Retention of arsenate using genetically modified coryneform bacteria and determination of arsenic in solid samples by ICP-MS

A novel method for the retention of arsenate [As(V)] combining time-controlled solid-phase extraction with living bacterial biomass is presented. As(V) retention was carried out by exposing the extractant, consisting of a living double-mutant of Corynebacterium glutamicum strain ArsC1-C2, to the sample for a retention time of 1-7 min, before the arsenic distribution equilibrium between the sample solution and the extractant was established. The amount of As(V) retained in the biomass was measured by inductively coupled plasma-mass spectrometry (ICP-MS) after the sample had been treated with nitric acid. A theoretical model of the retention process was developed to describe the experimental retention-time profiles obtained with the bacterial cells. This relationship provided a feasible quantification of the retention process before steady-state was reached, providing that the agitation conditions and the retention time had been controlled. An analytical procedure for the retention/quantification of As(V) was then developed; the detection limit was 0.1 ng As(V) mL⁻¹ and the relative standard deviation 2.4-3.0%. The maximum effective retention capacity for As(V) was about 12.5 mg As (g biomass)⁻¹. The developed procedure was applied to the determination of total arsenic in coal fly ash, using a sample that had undergone oxidative pre-treatment.     

Changes in fluorescent emission due to non-covalent interactions as a general detection procedure for thin-layer chromatography

Changes in fluorescence emission due to non-covalent analyte-fluorophore interactions in silica gel plates are studied and used as a general detection procedure for thin-layer chromatography (TLC). The presence of the analyte modifies the microenvironment of the fluorophore and thus changes the balance between radiative (k(r)) and non-radiative (k(nr)) emission constants. A model is proposed for analyte-fluorophore induced electrostatic interactions, which depend on analyte polarizability and are responsible for fluorescence enhancements. As consequence of these induced interactions, the analyte creates an apolar environment that prevents non-fluorescent decay mechanisms, decreasing k(nr). On the other hand, the effect of an increase in refractive index on k(r) is investigated, as it contributes to some extent to fluorescence enhancements in silica gel medium. Changes in fluorescence emission should be regarded as a general property of fluorophores in the presence of analytes, and criteria that fluorophores should meet to be used as sensitive TLC probes are discussed here.     

Postoptimal analysis in a multi-attribute decision model for restoring contaminated aquatic ecosystems

We describe the evaluation module of the MOIRA system, developed to identify optimal remedial strategies for restoring radionuclide contaminated aquatic ecosystems and drainage areas. This module includes a multiparametric sensitivity analysis, which is based on a multi-attribute additive value model, aimed at identifying optimal remedial strategies for restoring aquatic ecosystems contaminated by radionuclides. We introduce the sensitivity analysis to check the robustness of the conclusions on the inputs. This provides insights into the problem in the sense of making better use of the available information. This analysis is focused on judgemental inputs, imprecise value functions on attributes and imprecise scaling factors or weights for their aggregation. These are of utmost importance in determining the optimal countermeasures.     

Synthesis and Functionalization of Allenes by Direct Pd‐Catalyzed Organolithium Cross‐Coupling

A palladium‐catalyzed cross‐coupling between in situ generated allenyl/propargyl‐lithium species and aryl bromides to yield highly functionalized allenes is reported. The direct and selective formation of allenic products preventing the corresponding isomeric propargylic product is accomplished by the choice of SPhos or XPhos based Pd catalysts. The methodology avoids the prior transmetalation to other transition metals or reverse approaches that required prefunctionalization of substrates with leaving groups, resulting in a fast and efficient approach for the synthesis of tri‐ and tetrasubstituted allenes. Experimental and theoretical studies on the mechanism show catalyst control of selectivity in this allene formation.     

Double-Delta Potentials: One Dimensional Scattering The Casimir Effect and Kink Fluctuations

The path is explored between one-dimensional scattering through Dirac-δ walls and one-dimensional quantum field theories defined on a finite length interval with Dirichlet boundary conditions. It is found that two δ’s are related to the Casimir effect whereas two δ’s plus the first transparent P?sch-Teller well arise in the context of the sine-Gordon kink fluctuations, both phenomena subjected to Dirichlet boundary conditions. One or two delta wells will be also explored in order to describe absorbent plates, even though the wells lead to non unitary Quantum Field Theories.     

On saturation effects in the Neumann boundary control of elliptic optimal control problems

A Neumann boundary control problem for a linear-quadratic elliptic optimal control problem in a polygonal domain is investigated. The main goal is to show an optimal approximation order for discretized problems after a postprocessing process. It turns out that two saturation processes occur: The regularity of the boundary data of the adjoint is limited if the largest angle of the polygon is at least 2π/3. Moreover, piecewise linear finite elements cannot guarantee the optimal order, if the largest angle of the polygon is greater than π/2. We will derive error estimates of order h ^α with α∈[1,2] depending on the largest angle and properties of the finite elements. Finally, numerical test illustrates the theoretical results.     

Optimization,Stability, and Entropy in Endoreversible Heat Engines

The stability of endoreversible heat engines has been extensively studied in the literature. In this paper, an alternative dynamic equations system was obtained by using restitution forces that bring the system back to the stationary state. The departing point is the assumption that the system has a stationary fixed point, along with a Taylor expansion in the first order of the input/output heat fluxes, without further specifications regarding the properties of the working fluid or the heat device specifications. Specific cases of the Newton and the phenomenological heat transfer laws in a Carnot-like heat engine model were analyzed. It was shown that the evolution of the trajectories toward the stationary state have relevant consequences on the performance of the system. A major role was played by the symmetries/asymmetries of the conductance ratio σhc of the heat transfer law associated with the input/output heat exchanges. Accordingly, three main behaviors were observed: (1) For small σhc values, the thermodynamic trajectories evolved near the endoreversible limit, improving the efficiency and power output values with a decrease in entropy generation; (2) for large σhc values, the thermodynamic trajectories evolved either near the Pareto front or near the endoreversible limit, and in both cases, they improved the efficiency and power values with a decrease in entropy generation; (3) for the symmetric case (σhc=1), the trajectories evolved either with increasing entropy generation tending toward the Pareto front or with a decrease in entropy generation tending toward the endoreversible limit. Moreover, it was shown that the total entropy generation can define a time scale for both the operation cycle time and the relaxation characteristic time.     

Holographic phase transitions with fundamental matter

The holographic dual of a finite-temperature gauge theory with a small number of flavors typically contains D-brane probes in a black hole background. At low temperature, the branes sit outside the black hole and the meson spectrum is discrete and possesses a mass gap. As the temperature increases, the branes approach a critical solution. Eventually, they fall into the horizon and a phase transition occurs. In the new phase, the meson spectrum is continuous and gapless. At large Nc and large 't Hooft coupling, we show that this phase transition is always first order. In confining theories with heavy quarks, it occurs above the deconfinement transition for the glue.