M?ssbauer characterization of the iron-sulfur clusters in Desulfovibrio vulgaris hydrogenase.

The periplasmic hydrogenase of Desulfovibrio vulgaris (Hildenbourough) is an all Fe-containing hydrogenase. It contains two ferredoxin type [4Fe-4S] clusters, termed the F clusters, and a catalytic H cluster. Recent X-ray crystallographic studies on two Fe hydrogenases revealed that the H cluster is composed of two sub-clusters, a [4Fe-4S] cluster ([4Fe-4S](H)) and a binuclear Fe cluster ([2Fe](H)), bridged by a cysteine sulfur. The aerobically purified D. vulgaris hydrogenase is stable in air. It is inactive and requires reductive activation. Upon reduction, the enzyme becomes sensitive to O(2), indicating that the reductive activation process is irreversible. Previous EPR investigations showed that upon reoxidation (under argon) the H cluster exhibits a rhombic EPR signal that is not seen in the as-purified enzyme, suggesting a conformational change in association with the reductive activation. For the purpose of gaining more information on the electronic properties of this unique H cluster and to understand further the reductive activation process, variable-temperature and variable-field M?ssbauer spectroscopy has been used to characterize the Fe-S clusters in D. vulgaris hydrogenase poised at different redox states generated during a reductive titration, and in the CO-reacted enzyme. The data were successfully decomposed into spectral components corresponding to the F and H clusters, and characteristic parameters describing the electronic and magnetic properties of the F and H clusters were obtained. Consistent with the X-ray crystallographic results, the spectra of the H cluster can be understood as originating from an exchange coupled [4Fe-4S]-[2Fe] system. In particular, detailed analysis of the data reveals that the reductive activation begins with reduction of the [4Fe-4S](H) cluster from the 2+ to the 1+ state, followed by transfer of the reducing equivalent from the [4Fe-4S](H) subcluster to the binuclear [2Fe](H) subcluster. The results also reveal that binding of exogenous CO to the H cluster affects significantly the exchange coupling between the [4Fe-4S](H) and the [2Fe](H) subclusters. Implication of such a CO binding effect is discussed.     

Coupling 3D and 1D fluid-structure interaction models for blood flow simulations

Three-dimensional (3D) simulations of blood flow in medium to large vessels are now a common practice. These models consist of the 3D Navier-Stokes equations for incompressible Newtonian fluids coupled with a model for the vessel wall structure. However, it is still computationally unaffordable to simulate very large sections, let alone the whole, of the human circulatory system with fully 3D fluid-structure interaction models. Thus truncated 3D regions have to be considered. Reduced models, one-dimensional (1D) or zero-dimensional (0D), can be used to approximate the remaining parts of the cardiovascular system at a low computational cost. These models have a lower level of accuracy, since they describe the evolution of averaged quantities, nevertheless they provide useful information which can be fed to the more complex model. More precisely, the 1D models describe the wave propagation nature of blood flow and coupled with the 3D models can act also as absorbing boundary conditions. We consider in this work the coupling of a 3D fluid-structure interaction model with a 1D hyperbolic model. We study the stability of the coupling and present some numerical results. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A strategy for parallel implementation of finite difference numerical schemes associated to evolution differential equations

Within the framework of parallel numerical treatment, there are many more results on stationary (or time-frozen) PDE's than on their evolution (or time-dependent) counterparts. This is justified as computer simulation of time flow – an intrinsically sequential phenomenum – leads naturally to a sequential algorithm, thus inhibiting any search for concurrent ones. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Counterion Nature and Alkylammonium Halide Adsorption Thermodynamics

Two surfactants were synthesized by reacting hydrogen halides (hydrogen chloride and hydrogen bromide) with 1-dodecylamine. The resultant cationic surfactants, 1-dodecylammonium chloride (DDAC) and 1-dodecylammonium bromide (DDAB), were characterized by NMR spectrometry and FTIR spectroscopy and data related to their adsorption at the fluid liquid/gas interface were obtained employing bubble surface tensiometry, in pure water and in HCl 0.1 M. Data did not fit well to Langmuir isotherm but Frumkin isotherm did adequately describe to process of adsorption. Adsorption isotherms, as well as data related to critical micelle concentration, CMC, indicated that in HCl 0.1 M, the presence of electrolytes and a common ion to DDAC decreased chloride solvation, changing surface packing and adsorption profile for this surfactant.     

Direct determination of sodium,potassium, chromium and vanadium in biodiesel fuel by tungsten coil atomic emission spectrometry

High levels of sodium and potassium can be present in biodiesel fuel and contribute to corrosion, reduced performance and shorter engine lifetime. On the other hand, trace amounts of chromium and vanadium can increase the emission of pollutants during biodiesel combustion. Sample viscosity, immiscibility with aqueous solutions and high carbon content can compromise biodiesel analyzes. In this work, tungsten filaments extracted from microscope light bulbs are used to successively decompose biodiesel's organic matrix, and atomize and excite the analytes to determine sodium, potassium, chromium and vanadium by tungsten coil atomic emission spectrometry (WCAES). No sample preparation other than simple dilution in methanol or ethanol is required. Direct analysis of 10-μL sample aliquots using heating cycles with less than 150 s results in limits of detection (LOD) as low as 20, 70, 70 and 90 μg kg⁻¹ for Na, K, Cr and V, respectively. The procedure's accuracy is checked by determining Na and K in a biodiesel reference sample and carrying out spike experiments for Cr and V. No statistically significant differences were observed between reference and determined values for all analytes at a 95% confidence level. The procedure was applied to three different biodiesel samples and concentrations between 6.08 and 95.6 mg kg⁻¹ for Na and K, and between 0.22 and 0.43 mg kg⁻¹ for V were obtained. The procedure is simple, fast and environmentally friendly. Small volumes of reagents, samples and gases are used and no residues are generated. Powers of detection are comparable to other traditional methods.     

Anderson localization in a disordered chain with a finite nonlinear response time

In this work, we investigate the competition of disorder, nonlinearity and non-adiabatic process on the wave packet dynamics in 1D. We follow the time evolution of the second moment of the wave packet distribution to characterize its spreading behavior. In order to describe the dynamical behavior of one-electron wave packets, we solve a discrete nonlinear Schr?dinger equation which effectively takes into account a diagonal disorder and a nonlinear contribution. Going beyond the adiabatic regime, we consider that the nonlinearity relaxes in time according to a Debye-like law. In the adiabatic regime, it has been recently demonstrated that the interplay of disorder and nonlinearity leads to a sub-diffusive spread of the wave packet. Here, we numerically demonstrate that no sub-diffusive spreading of the second moment of the wave packet distribution takes place when the finite response time of the nonlinearity is taken into account.     

Compatibility studies of trioxsalen with excipients by DSC,DTA, and FTIR

Psoralens are widely used for the treatment of psoriasis. Trioxsalen is a drug prescribed low-dose, belonging to the group of substituted psoralen. The aim of this study was to evaluate the compatibility of trioxsalen with pharmaceutical excipients used in the solid forms by analytical techniques. Binary mixtures between the trioxsalen and pharmaceutical excipients (namely, magnesium stearate, α-lactose, microcrystalline cellulose 102, pregelatinized starch, mannitol, sodium lauryl sulfate, sodium starch glycolate, and croscarmellose sodium) were examined. The trioxsalen–sodium lauryl sulfate mixture displayed some physical interaction based on the DTA and DSC results, but the FTIR study ruled out any chemical change.     

Cobalt as chemical modifier to improve chromium sensitivity and minimize matrix effects in tungsten coil atomic emission spectrometry

Cobalt is used as chemical modifier to improve sensitivity and minimize matrix effects in Cr determinations by tungsten coil atomic emission spectrometry (WCAES). The atomizer is a tungsten filament extracted from microscope light bulbs. A solid-state power supply and a handheld CCD-based spectrometer are also used in the instrumental setup. In the presence of 1000 mg L⁻¹ Co, WCAES limit of detection for Cr (λ = 425.4 nm) is calculated as 0.070 mg L⁻¹; a 10-fold improvement compared to determinations without Co modifier. The mechanism involved in such signal enhancement is similar to the one observed in ICP OES and ICP-MS determinations of As and Se in the presence of C. Cobalt increases the population of Cr⁺ by charge transfer reactions. In a second step, Cr⁺/e⁻ recombination takes place, which results in a larger population of excited-state Cr atoms. This alternative excitation route is energetically more efficient than heat transfer from atomizer and gas phase to analyte atoms. A linear dynamic range of 0.25–10 mg L⁻¹ and repeatability of 3.8% (RSD, n = 10) for a 2.0 mg L⁻¹ Cr solution are obtained with this strategy. The modifier high concentration also contributes to improving accuracy due to a matrix-matching effect. The method was applied to a certified reference material of Dogfish Muscle (DORM-2) and no statistically significant difference was observed between determined and certified Cr values at a 95% confidence level. Spike experiments with bottled water samples resulted in recoveries between 93% and 112%.     

Regiospecific synthesis of polyfluorinated heterocycles

A series of 10 heterocycles was obtained from the reaction of 1,1,1-trifluoro-4,4-diethoxy-3-buten-2-one and 1,1,1,2,2-pentafluoro-4,4-diethoxy-3-penten-2-one with different dinucleofiles (hydrazine, methyl hydrazine, hydroxylamine and sodium cyanide). The pyrazoles, 4,5-dihydroisoxazoles and pyrrolidinones polyfluoroalkyl substituted were obtained in moderate to good yields under mild conditions.