The Effect of Organic Diluent on the Extraction of Eu(III) by HEH[EHP]

ABSTRACT

Because there are fewer tools available to probe the interactions therein, the effect of the fundamental chemistry of the organic diluent on solvent extraction equilibria has been under-characterized relative to the aqueous. As a result, diluents for solvent extraction are often selected for an application not for their utility as a medium for reaction, but for other (often equally) important reasons (like low flammability). To begin to improve this imbalance in the science, twenty different diluents have been used in a study of the extraction of radiotracer ^152/154Eu³⁺ from dilute nitric acid solutions using the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). To increase the utility of the study and to honor the memory of Professor Jan Rydberg, this investigation was conducted by a cadre of comparatively inexperienced separation scientists (who are as a result no longer inexperienced separation scientists) as a radioanalytical chemistry and solvent extraction educational exercise. Slope analysis was used to determine the apparent stoichiometry of the extracted metal complex. The results discussed in the following indicate that, while the pH dependence exhibits the expected three H⁺ exchanged per metal ion extracted, the extractant dependence suggests that the number of protonated extractant molecules in the extracted complex changes with the organic diluent. The experimentally observed “extractant dependency” ranges from 2.5 to 3.0 dimer equivalent molecules per extracted metal ion. Ironically, in the diluents exhibiting the highest apparent M:(HA)₃ stoichiometry, HEH[EHP] extracts Eu³⁺ less efficiently. Europium luminescence spectroscopy was used to probe for changes in the first coordination sphere of the complex in different diluents. A model and conceptual framework for understanding these observations is described.     

Choquet optimal set in biobjective combinatorial optimization

We study in this paper the generation of the Choquet optimal solutions of biobjective combinatorial optimization problems. Choquet optimal solutions are solutions that optimize a Choquet integral. The Choquet integral is used as an aggregation function, presenting different parameters, and allowing to take into account the interactions between the objectives. We develop a new property that characterizes the Choquet optimal solutions. From this property, a general method to easily generate these solutions in the case of two objectives is defined. We apply the method to two classical biobjective optimization combinatorial optimization problems: the biobjective knapsack problem and the biobjective minimum spanning tree problem. We show that Choquet optimal solutions that are not weighted sum optimal solutions represent only a small proportion of the Choquet optimal solutions and are located in a specific area of the objective space, but are much harder to compute than weighted sum optimal solutions.     

The multiobjective multidimensional knapsack problem: a survey and a new approach

The knapsack problem (KP) and its multidimensional version (MKP) are basic problems in combinatorial optimization. In this paper, we consider their multiobjective extension (MOKP and MOMKP), for which the aim is to obtain or approximate the set of efficient solutions. In the first step, we classify and briefly describe the existing works that are essentially based on the use of metaheuristics. In the second step, we propose the adaptation of the two‐phase Pareto local search (2PPLS) to the resolution of the MOMKP. With this aim, we use a very large scale neighborhood in the second phase of the method, that is the PLS. We compare our results with state‐of‐the‐art results and show that the results we obtained were never reached before by heuristics for biobjective instances. Finally, we consider the extension to three‐objective instances.     

Patterns in melanocytic lesions: impact of the geometry on growth and transport inside the epidermis

In glabrous skin, nevi and melanomas exhibit pigmented stripes during clinical dermoscopic examination. They find their origin in the basal layer geometry which periodically exhibits ridges, alternatively large (limiting ridges) and thin (intermediate ridges). However, nevus and melanoma lesions differ by the localization of the pigmented stripes along furrows or ridges of the epidermis surface. Here, we propose a biomechanical model of avascular tumour growth which takes into account this specific geometry in the epidermis where both kinds of lesions first appear. Simulations show a periodic distribution of tumour cells inside the lesion, with a global contour stretched out along the ridges. In order to be as close as possible to clinical observations, we also consider the melanin transport by the keratinocytes. Our simulations show that reasonable assumptions on melanocytic cell repartition in the ridges favour the limiting ridges of the basal compared with the intermediate ones in agreement with nevus observations but not really with melanomas. It raises the question of cell aggregation and repartition of melanocytic cells in acral melanomas and requires further biological studies of these cells in situ.     

Part 1. Qualitative comparison between polymer and monomer model compound sulfonation

The sulfonation kinetics of fluorine ended poly(ether ether ketone) (PEEK) in solution in 95.9% and 96.8% concentrated sulfuric acid was studied with the help of a model compound representative of the PEEK chain repeat unit. The reaction rate of the model compound sulfonation was found to be first order with respect to the aromatic ring to be sulfonated. Consequently, PEEK kinetic data were treated following a first order with respect to the unsulfonated repeat unit concentration. Two rate‐slowing effects were detected. They were attributed to ‘long range’ electronic effects resulting from the inductive nature of the fluorine atom, and from the electron‐withdrawing character of the grafted sulfonic acid group. © 2001 Society of Chemical Industry     

Comparison of the wound-activated transformation of caulerpenyne by invasive and noninvasive Caulerpa species of the Mediterranean

The invasive green alga, Caulerpa taxifolia, that has spread rapidly after its introduction into the Mediterranean and the North American Pacific, reacts to wounding by transforming its major metabolite caulerpenyne (1). This wound-activated reaction involves the transformation of the bis-enol acetate moiety of 1, releasing reactive 1,4-dialdehydes. The ability to perform this transformation is found also in both the noninvasive Mediterranean C. prolifera and the invasive C. racemosa. Trapping experiments, as well as transformation of the model substrate geranyl acetate, suggest that all three investigated Caulerpa spp. rely on esterases that act upon wounding of the algae by subsequently removing the three acetate residues of caulerpenyne. The resulting reactive 1,4-dialdehyde oxytoxin 2 (9) can be identified by liquid chromatography–mass spectrometry and is unstable in the wounded tissue. Caulerpenyne transformation occurs rapidly, and severe tissue damage caused degradation of more than 50% of the stored caulerpenyne within 1 min in all three algae. Prevention of the enzymatic reaction before extraction, by shock freezing the tissue with liquid nitrogen, was used for the determination of the caulerpenyne content in intact algae. It gives about twofold higher values compared to an established methanol extraction protocol. The speed and mechanism of the wound-activated transformation, as well as the caulerpenyne content in intact tissue of invasive and noninvasive Caulerpa spp., are comparable. Thus, this enzymatic , transformation, despite being fast and efficient, is likely not the key for the success of the investigated invasive species.     

Prebreakdown phenomena at high voltage in liquid nitrogen and comparison with mineral oil

This paper presents a study of prebreakdown phenomena (usually called streamers) occurring at high voltage in liquid nitrogen. A special cryostat has been constructed to allow dielectric measurements in liquid nitrogen up to 200 kV, and 0.5 MPa hydrostatic pressure. Streamers are detected and studied with various techniques: high speed visualization, streak camera, and recording of transient currents and emitted light. The propagation of positive and negative streamers is investigated at gap distances up to 80 mm. Streamers are then compared to similar phenomena observed in mineral oil. In liquid nitrogen, streamers are different compared to mineral oil. A transition from slow to fast positive streamers (velocity about 10 km/s) is observed at a threshold voltage below the breakdown voltage. The hydrostatic pressure has almost no influence on this phenomenon. Some experiments carried out with a solid barrier perpendicular to the gap axis are also presented. The practical consequences for the design of HV insulation in superconducting systems are then discussed.     

Characterisation and reaction to fire of “M5” rigid rod polymer fibres

In this work, the flammability properties of a new rigid rod polymer fibre are examined. This new fibre was called M5 and is formally poly[2,6-diimidazo[4,5-b:4,5-e]- pyridinylene–1,4(2,5-dihydroxy)phenylene or PIPD. In a first step, characterisation of PIPD (M5) by solid state NMR confirms the chemical composition of the fibre. The investigation of the fire performance of M5 fibers using the cone calorimeter has shown the excellent behaviour of M5 in comparison with poly-p-phenylenediamine-terephtalamide (PPTA). M5 fibre does not burn even in very severe conditions (flashover conditions). It can then be used where high level of safety is required. The investigation of its heat resistance shows that M5 degrades via exothermic reactions of 30% lower energy than PPTA and have a strong pyrolysis resistance which can explain, in part, its unique fire properties.     

Fiber optic applications of multiple quantum well electroabsorption modulators

Electroabsorption modulators (eam) have proved to be very attractive both as optical sources (monolithically integrated NRZ transmitters andrz pulse generators) as well as for very fast signal processing (demultiplexing, regeneration, wavelength conversion,...). Their design criteria, technology and implementation in future networks are reviewed, and the main issues are discussed.