Measurement of L&agr; and Lß X-ray fluorescence cross sections in Er, Ta, W and Au by 16.896–59.543 keV photons

La and Lb X-ray fluorescence cross sections in Er, Ta, W and Au at excitation energies of 16.896, 22.581, 25.770, 32.890, 38.184, 43.949, 50.214 and 59.5 keV were investigated. Measurements were made using a low energy Si(Li) detector coupled to a model 4096 computerized multi-channel analyser. The experimental results were compared with the theoretically calculated values of L X-rays fluorescence cross sections and other experimental results. Good agreement was observed between experimental and theoretical values.     

Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state

A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption systems.     

A femtosecond study of the infrared-driven cis-trans isomerization of nitrous acid (HONO)

We investigate the dynamics and mechanism of the IR-driven cis-trans isomerization of nitrous acid (HONO) in a low-temperature krypton matrix applying ultrafast time resolved IR spectroscopy. After excitation of the OH-stretching mode the trans HONO state decays biexponentially on a 8 and 260 ps time scale. The initially excited cis HONO state decays on a 20 ps time scale. Cis HONO isomerizes with 10% quantum yield on a 20 ps time scale to trans HONO. The quantum yield we observe is significantly smaller than the previously reported 100%, which could imply that additional, much slower reaction channels exist. We furthermore developed a four-dimensional model of the system, which includes the three proton intramolecular degrees of freedom of HONO fully quantum mechanically and one intermolecular translational degree of freedom of the molecule in the crystal cage. We find that cis-trans isomerization necessarily is accompanied by a translation of the molecule as a whole in the crystal cage. The translational degree of freedom tunes the intramolecular proton states of HONO with respect to each other. When resonances occur, the proton states might couple and transfer population. We suggest a possible reaction pathway, where the cis OH-stretch excited state first couples to a high cis torsional mode, which then may transfer almost instantaneously to the trans side. The model qualitatively explains all experimental observations.     

Development of a radiochemical neutron activation analysis procedure for determination of rhenium in biological and environmental samples at ultratrace level

Summary Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed for accurate determination of rhenium in biological and environmental samples at the sub-ng ^. g^-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng ^. g^-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng ^. g^-1 was found. Significantly elevated values of Re, up to 90 ng ^. g^-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated ⁹⁹Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process.     

Selective Voltammetric Detection of Epinephrine in the Presence of Ascorbic Acid at Poly(4-Methoxyphenol)-Modified Electrode1

A gold electrode was modified with electropolymerized films of 4-methoxyphenol by its oxidative polymerization from an alkaline solution by cyclic voltammetry. The modified electrode was then used to determine epinephrine (EP) in the presence of a high concentration of ascorbic acid (AA) by differential pulse voltammetry. The peak positions as well as relative sensitivity EP/AA were affected by the potential window used for the polymerization. For polymerization between 0 and 1.3 V, the peak potentials recorded in a phosphate buffer solution (pH = 7.2) were 516 and 312 mV vs. Ag/AgCl for EP and AA, respectively. In addition the effects of pH and the type of electrolyte on the linearity range and detection limit are investigated. The detection limit for 3s-test is 0.1 M. The high selectivity and sensitivity for epinephrine was found to be due to charge discrimination/analyte accumulation.     

Phosphorylation of phospholipase D1 and the modulation of its interaction with RhoA by cAMP-dependent protein kinase

Agents that elevate cellular cAMP are known to inhibit the activation of phospholipase D (PLD). We investigated whether PLD can be phosphorylated by cAMP-dependent protein kinase (PKA) and PKA-mediated phosphorylation affects the interaction between PLD and RhoA, a membrane regulator of PLD. PLD1, but not PLD2 was found to be phosphorylated in vivo by the treatment of dibutyryl cAMP (dbcAMP) and in vitro by PKA. PKA inhibitor (KT5720) abolished the dbcAMP-induced phosphorylation of PLD1, but dibutyryl cGMP (dbcGMP) failed to phosphorylate PLD1. The association between PLD1 and Val14RhoA in an immunoprecipitation assay was abolished by both dbcAMP and dbcGMP. Moreover, RhoA but not PLD1 was dissociated from the membrane to the cytosolic fraction in dbcAMP-treated cells. These results suggest that both PLD1 and RhoA are phosphorylated by PKA and the interaction between PLD1 and RhoA is inhibited by the phosphorylation of RhoA rather than by the phosphorylation of PLD1.     

Determination of adsorptive properties of clay/water system: methylene blue sorption

In this study, adsorption of methylene blue onto clay was investigated. The effect of adsorption time and temperature on the adsorption process was studied. To reveal the adsorptive characteristics of the clay studied, porosity and BET surface area measurements were made. It was observed that the adsorption capacity decreases with increasing temperature, and adsorption equilibrium was attained within 1 h. It was found that the data fit well to Langmuir, Halsey, Henderson, and Harkins-Jura models but experimental data deviate significantly from BET and Freundlich models at especially high concentrations. Furthermore, isosteric adsorption enthalpy and entropy are calculated as -7.99 kJ mol(-1) and 25.41 JK(-1)mol(-1), respectively.     

Synthesis of highly enantioenriched all-carbon quaternary centers: conjugate additions of chiral organolithium nucleophiles to alpha,alpha-dinitrile beta,beta-disubstituted olefins

[reaction: see text]. Highly enantioenriched quaternary centers are obtained by the reaction of chiral lithiated intermediates complexed to (-)-sparteine with tetrasubstituted, alpha,alpha-dinitrile activated olefins. Lithiated N-Boc-N-Aryl benzylamine furnishes products with drs from 78:22 to 95:5, with ers exceeding 94:6. Lithiated N-Boc-N-Aryl allylamine reactants provide enecarbamate products with drs from 55:45 to 99:1, with ers ranging from 87:13 to 97:3.     

One-pot enantioselective formation of eight-membered rings from alkenyl Fischer carbene complexes and ketone enolates

Eight-membered carbocycles with up to five new stereogenic centers are enantioselectively obtained following a one-pot procedure that involves the coupling of three components: an alkenyl Fischer carbene complex, a ketone enolate, and allyl lithium.