Kinetics and equilibrium parameters of Hg(II) adsorption on silica-dithizone

Sílica-dithizone (Sil-dtz) was synthesized and used to adsorb Hg(II) in solution at pH 6.0. Increasing the temperature accelerates the mass transfer of Hg(II) to the silica surface. The kinetic data were evaluated using the traditional pseudo-first-order Lagergren equation and an alternative Avrami kinetic equation. From the latter equation, two regions presenting distinct kinetic parameters were found, at 25 and 35 degrees C, and the use of the parameter n was also related to the determination of distinct kinetic orders. Variations of the adsorption kinetic rate in relation to the time and the temperature were also calculated and are discussed. The adsorption isotherms data were well fitted to the Freundlich model. Interestingly, good adsorption data correlation of the Langmuir model and experimental values was observed only at 45 and 50 degrees C, suggesting, for this temperature range, the formation of complexes with the proportion Hg:dithizone 1:1 on the silica surface.     

Electrocatalytic carboxylation of benzyl chlorides at silver cathodes in acetonitrile

Silver exhibits powerful electrocatalytic activities towards the reductive carboxylation of benzyl chlorides (RCl): in CO2-saturated CH3CN, reduction of RCl occurs at potentials that are about 0.6 V more positive than those of the same process at Hg or carbon electrodes and gives carboxylic acids in good to excellent yields.     

The Kernel of the Adjacency Matrix of a Rectangular Mesh

   Abstract. Given an m × n rectangular mesh, its adjacency matrix A , having only integer entries, may be interpreted as a map between vector spaces over an arbitrary field K . We describe the kernel of A : it is a direct sum of two natural subspaces whose dimensions are equal to

On the influence of laryngeal pathologies on acoustic and electroglottographic jitter measures

This study compared acoustic and electroglottographic (EGG) jitter from [a] vowels of 103 dysphonic speakers. The EGG recordings were chosen according to their intensity, signal-to-noise ratio, and percentage of unvoiced intervals, while acoustic signals were selected based on voicing detection and the reliability of jitter extraction. The agreement between jitter measures was expressed numerically as a normalized difference. In 63.1% (65/103) of the cases the differences fell within +/-22.5%. Positive differences above +22.5% were associated with increased acoustic jitter and occurred in 12.6% (13/103) of the speakers. These were, typically, cases of small nodular lesions without problems in the posterior larynx. On the other hand, substantial rises in EGG jitter leading to differences below -22.5% took place in 24.3% (25/103) of the speakers and were related to hyperfunctional voices, creaky-like voices, small laryngeal asymmetries affecting the arytenoids, or small-to-moderate glottal chinks. A clinically relevant outcome of the study was the possibility of detecting gentle laryngeal asymmetries among cases of large unilateral increase in EGG jitter. These asymmetries can be linked with vocal problems that are often overlooked in endoscopic examinations.     

Joint theoretical and experimental study of the gas‐phase elimination kinetics of tert‐butyl ester of carbamic,N, N‐dimethylcarbamic,N‐hydroxycarbamic acids and 1‐(tert‐butoxycarbonyl)‐imidazole

The gas‐phase elimination kinetics of the title compounds were carried out in a static reaction system and seasoned with allyl bromide. The working temperature and pressure ranges were 200–280 °C and 22–201.5 Torr, respectively. The reactions are homogeneous, unimolecular, and follow a first‐order rate law. These substrates produce isobutene and corresponding carbamic acid in the rate‐determining step. The unstable carbamic acid intermediate rapidly decarboxylates through a four‐membered cyclic transition state (TS) to give the corresponding organic nitrogen compound. The temperature dependence of the rate coefficients is expressed by the following Arrhenius equations: for tert‐butyl carbamate logk₁ (s^?1) = (13.02 ± 0.46) – (161.6 ± 4.7) kJ/mol(2.303 RT)^?1, for tert‐butyl N‐hydroxycarbamate logk₁ (s^?1) = (12.52 ± 0.11) – (147.8 ± 1.1) kJ/mol(2.303 RT)^?1, and for 1‐(tert‐butoxycarbonyl)‐imidazole logk₁ (s^?1) = (11.63 ± 0.21)–(134.9 ± 2.0) kJ/mol(2.303 RT)^?1. Theoretical studies of these elimination were performed at Møller–Plesset MP2/6‐31G and DFT B3LYP/6‐31G(d), B3LYP/6‐31G(d,p) levels of theory. The calculated bond orders, NBO charges, and synchronicity (Sy) indicate that these reactions are concerted, slightly asynchronous, and proceed through a six‐membered cyclic TS type. Results for estimated kinetic and thermodynamic parameters are discussed in terms of the proposed reaction mechanism and TS structure. Copyright © 2007 John Wiley & Sons, Ltd.     

Study of color centers produced in thulium doped YLF crystals irradiated by electron beam and femtosecond laser pulses

In this work, we report the influence of the presence of photochromic and color centers in the photobleaching of thulium ions blue emission in YLF (YLiF₄) crystals doped with 1 mol% Tm (3+). The samples were irradiated at room temperature both with electron beam and high intensity ultrashort pulses from a Ti:Sapphire CPA laser system. In both irradiations the production of photochromic and color centers was observed via the absorption bands in the UV and visible ranges. Pure LiF and pure and oxygen doped YLF crystals were used to identify the color centers produced and their optical properties. From a phenomenological model it was possible to study the interaction between color centers and thulium ions, and their effect in photobleaching and photodarkening behaviors. Finally, the blue up laser level population was computed using a rate equation analysis.     

Chemical isomerism as a key to explore free-energy landscapes in disordered matter

The effects of a minor chemical modification on the microscopic structure of a material in its glass and crystal phases are investigated by the concurrent use of neutron diffraction and computer simulation. Significant changes in short-, intermediate-, and long-range order are found, resulting from the change in molecular structure. These differences are explainable by a shift in the balance between directional and excluded-volume interactions.     

Magneto-optical trap and mass-separator system for the ultra-sensitive detection of <Superscript>135</Superscript>Cs and <Superscript>137</Superscript>Cs

We report the first magneto-optical trapping of radioactive ¹³⁵Cs and ¹³⁷Cs and a promising means for detecting these isotopes at ultra-sensitive levels by coupling a magneto-optical trap (MOT) to a mass separator. A sample containing both isotopes was placed in the source of a mass separator, ionized, mass-separated, and implanted in a Zr foil within the trapping cell. After implantation, atoms were released from the foil by inductive heating and then captured in a MOT that used large-diameter beams and a dry-film-coated cell to achieve high trapping efficiency. Trapped-atom numbers in the case of either isotope ranged from 10⁴ to 10⁷, as determined from the MOT fluorescence signal. Over this trapped-atom range, the MOT fluorescence signal was found to increase linearly with the number of atoms implanted in the foil and without isotopic bias to within 4%. In principle, this method can then provide a measurement of the ¹³⁷Cs/¹³⁵Cs ratio accurate to within 4% through the direct ratio of MOT fluorescence signals. The fluorescence signal from stable ¹³³Cs, when implanted and released from the foil, was suppressed relative to MOT signals by more than seven orders of magnitude when the system was tuned to trap ¹³⁵Cs or ¹³⁷Cs. When combined with the isotopic selectivity of ≥10⁵ for the mass separator, the overall suppression of ¹³³Cs is expected to exceed 10¹². At present our system delivers atoms from sample to MOT with an efficiency of 0.5%, has a trapped-atom detection limit of 4000 atoms, and achieves a sample-detection sensitivity of one million atoms. Received: 23 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +1-505/667-0440, E-mail: mdd@lanl.gov     

Mass spectrometric studies of cyclopentanol derivatives in the reductive coupling of alpha,beta-unsaturated ketones assisted by samarium diiodide

The mass spectrometric fragmentations of a series of cyclopentanol derivatives in positive fast-atom bombardment (FAB(+)) mode were investigated. The corresponding pathways proposed were confirmed by MS/MS data obtained using linked scans at constant B/E, high-resolution accurate mass data, and comparisons with corresponding information for a specifically deuterated molecule.