Charge carrier mobility and concentration as a function of composition in AgPO3-AgI glasses

Conductivity data of the xAgI(1 - x)AgPO(3) system (0 ≤ x ≤ 0.5) were collected in the liquid and glassy states. The difference in the dependence of ionic conductivity on temperature below and above their glass transition temperatures (T(g)) is interpreted by a discontinuity in the charge carrier's mobility mechanisms. Charge carrier displacement occurs through an activated mechanism below T(g) and through a Vogel-Fulcher-Tammann-Hesse mechanism above this temperature. Fitting conductivity data with the proposed model allows one to determine separately the enthalpies of charge carrier formation and migration. For the five investigated compositions, the enthalpy of charge carrier formation is found to decrease, with x, from 0.86 to 0.2 eV, while the migration enthalpy remains constant at ≈0.14 eV. Based on these values, the charge carrier mobility and concentration in the glassy state can then be calculated. Mobility values at room temperature (≈10(-4) cm(2) V(-1) s(-1)) do not vary significantly with the AgI content and are in good agreement with those previously measured by the Hall-effect technique. The observed increase in ionic conductivity with x would thus only be due to an increase in the effective charge carrier concentration. Considering AgI as a weak electrolyte, the change in the effective charge carrier concentration is justified and is correlated to the partial free energy of silver iodide forming a regular solution with AgPO(3).     

Thermal stability evaluation of methylic biodiesel obtained for different oilseeds

Biodiesel is defined as a mixture of mono- or di-alquil esters of vegetable oil or animal fats. During long-term storage, oxidation caused by contact with air (autoxidation) presents a legitimate concern in relation to monitoring and maintaining fuel quality. Extensive oxidative degradation may compromise the quality by adversely affecting kinematic viscosity, acid value, or peroxide value. The oxidation susceptibility of biodiesel, due to the presence of triacilglycerides of poly-unsaturated fatty acids, was evaluated in this study. Samples of sunflower, castor, and soybean biodiesels were obtained through the transesterification reaction, with the intention of achieving the thermal stability study through thermogravimetrical analyses and differential scanning calorimetry high pressure. It was furthermore observed through thermogravimetry and pressure differential scanning calorimetry curves that castor biodiesel exhibited the highest thermal and oxidative stability.     

Crystallization and characterization of an inflammatory lectin purified from the seeds of Dioclea wilsonii

DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins.     

Dynamics on certain sets of stochastic matrices

We study iteration of polynomials on symmetric stochastic matrices. In particular, we focus on a certain one-parameter family of quadratic maps which exhibits chaotic behavior for a wide range of the parameters. The well-known dynamical behavior of the quadratic family on the interval, and its dependence on the parameter, is reproduced on the spectrum of the stochastic matrices. For certain subclasses of stochastic matrices the referred dynamical behavior is also obtained in the matrix entries. Since a stochastic matrix characterizes a Markov chain, we obtain a discrete dynamical system on the space of reversible Markov chains. Therefore, depending on the parameter, there are initial conditions for which the corresponding reversible Markov chains will lead under iteration to a fixed point, to a periodic point, or to an aperiodic point. Moreover, there are sensitivity to initial conditions and the coexistence of infinite repulsive periodic orbits, both features of chaos.     

A study of amino-protecting groups using the polarizable continuum model (PCM)

In order to better understand the performance of 1,2-dimethyl-5-acetyl barbituric acid (DMB) as an amino protecting group relative to 5,5-dimethylcyclohexane-1,3-dione (DMD), ab initio calculations were performed. pK_a calculations using the PCM model indicated that both molecules are more acidic in the enol form. Therefore, the protecting reaction of these molecules should involve the anions formed from the loss of a proton from the enol compounds. Contrary to what would be expected, the larger efficiency exhibited by the DMB molecule cannot be attributed to an extension of the electronic conjugation effect. In the absence of any other noticeable effect that could be responsible for the greater efficiency of the DMB molecule, we are inclined to believe that the difference could be accounted for by the presence of two independent centers of conjugation.This paper is dedicated to Jacopo Tomasi in recognition of his outstanding contribution to the field of computational chemistry in solution. The authors are honored to contribute to this volume; especially so for two of them (COS and MACN) who have the privilege of his friendship.Acknowledgements The authors would like to thank the Brazilian research agencies CNPq, CAPES and FAPERJ for the financial support. C. O. da Silva thanks the Dipartimento di Chimica e Chimica Industriale, University of Pisa, where the MCSCF calculations were performed.     

Theoretical and experimental analysis of ammonia ionic clusters produced by 252Cf fragment impact on an NH3 ice target

Positive and negatively charged ammonia clusters produced by the impact of (252)Cf fission fragments (FF) on an NH(3) ice target have been examined theoretical and experimentally. The ammonia clusters generated by (252)Cf FF show an exponential dependence of the cluster population on its mass, and the desorption yields for the positive (NH(3))(n)NH(4)(+) clusters are 1 order of magnitude higher than those for the negative (NH(3))(n)NH(2)(-) clusters. The experimental population analysis of (NH(3))(n)NH(4)(+) (n = 0-18) and (NH(3))(n)NH(2)(-) (n = 0-8) cluster series show a special stability at n = 4 and 16 and n = 2, 4, and 6, respectively. DFT/B3LYP calculations of the (NH(3))(0)(-)(8)NH(4)(+) clusters show that the structures of the more stable conformers follow a clear pattern: each additional NH(3) group makes a new hydrogen bond with one of the hydrogen atoms of an NH(3) unit already bound to the NH(4)(+) core. For the (NH(3))(0)(-)(8)NH(2)(-) clusters, the DFT/B3LYP calculations show that, within the calculation error, the more stable conformers follow a clear pattern for n = 1-6: each additional NH(3) group makes a new hydrogen bond to the NH(2)(-) core. For n = 7 and 8, the additional NH(3) groups bind to other NH(3) groups, probably because of the saturation of the NH(2)(-) core. Similar results were obtained at the MP2 level of calculation. A stability analysis was performed using the commonly defined stability function E(n)(-)(1) + E(n)(+1) - 2E(n), where E is the total energy of the cluster, including the zero point correction energy (E = E(t) + ZPE). The trend on the relative stability of the clusters presents an excellent agreement with the distribution of experimental cluster abundances. Moreover, the stability analysis predicts that the (NH(3))(4)NH(4)(+) and the even negative clusters [(NH(3))(n)NH(2)(-), n = 2, 4, and 6] should be the most stable ones, in perfect agreement with the experimental results.     

Analysis of signal fluctuations of Cortical Spreading Depression: Preliminary findings

In this work, we apply Detrended Fluctuation Analysis (DFA) to study the dynamics of electrical cortical activity in rats during the phenomenon of Cortical Spreading Depression (CSD), as well as the periods before and after this phenomenon. The characteristic of CSD is reduced electrical activity that occurs and spreads in the cerebral cortex after the application of electrical, chemical or mechanical stimulus. Our results show that the electrocorticogram signal shows long range temporal correlations and scaling behavior, except during the pre-CSD burst phase (significant increase of amplitude provoked by stimulus).     

Requirements for Efficient Raman Amplification and Dispersion Compensation Using Microstructured Optical Fibers

Abstract

The design and performance of microstructured optical fibers (MOFs) for simultaneous dispersion compensation and Raman amplification is numerically investigated. We studied a lumped Raman amplifier designed to compensate the signal loss and dispersion introduced by a 100-km, 16-channel C-band WDM link. The impairments induced by the nonlinearities caused by the small mode area of the designed MOF are investigated and the analysis is extended to include non-ideal factors such as excess background losses, splice loss, and the geometry variations during the fabrication process. The results are discussed and compared to those obtained for conventional dispersion compensating fibers (DCFs).     

Evaluation of the concentration of chemical elements in suspended particulate matter inside a small bronze and iron foundry industry,using a streaker sampler and EDXRF

The aim of this study was to determine and evaluate the temporal profiles of the concentration of chemical elements in the suspended particulate matter present inside a small bronze and an iron foundry industry. To collect the samples, we used a streaker sampler that separates particles with aerodynamic diameters smaller than 10 µm (PM₁₀) in two fractions: fine (particles with aerodynamic diameters less than 2.5 µm; PM_2.5) and coarse (between 2.5 µm and less than 10 µm; PM_10–2.5). The collection of samples was taken every 20 min during a total time of 8 and 5 h of molding and casting of bronze and iron, respectively. The samples collected in the form of strips on a filter (fine fraction) and an impactor (coarse fraction) were analyzed by the energy dispersive X‐ray fluorescence technique. In the excitation, an X‐ray tube with Mo target and Zr filter was used, operated at 30 mA/30 kV. For detecting the characteristic of X‐rays, a semiconductor Si(Li) detector was used, coupled to a multi‐channel spectrometer, with a 300 s excitation/detection time. The results of the temporal profiles of chemical element concentrations in coarse and fine fractions were discussed and compared with the maximum levels set by the Brazilian and international environmental agencies. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and Structure of the Dimeric Copper(II) Complex Tetrakis[<Emphasis Type="Italic">N</Emphasis>-thiazol-2-yl-(4-methylphenyl)sulfonamidate]dicopper(II)

Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of this complex was elucidated and is discussed. The compound crystallised in the monoclinic crystal system, P2₁/c space group with a = 17.3888(9), b = 16.3003(9), c = 18.3679(9) ? and β = 114.3640(10)°. Four bidentate sulfathiazolato anions bridge two metal centers in a paddle-wheel fashion, with the nitrogen atoms as donors to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?. Graphical Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of the product has been elucidated and is discussed. Sulfathiazolato anions act as bridging ligands to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?.