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.

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.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. 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.

Spectroscopic investigation of the interactions between emeraldine base polyaniline and Eu(III) ions

The interactions of emeraldine base form of polyaniline (EB-PANI) and Eu(III) ions in 1-methyl-2-pyrrolidinone (NMP) solution and in films have been investigated by UV-vis-NIR, resonance Raman. luminescence and electron paramagnetic resonance (EPR) spectroscopies. These spectroscopic techniques allowed to characterize quinone and semiquinone segments in the polymeric chains. and the oxidation state of europium ions in Eu-PANI samples. For high values of Eu(III)/N molar ratio (24/1) the presence of a weak polaronic absorption band at 980 nm in UV-vis-NIR spectrum and the observation of bands at 1330 and 1378 (nu(center dot)(C-N+)) cm(-1) due to emeraldine salt in the Raman spectrum at 1064 nm indicate a low doping degree. Oxidation of EB-PANI to pernigraniline base (PB-PANI) occurs in diluted solutions. The experimental data showed that the solvent plays an important role on the nature of formed species. The narrow EPR signal at g = 2.006 (line width 8G) confirms the presence of PANI radical cations in Eu-PANI film. The absence of broad signal characteristic of Eu(II) in EPR spectrum suggested that europium ions are primarily at Eu(III) oxidation state. The luminescence spectra of Eu-PANI film presented emission bands at 405 and 418 nm assigned to PANI moieties and bands at 594,615 and 701 nm assigned to (5)D(0) -> (7)F(J) (J = 1, 2 and 4, respectively) transitions of Eu(III). EPR and photoluminescence data confirm that europium ions are mainly in Eu(III) oxidation state in Eu(III)/PANI films. (C) 2008 Elsevier B.V. All rights reserved.

Oxidation of anilinium ions intercalated in montmorillonite clay by electrochemical route

Resonance Raman, FTIR, X-ray diffraction, UV-vis-NIR, electron paramagnetic resonance, X-ray absorption at Si K-edge and electron microscopy were employed for characterizing the products formed through electrochemical oxidation of intercalated anilinium ions inside the cationic montmorillonite (MMT) clay. The layer silicate structure was not affected by the anilinium oxidation between the layers. The intercalated products present only an electronic absorption band at 400 nm, very low conductivity (ca. 10(-7) S cm(-1)) and their Raman spectrum displays bands, with high relative intensities, assigned to the benzidine dication, indicating that this product was formed in high amount. Nevertheless, bands that can be correlated to phenazine-like segments and 1,4-phenylenediamine repeat units (PANI like segments) are also observed. The very low EPR signal indicates that diamagnetic species are predominant. All results are compared to those obtained by anilinium-MMT chemically oxidized by persulfate and the differences are pointed out. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis and spectroscopic characterization of polymer and oligomers of ortho-phenylenediamine

Poly(ortho-phenylenediamine) and oligomers of ortho-phenylenediamine were chemically synthesized and characterized by UV-vis, (1)H and (13)C NMR, FTIR and resonance Raman spectroscopies. Polymerization of ortho-phenylenediamine in HCl medium with ammonium persulfate only leads the trimer compound, in disagreement with some previous reports. Nevertheless, in acetic acid medium it was possible to prepare a polymer constituted by ladder phenazinic segments with different protonation levels and quinonediimine rings (polyaniline-like). X-ray absorption at N K-edge (N K XANES), X-ray photoelectron (XPS) and Electron paramagnetic resonance (EPR) spectroscopies were used to determine the different kinds of nitrogen presents in this class of polymer. N K XANES spectrum of poly(ortho-phenylenediamine) shows the band of -N=nitrogen of non-protonated phenazinic rings at 398.2 eV. In addition, XPS and N K XANES data confirm the presence of different types of protonated nitrogens in the polymeric poly(ortho-phenylenediamine) chain and the EPR spectrum shows that the polymer has a very weak polaronic signal. (C) 2009 Elsevier Ltd. All rights reserved.

Structure of chemically prepared poly-(para-phenylenediamine) investigated by spectroscopic techniques

The structure of chemically prepared poly-p-phenylenediamine (PpPD) was investigated by Resonance Raman (RR), FTIR, UV-VIS-NIR, X-ray photoelectron (XPS), X-ray Absorption at Nitrogen K edge (N K XANES), and Electron paramagnetic Resonance (EPR) spectroscopies. XPS, EPR and N K XANES data reveal that polymeric structure is formed mainly by radical cations and dication nitrogens. It excludes the possibility that PpPD chains have azo or phenazinic nitrogens, as commonly is supposed in the literature. The RR spectrum of PpPD shows two characteristic bands at 1527 cm(-1) and 1590 cm(-1) that were assigned to nu C=N and nu C=C of dication units, respectively, similar to polyaniline in pernigraniline base form. The presence of radical cations was confirmed by Raman data owing to the presence of bands at 1325/1370 cm(-1), characteristic of nu C-N of polaronic segments. Thus, all results indicate that PpPD has a doped PANT-like structure, with semi-quinoid and quinoid rings, and has no phenazinic rings, as observed for poly-o-phenylenediamine. (C) 2009 Elsevier Ltd. All rights reserved.

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

SEM, EPR and ToF-SIMS analyses applied to unravel the technology employed for pottery-making by pre-colonial Indian tribes from Pantanal, Brazil

The present work aims at elucidating the technology applied in the fabrication of ceramic objects by the ancient ceramists that inhabited the western border of Pantanal, Mato-Grosso do Sul, with the help of a multidisciplinary approach making use of chemical and physical methods of analysis. The potshards under study show the presence of different types of additives, as determined by scanning electron microscopy (SEM) and time of flight secondary ion mass spectrometry (ToF-SIMS). The dispersion of the additives within the ceramic matrix was also addressed by SEM, which shed light on the mounting technique used by the potters to assemble the ceramic vessels. Moreover, the tensile strength conferred to the pottery by the use of a specific type of additive was evaluated by applying a mechanical test. These results were correlated with the firing temperature of the potshards, determined by means of electron paramagnetic resonance (EPR). (C) 2010 Elsevier Ltd. All rights reserved.

A novel nanostructured composite formed by interaction of copper octa(3-aminopropyl)octasilsesquioxane with azide ligands: Preparation, characterization and a voltammetric application

This study presents the preparation, characterization and application of copper octa(3-aminopropyl)octasilsesquioxane following its subsequent reaction with azide ions (ASCA). The precursor (AC) and the novel compound (ASCA) were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), scanning electronic microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analyses and voltammetric technique. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E(1/2)(ox)) = 0.30 V and an irreversible process at 1.1 V (vs. Ag/AgCl; NaCl 1.0 M; v = 20 mV s(-1)). The material is very sensitive to nitrite concentrations. The modified graphite paste electrode (GPE-ASCA) gives a linear range from 1.0 x 10(-4) to 4.0 x 10(-3) mol L(-1) for the determination of nitrite, with a detection limit of 2.1 x 10(-4) mol L(-1) and the amperometric sensitivity of 8.04 mA/mol L(-1). (C) 2010 Elsevier Ltd. All rights reserved.

Magnetic properties of synthetic eumelanin - Preliminary results

We report an experimental and theoretical study of magnetic properties of synthetic eumelanin. The magnetization curves are determined by using both a vibrating sample magnetometer and a superconducting quantum interferometer device in an extended range of magnetic fields ranging from -10 kOe to 10 kOe at different temperatures. We find that the eumelanin magnetization can be qualitatively explained in terms of a simple model of dipolar spheres with an intrinsic magnetic moment. The latter one is experimentally measured by using X-band electron paramagnetic resonance. Our findings indicate that synthetic melanins are superparamagnetic.

Experimental and theoretical correlation of very intense visible green photoluminescence in BaZrO3 powders

Very intense visible green photoluminescence (PL) was observed at room temperature in structurally ordered-disordered BaZrO3 powders. Ab initio calculations, ultraviolet-visible absorption spectroscopy, electron paramagnetic resonance, and PL were performed. Theoretical and experimental results showed that local defects in the cubic structure caused by [ZrO5 center dot V-O(z)] complex clusters, where V-O(z) = V-O(x), V-O(center dot), and V-O(center dot center dot), play an important role in the formation of hole-electron pairs, giving rise to a charge gradient in the structure which is responsible for PL emission. (c) 2008 American Institute of Physics.