Radicals from the atmospheric pressure pyrolysis and oxidative pyrolysis of hydroquinone, catechol, and phenol

The burning of tobacco creates various types of free radicals that have been reported to be biologically active. Some radicals are transient but can initiate catalytic cycles that generate other free radicals. Other radicals are environmentally persistent and can exist in total particulate matter (TPM) for extended periods. In spite of their importance, little is known concerning the precursors of these radicals or under what pyrolysis/combustion conditions they are formed. We performed studies of the formation of radicals from the gas-phase pyrolysis and oxidative pyrolysis of hydroquinone (HQ) and catechol (CT) between 750 and 1000 °C and phenol from 500 to 1000 °C. The initial electron paramagnetic resonance (EPR) spectra were complex, indicating the presence of multiple radicals. Using matrix annealing and microwave power saturation techniques, phenoxyl, cyclopentadienyl, and peroxyl radicals were identifiable, but only cyclopentadienyl radicals were stable above 750 °C.

Synthesis, crystal structures, magnetic properties and catecholase activity of double phenoxido-bridged penta-coordinated dinuclear nickel(II) complexes derived from reduced Schiff-base ligands: mechanistic inference of catecholase activity

Three double phenoxido-bridged dinuclear nickel(II) complexes, namely [Ni-2(L-1)(2)(NCS)(2)] (1), [Ni-2(L-2)(2)(NCS)(2)] (2), and [Ni-2(L-3)(2)(NCS)(2)] (3) have been synthesized using the reduced tridentate Schiff-base ligands 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL1), 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL2), and 2-[1-(3-dimethylarnino-propylamino)-ethyl]-phenol (HL3), respectively. The coordination compounds have been characterized by X-ray structural analyses, magnetic-susceptibility measurements, and various spectroscopic methods. In all complexes, the nickel(II) ions are penta-coordinated in a square-pyramidal environment, which is severely distorted in the case of 1 (Addison parameter tau = 0.47) and 3 (tau = 0.29), while it is almost perfect for 2 (tau = 0.03). This arrangement leads to relatively strong antiferromagnetic interactions between the Ni(II) (S = 1) metal centers as mediated by double phenoxido bridges (with J values of -23.32 (1), -35.45 (2), and -34.02 (3) cm(3) K mol(-1), in the convention H = -2JS(1)S(2)). The catalytic activity of these Ni compounds has been investigated for the aerial oxidation of 3,5-di-tert-butylcatechol. Kinetic data analysis following Michaelis-Menten treatment reveals that the catecholase activity of the complexes is influenced by the flexibility of the ligand and also by the geometry around the metal ion. Electrospray ionization mass spectroscopy (ESI-MS) studies (in the positive mode) have been performed for all the coordination compounds in the presence of 3,5-DTBC to characterize potential complex-substrate intermediates. The mass-spectrometry data, corroborated by electron paramagnetic resonance (EPR) measurements, suggest that the metal centers are involved in the catecholase activity exhibited by the complexes.

Multivariate analysis of the dielectric response of materials modeled using networks of resistors and capacitors

We discuss the modeling of dielectric responses of electromagnetically excited networks which are composed of a mixture of capacitors and resistors. Such networks can be employed as lumped-parameter circuits to model the response of composite materials containing conductive and insulating grains. The dynamics of the excited network systems are studied using a state space model derived from a randomized incidence matrix. Time and frequency domain responses from synthetic data sets generated from state space models are analyzed for the purpose of estimating the fraction of capacitors in the network. Good results were obtained by using either the time-domain response to a pulse excitation or impedance data at selected frequencies. A chemometric framework based on a Successive Projections Algorithm (SPA) enables the construction of multiple linear regression (MLR) models which can efficiently determine the ratio of conductive to insulating components in composite material samples. The proposed method avoids restrictions commonly associated with Archie’s law, the application of percolation theory or Kohlrausch-Williams-Watts models and is applicable to experimental results generated by either time domain transient spectrometers or continuous-wave instruments. Furthermore, it is quite generic and applicable to tomography, acoustics as well as other spectroscopies such as nuclear magnetic resonance, electron paramagnetic resonance and, therefore, should be of general interest across the dielectrics community.

Nox2 B-loop peptide, Nox2ds, specifically inhibits the NADPH oxidase Nox2

In recent years, reactive oxygen species (ROS) derived from the vascular isoforms of NADPH oxidase, Nox1, Nox2, and Nox4, have been implicated in many cardiovascular pathologies. As a result, the selective inhibition of these isoforms is an area of intense current investigation. In this study, we postulated that Nox2ds, a peptidic inhibitor that mimics a sequence in the cytosolic B-loop of Nox2, would inhibit ROS production by the Nox2-. but not the Noxl- and Nox4-oxidase systems. To test our hypothesis, the inhibitory activity of Nox2ds was assessed in cell-free assays using reconstituted systems expressing the Nox2-, canonical or hybrid Nox1- or Nox4-oxidase. Our findings demonstrate that Nox2ds, but not its scrambled control, potently inhibited superoxide (O(2)(center dot-)) production in the Nox2 cell-free system, as assessed by the cytochrome c assay. Electron paramagnetic resonance confirmed that Nox2ds inhibits O(2)(center dot-) production by Nox2 oxidase. In contrast, Nox2ds did not inhibit ROS production by either Nox1- or Nox4-oxidase. These findings demonstrate that Nox2ds is a selective inhibitor of Nox2-oxidase and support its utility to elucidate the role of Nox2 in organ pathophysiology and its potential as a therapeutic agent. (C) 2011 Elsevier Inc. All rights reserved.

Angiotensin II modulates CD40 expression in vascular smooth muscle cells

The signalling pathway CD40/CD40L (CD40 ligand) plays an important role in atherosclerotic plaque formation and rupture. AngII (angiotensin II), which induces oxidative stress and inflammation, is also implicated in the progression of atherosclerosis. In the present study, we tested the hypothesis that AngII increases CD40/CD40L activity in vascular cells and that ROS (reactive oxygen species) are part of the signalling cascade that controls CD40/CD40L expression. Human CASMCs (coronary artery smooth muscle cells) in culture exposed to IL (interleukin)-1 beta or TNF-alpha (tumour necrosis factor-a) had increased superoxide generation and enhanced CD40 expression, detected by EPR (electron paramagnetic resonance) and immunoblotting respectively. Both phenomena were abolished by previous incubation with membrane-permeant antioxidants or cell transfection with P22(phox) antisense. AngII (50-200 nmol/l) induced an early and sustained increase in CD40 mRNA and protein expression in CASMCs, which was blocked by treatment with antioxidants. Increased CD40 expression led to enhanced activity of the pathway, as AngII-treated cells stimulated with recombinant CD40L released higher amounts of IL-8 and had increased COX-2 (cyclo-oxygenase-2) expression. We conclude that AngII stimulation of vascular cells leads to a ROS-dependent increase in CD40/CD40L signalling pathway activity. This phenomenon may be an important mechanism modulating the arterial injury observed in atherosclerosis-related vasculopathy.

Crystal growth and magnetic properties of tin selenide-doped europium Sn(1-x)Eu(x)Se

The growth and magnetic properties of Tin Selenide (SnSe) doped with Eu(2+) Sn(1-x)Eu(x)Se (x=2.5%) were investigated. Q-band (34 GHz) electron paramagnetic resonance measurements show that the site symmetry of Eu(2+) at 4.2 K is orthorhombic and the Lande factor was determined to be g=1.99 +/- 0.01. The exchange coupling between nearest-neighbor (NN) Eu(2+) ions was estimated from magnetization and magnetic-susceptibility measurements using a model that takes into account the magnetic contributions of single ions, pairs and triplets. The exchange interaction between Eu(2+) nearest neighbors was found to be antiferromagnetic with an estimated average value of J(p)/k(B) =-0.18 +/- 0.03 K. (C) 2009 Elsevier B.V. All rights reserved.

Thermoluminescence properties of natural zoisite mineral under gamma-irradiations and high temperature annealing

Natural silicate mineral of zoisite, Ca(2)Al(3)(SiO(4))(Si(2)O(7))O(OH), has been investigated concerning gamma-radiation, UV-radiation and high temperature annealing effects on thermoluminescence (TL). X-ray diffraction (XRD) measurement confirmed zoisite structure and X-ray fluorescence (XRF) analysis revealed besides Si, Al and Ca that are the main crystal components, other oxides of Fe, Mg, Cr, Na, K, Sr, Ti, Ba and Mn which are present in more than 0.05 wt%. The TL glow curve of natural sample contains (130-150), (340-370) and (435-475)degrees C peaks. Their shapes indicated a possibility that they are result of composition of two or more peaks strongly superposed, a fact confirmed by deconvolution method. Once pre-annealed at 600 degrees C for 1 h, the shape of the glow curves change and the zoisite acquires high sensitivity. Several peaks between 100 and 400 degrees C appear superposed, and the high temperature peak around 435 degrees C cannot be seen. The ultraviolet radiation, on the other hand, produces one TL peak around 130 degrees C and the second one around 200 degrees C and no more. (C) 2010 Elsevier B.V. All rights reserved.

Mechanisms of TL for production of the 230 degrees C peak in natural sodalite

The thermoluminescence (TL) peak in natural sodalite near 230 degrees C which appears only after submitted to thermal treatments and to gamma irradiation has been studied in parallel with electron paramagnetic resonance (EPR) spectrum appearing under the same procedure This study revealed a full correlation between the 230 degrees C TL peak and the eleven hyperfine lines from EPR spectrum In both case the centers disappear at the same temperature and are restored after gamma irradiation A complete model for the 230 C TL peak is presented and discussed In addition to the correlation and TL model specific characteristics of the TL peaks are described (C) 2010 Elsevier B V 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.

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.

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.