Luminescence and defect centres in Tb(3+) doped LaMgAl(11)O(19) phosphors

Terbium (Tb) doped LaMgAl(11)O(19) phosphors have been prepared by the combustion of corresponding metal nitrates (oxidizer) and urea (fuel) at furnace temperature as low as 500 C Combustion synthesized powder phosphor was characterized by X-ray diffraction and field emission scanning electron microscopy techniques LaMgAl(11)O(19) doped with trivalent terbium ions emit weakly in blue and orange light region and strongly in green light region when excited by the ultraviolet light of 261 nm Electron Spin Resonance (ESR) studies were carried out to study the defect centres Induced in the phosphor by gamma irradiation and also to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of at least two defect centres One of the centres (centre I) with principal g-values g(parallel to) = 2 0417 and g(perpendicular to) = 2 0041 is identified as O(2)(-) ion while centre II with an axially symmetric g-tensor with principal values g(parallel to) = 19698 and g(perpendicular to) = 1 9653 is assigned to an F(+) centre (singly ionized oxygen vacancy) An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons) The F centre and also the F+ centre appear to correlate with the observed high temperature TSL peak in LaMgAl(11)O(19) Tb phosphor (C) 2010 Elsevier Masson SAS All rights reserved

Defect centre responsible for production of 110 degrees C TL peak in quartz

110 degrees C thermoluminescence (TL) peak in quartz is well known due to its pre-dose effect, which is used in dating technique. The generally accepted mechanism for the production of this peak is based on Ge impurity contained in quartz. Its role is to substitute for Si in SiO(4) tetrahedron and under irradiation gives rise to [GeO(4)/e(-)](-) electron centre. Heating for TL read out liberates electron that recombines with hole in [AlO(4)/h]degrees or [H(3)O(4)/h]degrees centres emitting photon. The investigation, carried out on blue quartz, green quartz, black quartz, pink quartz, red quartz, sulphurous quartz, milky quartz, alpha quartz and synthetic quartz, has shown that the 110 degrees C TL peak in all these varieties of quartz has no correlation with the respective Ge content. Electron paramagnetic resonance (EPR) measurements on any of these varieties of quartz revealed a signal with g(1) = 2.0004, g(2) = 1.9986 and g(3) = 1.974 and this signal does not appear to correspond to any known EPR signals in alpha quartz. Furthermore, isothermal decay measurements are carried out on the above mentioned EPR signal and 110 degrees C TL peak in alpha, blue and green quartz. A close correlation has been observed in the decay behavior. A new mechanism is proposed based on an interstitial O(-) centre. (C) 2009 Elsevier Ltd. All rights reserved.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na(G)(H(2)W(12)O(40))center dot H(2)O] becomes useful. However, the sodium polytungstate is very expensive in Brazil: hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCI, HNO(3) and H(2)O(2) for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g= 2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. lkeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under -gamma-irradiation. However, still due to iron influence, the additive method yielded too old age-value. Since annealing at 300 degrees C, Toyoda and Ikeya IS. Toyoda, M. Ikeya, Geochem. J. 25 (1991) 427-445] states that E `(1)-signal with maximum intensity is obtained, while annealing at 400 degrees C E`(1)-signal is completely eliminated, the subtraction of the second one from 300 degrees C heat-treated sample isolate E`(1)-like signal. Since this is radiation dose-dependent, we show that now EPR dating becomes possible. (C) 2008 Elsevier B.V. All rights reserved.

Thermo luminescence of natural and synthetic diopside

Diopside, a natural silicate mineral of formula CaMgSi2O6, has been investigated concerning its thermoluminescence (TL) and electron paramagnetic resonance (EPR) properties. Glow curves and TL vs. gamma-dose were obtained irradiating natural samples to additional dose varying from 50 to 10,000Gy. Except for a 410 degrees C peak found in the Al-doped artificial diopside, all the other peaks grow linearly with radiation dose, but saturate beyond -1 kGy. To investigate high-temperature effect before irradiation, measurements of TL intensity in samples annealed at 500-900 degrees C and then irradiated to I kGy gamma-dose were carried out. Also the TL emission spectrum has been obtained. To compare with natural diopside, a synthetic pure polycrystal was produced and further those doped with iron, aluminum and manganese were also produced. (c) 2007 Elsevier B.V. All rights reserved.

First evidence of crystalline KHSO(4):Mn grown by an aqueous solution method and the investigation of the effect of ionizing radiation exposure

In this work, KHSO(4):Mn crystals doped with Mn and K(2)SO(4) were synthesized using an aqueous solution method. The samples were exposed to ionizing radiation in order to observe the effects on their physical properties. Raman spectroscopy was used to identify the structure of the crystals by detecting the vibrational frequencies of the crystalline lattice. Electron paramagnetic resonance (EPR) was used to study the creation of paramagnetic centers arising from exposure to ionizing radiation. This new synthesis method produces high quality K(2)SO(4) and KHSO(4):Mn crystals and allows control of structural, morphological, optical and magnetic properties. (C) 2009 Elsevier B.V. All rights reserved,

Magnetic and optical characterization of Mn-doped PbS nanocrystals supported in oxide glass matrix

The evidence of successful growth of Mn-doped PbS (Pb(1-x)Mn(x)S) nanocrystals (NCs) in SiO(2)-Na(2)CO(3)-Al(2)O(3)-PbO(2)-B(2)O(3) template, using the fusion method, is reported on in this study. The as-grown Pb(1-x)Mn(x)S NC is characterized using optical absorption, electron paramagnetic resonance, and atomic force microscopy. The data are discussed in terms of two distinct scenarios, namely a core-doped and a shell-doped nanostructure. (C) 2008 Elsevier B.V. All rights reserved.

Thermoluminescence, structural and magnetic properties of a Li(2)O-B(2)O(3)-Al(2)O(3) glass system doped with LiF and TiO(2)

A Li(2)O-B(2)O(3)-Al(2)O(3) glass system, un-doped and doped with LiF, and/or TiO(2) was synthesized by the fusion method and its physical properties were investigated by thermoluminescence (TL), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), atomic force microscopy (AFM) and differential thermal analysis (DTA). The samples were subjected to gamma-rays from a colbalt-60 ((60)Co) source. These techniques provided evidence of LiF and LiF doped with Ti crystal formation in the glass system. A TL glow peak at about 433 K was sensitive to (60)Co gamma-rays and showed good linearity with doses and consequently could be used to quantify radiation doses. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Magnetic resonance and conductivity study of gelatin-based proton conductor polymer electrolytes

This work report results from proton nuclear magnetic resonance (NMR), continuous-wave (CW-EPR) and pulsed electron paramagnetic resonance (P-EPR) and complex impedance spectroscopy of gelatin-based polymer gel electrolytes containing acetic acid. cross-linked with formaldehyde and plasticized with glycerol. Ionic conductivity of 2 x 10(-5) S/cm was obtained at room temperature for samples prepared with 33 wt% of acetic acid. Proton ((1)H) line shapes and spin-lattice relaxation times were measured as a function of temperature. The NMR results show that the proton mobility is dependent on acetic acid content in the plasticized polymer gel electrolytes. The CW-EPR spectra, which were carried out in samples doped with copper perchlorate, indicate the presence of the paramagnetic Cu(2+) ions in axially distorted sites. The P-EPR technique, known as electron spin echo envelope modulation (ESEEM), was employed to show the involvement of both, hydrogen and nitrogen atoms, in the copper complexation of the gel electrolyte. (C) 2009 Elsevier Ltd. All rights reserved.

Biological effects of anionic meso-tetrakis (para-sulfonatophenyl) porphyrins modulated by the metal center. Studies in rat liver mitochondria

In this paper, we present a study about the influence of the porphyrin metal center and mesa ligands on the biological effects of meso-tetrakis porphyrins. Different from the cationic meso-tetrakis 4-N-methyl pyridinium (Mn(III)TMPyP), the anionic Mn(III) meso-tetrakis (para-sulfonatophenyl) porphyrin (Mn(III)TPPS4) exhibited no protector effect against Fe(citrate)-induced lipid oxidation. Mn(III)TPPS4 did not protect mitochondria against endogenous hydrogen peroxide and only delayed the swelling caused by tert-BuOOH and Ca(2+). Fe(III)TPPS4 exacerbated the effect of the tert-BuOOH, and both porphyrins did not significantly affect Fe(II)citrate-induced swelling. Consistently, Fe(III)TPPS4 predominantly promotes the homolytic cleavage of peroxides and exhibits catalytic efficiency ten-fold higher than Mn(III)TPPS4. For Mn(III)TPPS4, the microenvironment of rat liver mitochondria favors the heterolytic cleavage of peroxides and increases the catalytic efficiency of the manganese porphyrin due to the availability of axial ligands for the metal center and reducing agents such as glutathione (GSH) and proteins necessary for Compound II (oxomanganese IV) recycling to the initial Mn(III) form. The use of thiol reducing agents for the recycling of Mn(III)TPPS4 leads to GSH depletion and protein oxidation and consequent damages in the organelle. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Vanadium complexes with thiosemicarbazones: Synthesis, characterization, crystal structures and anti-Mycobacterium tuberculosis activity

The development of more efficient anti-tuberculosis drugs is of interest. Three oxovanadium(IV) and three cis-dioxovanadium(V) complexes with thiosemicarbazone derivatives bearing moieties with different lipophilicity have been prepared and had their inhibitory activity against Mycobacterium tuberculosis H(37)Rv ATCC 27294 evaluated. The analytical methods used by the complexes` characterization included IR, EPR, (1)H, (13)C and (51)V NMR spectroscopies, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. [VO(acac)(aptsc)], [VO(acac)(apmtsc)] and [VO(acac)(apptsc)] (acac = acetylacetonate; Haptsc = 2-acetylpyridinethiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone) are paramagnetic and their EPR spectra are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral structures of rhombic symmetry and with the oxidation state +IV for the vanadium atom. As result of oxidation of the vanadium(IV) complexes above, the diamagnetic cis-dioxovanadium(V) complexes [VO(2)(aptsc)[, [VO(2)(apmtsc)[ and [VO(2)(apptsc)] are formed. Their (1)H, (13)C and (51)V NMR spectra were acquired and support a distorted square pyramidal geometry for them, in accord with the solid state X-ray structures determined for [VO(2)(aptsc)] and [VO(2)(apmtsc)]. In general, the vanadium compounds show comparable or larger anti-M. tuberculosis activities than the free thiosemicarbazone ligands, with MIC values within 62.5-1.56 (mu g/mL). (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, characterization, crystal structure, and biological studies of vanadium complexes with glycolic acid

Synthesis, characterization, crystal structure, and biological studies of two complexes with glycolic acid are described. The solid complexes were formulated as K2[VO(C2H2O3)(C2H3O3)2] H2O (1) and K2[{VO2(C2H2O3)}2] (2) and characterized by X-ray studies, Fourier transform infrared spectroscopy (FTIR), Electron paramagnetic resonance (EPR), and magnetic susceptibility. Conversion of 1 to 2 was studied in aqueous solution by UV-Vis spectroscopy and in the solid state by diffuse reflectance spectroscopy. Complex 2 contains dinuclear [{VO2(C2H2O3)}2]2- anions in which glycolate(2-) is a five-membered chelating ring formed by carboxylate and -hydroxy groups. The geometry around the vanadium in 2 was interpreted as intermediate between a trigonal bipyramid and a square pyramid. Vanadium(IV) is pentacoordinate in 1 as a distorted square pyramid. Complex 1 contains a vanadyl group (V=O) surrounded by two oxygens from deprotonated carboxylate and hydroxy groups forming a five-membered ring. Two oxygens from different glycolates(1-) are bonded to the (V=O) also. Biological analysis for potential cytotoxic effects of 1 was performed using Human Cervix Adenocarcinoma (HeLa) cells, a human cervix adenocarcinoma-derived cell line. After incubation for 48 h, 1 causes 90 and 95% of HeLa cells death at 20 and 200 mol L-1, respectively.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Evidence for magnetic phase separation in La(0.86)Sr(0.14)Mn(1-x)Cu(x)O(3+delta) manganites from NMR and magnetic measurements

Polycrystalline La(0.86)Sr(0.14)Mn(1-x)Cu(x)O(3+delta) (x = 0, 0.05, 0.10, 0.15, 0.20) manganites were investigated by means of magnetic measurements and zero-field (139)La and (55)Mn nuclear magnetic resonance (NMR) spectroscopy. Magnetization versus temperature measurements revealed a paramagnetic to ferromagnetic transition in most samples, with lower Curie temperatures and broader transitions for samples with higher Cu contents. The details of the magnetization measurements suggested a phase-separated scenario, with ferromagnetic clusters embedded in an antiferromagnetic matrix, especially for the samples with large Cu contents (x = 0.15 and 0.20). Zero-field (139)La NMR measurements confirmed this finding, since the spectral features remained almost unchanged for all Cu-doped samples, whereas the bulk magnetization was drastically reduced with increasing Cu content. (55)Mn NMR spectra were again typical of ferromagnetic regions, with a broadening of the resonance line caused by the disorder introduced by the Cu doping. The results indicate a coexistence of different magnetic phases in the manganites studied, with the addition of Cu contributing to the weakening of the double-exchange interaction in most parts of the material.

Magnetic resonance study of a vanadium pentoxide gel

In this work we report results from continuous-wave (CW) and pulsed electron paramagnetic resonance (EPR) and proton nuclear magnetic resonance (NMR) studies of the vanadium pentoxide xerogel V2O5:nH(2)O (n approximate to 1.6). The low temperature CW-EPR spectrum shows hyperfine structure due to coupling of unpaired V4+ electron with the vanadium nucleus. The analysis of the spin Hamiltonian parameters suggests that the V4+ ions are located in tetragonally distorted octahedral sites. The transition temperature from the rigid-lattice low-temperature regime to the high temperature liquid-like regime was determined from the analysis of the temperature dependence of the hyperfine splitting and the V4+ motional correlation time. The Electron Spin Echo Envelope Modulation (ESEEM) data shows the signals resulting from the interaction of H-1 nuclei with V4+ ions. The modulation effect was observed only for field values in the center of the EPR absorption spectrum corresponding to the single crystals orientated perpendicular to the magnetic field direction. At least three protons are identified in the xerogel by our magnetic resonance experiments: (I) the OH groups in the equatorial plane, (ii) the bound water molecules in the axial V=O bond and (iii) the free mobile water molecules between the oxide layers. Proton NMR lineshapes and spin-lattice relaxation times were measured in the temperature range between 150 K and 323 K. Our analysis indicates that only a fraction of the xerogel protons contribute to the measured conductivity.