forming after Eu2+ and Ce3+ entering the host lattice, cerium ions occupy the positions of nearest neighbors of the europium ions. The energy transfer probability and critical distance are calculated. (C) 1999 Elsevier Science Ltd. All rights reserved.

EXAFS, SAXS and Eu3+ luminescence spectroscopy of sol-gel derived siloxane-polyethyleneoxide hybrids

Hybrid Eu3+-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu3+ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu3+ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu3+ concentration, while non radiative decay paths from the D-5(0) excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.

Complexos de európio e /ou de zinco com ácido 3-piridinocarboxílico

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

Propriedades estruturais e espectroscópicas de WO3 e WO3:Eu3+

Used as catalysts even in organic and inorganic molecules, as additives on catalysts, electrochromic films on smart windows the tungsten trioxide have been largely studied on the lasts decades, but there is just a few about it's luminescence. Using as precursors nitric acid and sodium tungstate the tungsten trioxide were been prepared thru wet process then treating on thermic and hydrothermal treatments. Where been evaluated the effects of methodology, nitric acid concentration, duration and temperature of treatments. The samples were characterized by X-ray diffraction (XRD), Raman scattering spectroscopy (RSS), Fourier transformed infrared spectroscopy, photoluminescence spectroscopy (PLS) and X-ray excited optical luminescence (XEOL). Hydrated phases of tungsten trioxide were obtained through hydrothermal treatments and the non-hydrated phases occur with thermic treatments. The acid concentration has the ability to determine the major phase formed as well the temperature determine the hydratation of the product. With lower temperatures dihydrate phase were preferable formed and with the rise of temperature, the water molecules were lost up to the fractionary hydratation and then the non-hydrated phase with higher temperatures depending on the atmosphere used on the thermal treatment. Doping the system with europium ions even substituting tungsten or in the interstices of the matrix were not been successful, as well the XEOL spectroscopy intensity were null and quite low for ultraviolet and visible excitation photoluminescence because of oxygen defect levels localized into the prohibited band.

Propriedades estruturais e espectroscópicas de WO3 e WO3:Eu3+

Used as catalysts even in organic and inorganic molecules, as additives on catalysts, electrochromic films on smart windows the tungsten trioxide have been largely studied on the lasts decades, but there is just a few about it's luminescence. Using as precursors nitric acid and sodium tungstate the tungsten trioxide were been prepared thru wet process then treating on thermic and hydrothermal treatments. Where been evaluated the effects of methodology, nitric acid concentration, duration and temperature of treatments. The samples were characterized by X-ray diffraction (XRD), Raman scattering spectroscopy (RSS), Fourier transformed infrared spectroscopy, photoluminescence spectroscopy (PLS) and X-ray excited optical luminescence (XEOL). Hydrated phases of tungsten trioxide were obtained through hydrothermal treatments and the non-hydrated phases occur with thermic treatments. The acid concentration has the ability to determine the major phase formed as well the temperature determine the hydratation of the product. With lower temperatures dihydrate phase were preferable formed and with the rise of temperature, the water molecules were lost up to the fractionary hydratation and then the non-hydrated phase with higher temperatures depending on the atmosphere used on the thermal treatment. Doping the system with europium ions even substituting tungsten or in the interstices of the matrix were not been successful, as well the XEOL spectroscopy intensity were null and quite low for ultraviolet and visible excitation photoluminescence because of oxygen defect levels localized into the prohibited band.

Formation of thin luminescent Eu3+-LB films by in situ coordination with 2,3,5,6-tetra(2 '-pyridyl)pyrazine and 1-octadecanol in pure and mixed Langmuir monolayers

The in situ complexation between 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) molecules and europium ions at the air-liquid interface by means of mixed 1-octadecanol Langmuir films is reported. These films were transferred to solid supports by means of the Langmuir-Blodgett (LB) technique. The EDS maps attested the homogeneity of the LB films as well as the presence of the europium ions. The mixed alcohol/tppz LB film contained a larger amount of europium ions as compared to the pure octadecanol LB film. This work reports the production of a thin luminescent Eu3+ film containing europium ions using only alcohol molecules as ligands an unexpected result, since it is well known that there is an occurrence of non-radiative deactivation of excited europium by hydroxyl groups. Europium ion multiple binding sites were detected from lifetime decay measurements of these films in the presence of tppz molecules. (C) 2012 Elsevier B.V. All rights reserved.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.