Saturation recovery EPR and ELDOR at W-band for spin labels

A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE₀₁₁ cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW^−1/2 with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T_1e previously reported for these molecules in the range of 2–35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T₁ values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524–9529]. The values of T_1e decrease at 94 GHz relative to values at 35 GHz.     

Effect of temperature on spectroscopic features relevant to laser performance of YVO4:Tm3+, GdVO4:Tm3+, and LuVO4:Tm3+ crystals

Optical spectra and luminescence decay curves were measured for thulium-doped YVO(4), GdVO(4), and LuVO(4) single crystals as a function of temperature in the 300-670 K temperature region. In spite of structural similarity, the three systems studied display significantly different transition intensities and nonradiative relaxation rates. It was found, in particular, that the peak value of the pump band absorption intensity diminishes by about 30% for Tm:YVO(4) and Tm:GdVO(4), and the effective emission cross section for the laser transition of Tm(3+) diminishes by a factor of 2 roughly when temperature increases from 300 to 500 K. An unusually small quantum efficiency of the upper laser level in Tm:LuVO(4) has been derived from the analysis of luminescence decay curves.     

Some remarks on the Hook formula

Summary Without the Frame-Robinson-Thral hook formula we establish some divisibility properties of degrees of irreducible representations of the symmetric group.

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Riassunto Senza utilizzare una nota formula di Frame-Robinson-Thrall stabiliamo alcune proprietà di divisibilità di gradi di rappresentazioni irriducibili del grupposimmetrico.

     

Flow injection analysis simulations and diffusion coefficient determination by stochastic and deterministic optimization methods

Stochastic and deterministic simulations of dispersion in cylindrical channels on the Poiseuille flow have been presented. The random walk (stochastic) and the uniform dispersion (deterministic) models have been used for computations of flow injection analysis responses. These methods coupled with the genetic algorithm and the Levenberg–Marquardt optimization methods, respectively, have been applied for determination of diffusion coefficients. The diffusion coefficients of fluorescein sodium, potassium hexacyanoferrate and potassium dichromate have been determined by means of the presented methods and FIA responses that are available in literature. The best-fit results agree with each other and with experimental data thus validating both presented approaches.     

Die keimbildungskinetik im glasigen selen mit der beimischung des jods

The rate of crystallization of vitreous selenium containing 2 at.% of iodine was studied by calorimetric method in the temperature range 60–90°C. The obtained results satisfy an equation of Avrami. It was found that the exponential parameter z in this equation decreases as the temperature of crystallization increases. It was assumed in the discussion that the parameter z does not depend on the number of all processes occurring during nucleation. It depends only on slowly occurring processes. The increase of temperature probably causes a decrease of the number of slow processes and thus the value of the parameter z is diminished.The activation energy of crystallization is equal to $\text{E}{}_{\mathrm{kr}}\text{= 80}\text{kJ}\text{mol}$ with the standard deviation $\text{s}{}_{\mathrm{E}}\text{= 5.0}\text{kJ}\text{mol}$.     

On the Levi and Lebesgue properties

The paper is devoted to a question if the Levi property is preserved by direct sums and quotients. The three-space problem for the Levi and Lebesgue properties in topological Riesz spaces is also investigated.     

Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

Ion-molecule reactions of Me₂S₂ with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction (m/z 47), S_N2 (m/z 79), and E2 elimination – addition sequence of reactions (m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent S_N2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results.

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Graphical Abstract ?

     

Application of image analysis technique for the determination of thiophanate methyl by thin-layer chromatography

A simple and convenient thin-layer chromatography (TLC) method combined with image analysis technique was developed to determine thiophanate methyl. The detection of pesticide was based on iodine–azide reaction. Digital images of TLC plate chromatograms were analysed using TLSee software, and quantitative analysis was conducted. The linearity (0.3–3.0 µg per spot), sensitivity, accuracy and precision of the system were investigated.