In situ extended X-ray absorption fine structure study during selective alcohol oxidation over Pd/Al2O3 in supercritical carbon dioxide

High-pressure in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data are reported during the selective oxidation of benzyl alcohol to benzaldehyde in supercritical carbon dioxide over a Pd/Al(2)O(3) catalyst (shell impregnated). For this purpose, a continuous-flow system with a spectroscopic cell suitable for in situ X-ray absorption studies on heterogeneous catalysts up to 200 degrees C and 200 bar has been developed. Due to the high contribution of the dense fluid to the overall X-ray absorption, high stability of the process pressure is mandatory, particularly when recording EXAFS spectra. According to EXAFS and XANES results, the palladium particles were fully reduced after exposure to benzyl alcohol in scCO(2). In contrast to Pd-catalyzed liquid-phase oxidation, a higher oxygen tolerance of the catalyst was observed. Palladium was partially oxidized on the surface under typical reaction conditions (0.9 mol % benzyl alcohol/0.5 mol % O(2) in carbon dioxide), which gradually increased when the concentration of oxygen in the feed was raised. Both XANES and EXAFS data uncovered that palladium is mainly oxidized on the surface or within the outermost layers. These results are in accordance with simulations of the XANES data using the FEFF8.20 code (program for ab initio calculations on multiple scattering XAS) and EXAFS data fitting/simulation.     

Phase transformations in bulk nanostructured potassium niobiosilicate glasses

In potassium niobiosilicate (KNS) glasses, nanostructuring can be driven and controlled by thermal treatments at the glass transition temperature and/or by modulation of the chemical composition. The tight relationship between nanostructure and nonlinear optical properties suggests these bulk nanomaterials as an appealing route to nanophotonics. The focus of this paper is placed on assessing the phase transformations which occur in these materials upon annealing at the glass transition temperature and subsequent heating. High-temperature resolved X-ray diffraction (HTXRD) and high-resolution transmission electron microscopy (HRTEM) experiments are integrated with previously published results for in-depth insight. It will be shown that nanostructuring evolves from nucleation of niobium-rich nanocrystals, which are up to 20 nm large, uniformly distributed in the matrix bulk, and metastable. Formation kinetics as well as phase transformation of the nanocrystals are determined by the glass composition. Depending on it, nanocrystal nucleation can be preceded or not by phase separation, and the nanocrystals' phase transition can be of first or second order.     

Functionally relevant electric-field induced perturbations of the prosthetic group of yeast ferrocytochrome c mutants obtained from a vibronic analysis of low-temperature absorption spectra

We have measured the low temperature (T = 20 K) absorption spectra of the N52A, N52V, N52I, Y67F, and N52AY67F mutants of ferrous Saccharomyces cerevisiae (baker's yeast) cytochrome c. All the bands in the Q0- and Q(v)-band region are split, and the intensity distributions among the split bands are highly asymmetric. The spectra were analyzed by a decomposition into Voigtian profiles. The spectral parameters thus obtained were further analyzed in terms of the vibronic coupling model of Schweitzer-Stenner and Bigman (Schweitzer-Stenner, R.; Bigman, D. J. Phys. Chem. B 2001, 7064-7073) to identify parameters related to electronic and vibronic perturbations of the heme macrocycle. We report that the electronic perturbation is of B(1g) symmetry and reflects the heterogeneity of the electric field at the heme, that is, the difference between the gradients along the perpendicular N-Fe-N axis of the heme core. We found that all the investigated mutations substantially increase this electronic perturbation, so that the spectral properties become similar to those of horse heart cytochrome c. Moreover, the electronic perturbation was found to correlate nonlinearly with the enthalpy changes associated with the reduction of the heme iron. Group theoretical arguments are invoked to propose a simple model which explains how a perturbation of the obtained symmetry can stabilize the reduced state of the heme iron. Finally, vibronic coupling parameters obtained from the analysis of the Q(v)-band region suggest that the investigated mutations decrease the nonplanar deformations of the heme group. This finding was reproduced by a normal mode structural decomposition (NSD) analysis of the N52V and N52VY67F heme conformations obtained from a 1 ns molecular dynamics simulation. We argue that the reduced nonplanarity contributes to the stabilization of the reduced state.     

Determination of amphetamines in human urine by liquid chromatography with fluorimetric detection using a solid-phase extraction procedure

A precise and feasible HPLC method has been developed for the analysis of amphetamine (AMPH), methamphetamine (MAMPH) and methylenedioxymethamphetamine (MDMA, ecstasy) in human urine. A chromatographic run on a C8 Genesis (150 mm x 4.6 mm, 5 microm) column maintained at 30 degrees C lasts about 17 min, using a mobile phase composed of ACN (12%) and a pH 2.5 phosphate buffer (88%) containing 0.3% triethylamine. Mirtazapine was used as the internal standard. Good linearity was found in the 100-2000 ng/mL concentration range for AMPH and MAMPH and in the 12-2000 ng/mL concentration range for MDMA. The pretreatment of urine samples was carried out by means of a careful SPE procedure on C2 cartridges. The extraction yields were very satisfactory for all analytes, with average values greater than 97%. The leading conditions allowed the determination of AMPH, MAMPH and MDMA with satisfactory precision and accuracy. The method has been successfully applied to the determination of the analytes in urine of AMPH users.     

The VIP Experimental Limit on the Pauli Exclusion Principle Violation by Electrons

In this paper we describe an experimental test of the validity of the Pauli Exclusion Principle (for electrons) which is based on a straightforward idea put forward a few years ago by Ramberg and Snow (Phys. Lett. B 238:438, 1990). We perform a very accurate search of X-rays from the Pauli-forbidden atomic transitions of electrons in the already filled 1S shells of copper atoms. Although the experiment has a very simple structure, it poses deep conceptual and interpretational problems. Here we describe the experimental method and recent experimental results, which we interpret in the framework of quon theory. We also present future plans to upgrade the experimental apparatus using Silicon Drift Detectors.     

Regularity of line configurations

We show that in arithmetically-Gorenstein line arrangements with only planar singularities, each line intersects the same number of other lines. This number has an algebraic interpretation: it is the Castelnuovo–Mumford regularity of the coordinate ring of the arrangement.We also prove that every $(d?1)$-dimensional simplicial complex whose 0-th and 1-st homologies are trivial is the nerve complex of a suitable d-dimensional standard graded algebra of depth ≥3. This provides the converse of a recent result by Katzman, Lyubeznik and Zhang.     

Clustering dynamics in a class of normalised generalised gamma dependent priors

Normalised generalised gamma processes are random probability measures that induce nonparametric prior distributions widely used in Bayesian statistics, particularly for mixture modelling. We construct a class of dependent normalised generalised gamma priors induced by a stationary population model of Moran type, which exploits a generalised Pólya urn scheme associated with the prior. We study the asymptotic scaling for the dynamics of the number of clusters in the sample, which in turn provides a dynamic measure of diversity in the underlying population. The limit is formalised to be a positive non-stationary diffusion process which falls outside well-known families, with unbounded drift and an entrance boundary at the origin. We also introduce a new class of stationary positive diffusions, whose invariant measures are explicit and have power law tails, which approximate weakly the scaling limit.     

A fractional isoperimetric problem in the Wiener space

We introduce a notion of fractional perimeter in an abstract Wiener space and show that half-spaces are the only volume-constrained minimisers.     

Personal income tax reforms: A genetic algorithm approach

Given a settled reduction in the present level of tax revenue, and by exploring a very large combinatorial space of tax structures, in this paper we employ a genetic algorithm in order to determine the ‘best’ structure of a real world personal income tax that allows for the maximisation of the redistributive effect of the tax, while preventing all taxpayers being worse off than with the present tax structure. We take Italy as a case study.