On the conformal geometry of transverse Riemann–Lorentz manifolds

Physical reasons suggested in [J.B. Hartle, S.W. Hawking, Wave function of the universe, Phys. Rev. D41 (1990) 1815–1834] for the Quantum Gravity Problem lead us to study type-changing metrics on a manifold. The most interesting cases are Transverse Riemann–Lorentz Manifolds. Here we study the conformal geometry of such manifolds.     

On the Ligand‐to‐Metal Charge‐Transfer Photochemistry of the Copper(II) Complexes of Quercetin and Rutin

In contrast to the UV‐photoinduced ligand photoionization of the flavonoid complexes of Fe^III, redox reactions initiated in ligand‐to‐metal charge‐transfer excited states were observed on irradiation of the quercetin ( 1 ) and rutin ( 2 ) complexes of Cu^II. Solutions of complexes with stoichiometries [Cu^IIL₂] (L=quercetin, rutin) and [Cu^II₂L_n] (n=1, L=quercetin; n=3, L=rutin) were flash‐irradiated at 351 nm. Transient spectra observed in these experiments showed the formation of radical ligands corresponding to the one‐electron oxidation of L and the reduction of Cu^II to Cu^I. The radical ligands remained coordinated to the Cu^I centers, and the substitution reactions replacing them by solvent occurred with lifetimes τ<350 ns. These are lifetimes shorter than the known lifetimes (τ>1 ms) of the quercetin and rutin radical's decay.     

Efficient polymers in conjunction with membranes to remove As(V) generated in situ by electrocatalytic oxidation

Electrochemistry and ultrafiltration membrane methods (electro‐oxidation and liquid phase polymer based retention technique LPR, respectively) were coupled to remove As(III) inorganic species from aqueous solutions. Our main objective was to achieve an efficient extraction of arsenic species by associating a polymer‐assisted liquid phase retention procedure, based on the As(V) adsorption properties of cationic water‐soluble polymers, with the electrocatalytic oxidation process of As(III) into its more easily removable analog As(V). The exhaustive oxidation of As(III)–As(V) was readily performed in high yield at iridium oxide film modified carbon felt electrodes in the presence of different water‐soluble poly(quaternary ammonium) salts acting also as supporting electrolyte. The progress of the macro‐scale oxidation of As(III)–As(V) was followed using iridium oxide film modified glassy carbon electrodes. Finally, a study on arsenic retention by LPR‐technique performed on fully oxidized solutions of arsenic, showing that complete (100%) retention of the arsenic could be achieved using a 20:1 polyammonium:As(III) mole ratio. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of stir-bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry for the analysis of musks in vegetables and amended soils

The aim of this study was to develop a sensitive and environment-friendly method based on stir-bar sorptive extraction (SBSE) followed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) to determine 8 synthetic musks (musk ambrette, musk ketone, celestolide, tonalide, galaxolide, phantolide, traseolide, and cashmeran) in vegetables (lettuce, carrot, and pepper) and amended soil samples. In a first step sorptive extraction was studied both in the headspace (HSSE) and in the immerse mode (SBSE). The best results were obtained in the immersion mode which was further studied. The influence of the main factors: methanol (20%) and NaCl addition (0%), extraction temperature (40 °C) and time (180 min), extraction solvent volume (9 mL) and stirring rate (600 rpm) on the efficiency of SBSE was evaluated by means of experimental designs. In the case of TD, desorption time (10 min), desorption temperature (300 °C), cryo-focusing temperature (−30 °C), vent flow (75 mL/min) and vent pressure (7.2 psi) were studied using both a fractioned factorial design and a central composite design (CCD). The method was validated in terms of apparent recoveries (AR%), method detection limits (MDLs) and precision at two different concentration levels. Although quantification using instrumental calibration rendered odd results in most of the cases, satisfactory recoveries (74–126%) were obtained in the case of matrix-matched calibration approach for all of the analytes and matrices studied at the two concentration levels evaluated. MDLs in the range of 0.01–0.8 ng/g and 0.01–1.1 ng/g were obtained for vegetables and amended soil samples, respectively. RSD values within 1–23% were obtained for all the analytes and matrices. Finally, the method was applied to the determination of musks in vegetable and amended soil samples.     

CaMn(1-x)Nb(x)O3 (x < or = 0.08) perovskite-type phases as promising new high-temperature n-type thermoelectric materials

Perovskite-type CaMn(1-x)Nb(x)O(3+/-delta) (x = 0.02, 0.05, and 0.08) compounds were synthesized by applying both a "chimie douce" (SC) synthesis and a classical solid state reaction (SSR) method. The crystallographic parameters of the resulting phases were determined from X-ray, electron, and neutron diffraction data. The manganese oxidations states (Mn(4+)/Mn(3+)) were investigated by X-ray photoemission spectroscopy. The orthorhombic CaMn(1-x)Nb(x)O(3+/-delta) (x = 0.02, 0.05, and 0.08) phases were studied in terms of their high-temperature thermoelectric properties (Seebeck coefficient, electrical resistivity, and thermal conductivity). Differences in electrical transport and thermal properties can be correlated with different microstructures obtained by the two synthesis methods. In the high-temperature range, the electron-doped manganate phases exhibit large absolute Seebeck coefficient and low electrical resistivity values, resulting in a high power factor, PF (e.g., for x = 0.05, S(1000K) = -180 microV K(-1), rho(1000K) = 16.8 mohms cm, and PF > 1.90 x 10(-4) W m(-1) K(-2) for 450 K < T < 1070 K). Furthermore, lower thermal conductivity values are achieved for the SC-derived phases (kappa < 1 W m(-1) K(-1)) compared to the SSR compounds. High power factors combined with low thermal conductivity (leading to ZT values > 0.3) make these phases the best perovskitic candidates as n-type polycrystalline thermoelectric materials operating in air at high temperatures.     

Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations

A model for studying polar-pi interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (DeltaG(not equal) vs. sigma(0)). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.     

Electrooxidation of Nitrite Mediated by Cu‐x‐Tetraaminophenylporphyrin (x=2, 3, and 4) Glassy Carbon‐Modified Electrodes: Effect of Substituent Position

A study of glassy carbon electrodes modified with poly‐Cu‐x‐tetraaminophenylporphyrin (TAPP) (x=2, 3, and 4) toward the electrooxidation of nitrite is reported. The position of the amino group influences the degree of electropolymerization and the response toward the electrooxidation of nitrite. The influence of pH on the electrocatalytic oxidation of nitrite was also studied, finding that the activity is strongly pH‐dependent. For each system (polymeric porphyrins, poly‐Cu‐2‐TAPP, poly‐Cu‐3‐TAPP, and poly‐Cu‐4‐TAPP), the behavior of the modified electrode as amperometric nitrite sensor was studied at the best pH response, finding a linear correlation over a wide range of concentrations for poly‐Cu‐3‐TAPP. With poly‐Cu‐2‐TAPP, the range is smaller, and there is no linear relationship for poly‐Cu‐4‐TAPP. The plot of I_p vs. the square root of the scan rate shows a linear relationship for all the polymer systems, indicating that the electrooxidation of nitrite in the modified electrodes is a process controlled by diffusion. The Tafel slope was calculated, indicating that the determining step in the electrooxidation of nitrite varies depending on the position of the substituent, showing a dramatic change in the nature of the active sites.     

Spectral methods based on Hermite functions for linear hyperbolic equations

We consider the approximation by spectral and pseudo‐spectral methods of the solution of the Cauchy problem for a scalar linear hyperbolic equation in one space dimension posed in the whole real line. To deal with the fact that the domain of the equation is unbounded, we use Hermite functions as orthogonal basis. Under certain conditions on the coefficients of the equation, we prove the spectral convergence rate of the approximate solutions for regular initial data in a weighted space related to the Hermite functions. Numerical evidence of this convergence is also presented. © 2011 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2012