Electrochemical oxidation of hydrophobic compounds in aqueous micellar solutions and oil-in-water emulsions

The electrochemical oxidation of ferrocene (Fc) and tetrathiofulvalene (TTF) has been investigated in micelles and dodecane-in-water emulsions in order to compare the diffusional process involved in these systems. It is found that the diffusion coefficients of Fc and TTF, determined from the observed limiting currents at the rotating disc electrode, are governed by the solubilization equilibrium of the neutral substrates which are predominantly solubilized in the micelle or oil-droplet phase. In the emulsion, the cyclic voltammograms show that the current is controlled also by the rate constants of the substrate partition, which depend on the size of the emulsion droplets. The determination of the diffusion coefficients of Fc⁺ and TTF⁺, produced in situ by controlled potential electrolysis, showed that, except in SDS micellar solutions, the monocation radicals are solubilized mainly in the aqueous phase. As a result, the diffusion coefficients of the species involved in the redox system are different. In the case of TTF, the above results have a great influence upon the second oxidation step TTF⁺ → TTF²⁺. Indeed, the homogeneous solution reaction between TTF and the electrogenerated dication TTF²⁺ leads to the monocation TTF⁺ which diffuses more rapidly than its parent molecule TTF. The ratios of the two waves in cyclic and rotating disc electrode voltammetry show that the enhancement of the second wave depends mainly on the difference between the diffusion coefficients of TTF and TTF⁺ and that the nature of the solution or the size of the disperse phase has little influence upon the reaction rate of the homogeneous solution reaction.     

Microstructural investigation of magnetic CoFe2O4 nanowires inside carbon nanotubes by electron tomography

Magnetic nanowires of CoFe 2O4 were casted inside the channel of multiwall carbon nanotubes by mild chemical synthesis. A detailed investigation of these nanowires was performed using mainly the electron tomography technique; this study provides a complete characterization of their microstructure in terms of the spatial organization and the size distribution of individual particles forming the nanowire as well as its residual porosity. In particular, we have shown that the size of the CoFe 2O4 monocrystalline particles is closely dependent on the location of the particle within the nanotube, i.e., small particles close to the tube tip (5 nm) and bigger particles inside the tube channel (15 nm). As the theoretical critical size for superparamagnetic relaxation in CoFe 2O4 is estimated within the range of 4-9 nm, the size distribution obtained by 3D-TEM agrees with the Mossbauer study that suggests the presence of two different magnetic components inside the nanowire. We have shown also that, by using this preparation method and for this internal diameter of nanotube, the CoFe 2O4 nanowire exhibits a continuous structure along the tube, has a residual porosity of 38%, and can fill the tube at only 50%, parameters which influence in a significant manner the magnetic behavior of this system.     

Differential Effects of STCH and Stress-Inducible Hsp70 on the Stability and Maturation of NKCC2

Mutations in the Na-K-2Cl co-transporter NKCC2 lead to type I Bartter syndrome, a life-threatening kidney disease. We previously showed that export from the ER constitutes the limiting step in NKCC2 maturation and cell surface expression. Yet, the molecular mechanisms involved in this process remain obscure. Here, we report the identification of chaperone stress 70 protein (STCH) and the stress-inducible heat shock protein 70 (Hsp70), as two novel binding partners of the ER-resident form of NKCC2. STCH knock-down increased total NKCC2 expression whereas Hsp70 knock-down or its inhibition by YM-01 had the opposite effect. Accordingly, overexpressing of STCH and Hsp70 exerted opposite actions on total protein abundance of NKCC2 and its folding mutants. Cycloheximide chase assay showed that in cells over-expressing STCH, NKCC2 stability and maturation are heavily impaired. In contrast to STCH, Hsp70 co-expression increased NKCC2 maturation. Interestingly, treatment by protein degradation inhibitors revealed that in addition to the proteasome, the ER associated degradation (ERAD) of NKCC2 mediated by STCH, involves also the ER-to-lysosome-associated degradation pathway. In summary, our data are consistent with STCH and Hsp70 having differential and antagonistic effects with regard to NKCC2 biogenesis. These findings may have an impact on our understanding and potential treatment of diseases related to aberrant NKCC2 trafficking and expression.     

Preference-based English reverse auctions

This paper studies English reverse auctions within a unified framework for preference-based English reverse auctions. In this context, and particularly for electronic auctions, representing and handling the buyer?s preferences, so as to enable him/her to obtain the best possible outcome, is a major issue. Existing auction mechanisms, which are based on single or multi-attribute utility functions, are only able to represent transitive and complete preferences. It is well known, however, in the preference modeling literature that more general preference structures, allowing intransitivity and incomparability, are more appropriate to capture preferences. On the other hand, we must also consider properties on the evolution and, above all, on the outcome of any auction executed by an auction mechanism. These properties, as well as properties of non-dominance and fair competition defined for multiple criteria auctions, impose restrictions on the preference relation. This leaves room for interesting preference models to be implemented within English reverse auction mechanisms.     

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM-diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D_F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D_F compared to B, C_F, C_M and D_M increasing diuron-DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D_F and D_M. After equilibrium dialysis measurement of diuron-DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.     

Agglomeration for heap leaching: Equipment design, agglomerate quality control, and impact on the heap leach process

In preparation for demonstration heaps, the optimum conditions for agglomeration were determined through testwork. Producing a narrow size distribution of agglomerates in which few agglomerates were smaller than a rice grain, controlling the moisture content to 8–10%, and adding 0.3 kg/t of a commercial polymeric binder were the most important conditions for creating a porous packed bed, as determined from column tests.In a continuous operation, these conditions could be controlled effectively via the ore and solution feed rates to achieve a residence time of 2 min. This ensured that very large, poorly-shaped agglomerates formed before 1.5 min were fragmented into mid-size, well-shaped agglomerates, as well as allowed consolidation of small agglomerates into mid-size ones. Although the residence time of 2 min may not be the optimum for other ores, this study proved that the residence time was the same in a batch or continuous operation regardless of ore type or size distribution.Under the same conditions of agglomeration, the demonstration heaps did not validate the results of the column tests. The heaps were more compact because of the absence of structural support otherwise present in columns through the wall effect. These results highlight the value of demonstration heaps in the scale-up process.     

Empirical Study on Collaborative Writing: What Do Co-authors Do, Use, and Like?

How do people work when they are collaborating to write a document? What kind of tools do they use and, in particular, do they resort to groupware for this task? Forty-one people filled out a questionnaire placed on the World Wide Web. In spite of the existence of specialized collaborative writing tools, most respondents reported using individual word processors and email as their main tools for writing joint documents. Respondents noted the importance of functions such as change tracking, version control, and synchronous work for collaborative writing tools. This study also confirmed the great variability that exists between collaborative writing projects, whether it be group membership, management, writing strategy, or scheduling issues.     

Medial prefrontal lesions in the rat and spatial navigation: Evidence for impaired planning.

Rats with medial prefrontal cortical lesions were tested in a modified water maze navigation task. In Stage 1, the rats were trained to locate a hidden platform from a single start location. They were then subjected to a series of trials during which a second start position was used (Stage 2). In Stage 3, the rats had to navigate to a new goal location from the 2 experienced start positions. Stage 4 required the rats to navigate to the same goal as in Stage 3, starting from 4 distinct positions. Finally, a single probe trial with no platform was conducted. Rats with prefrontal lesions were impaired only during Stage 4. This deficit was specific to the 2 start positions newly introduced during this stage, suggesting a dysfunction of planning processes. This impairment might result from a working memory deficit, precluding the animal from forming an adequate representation of the whole course of movements required to reach the platform. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Anionic polymerization and copolymerization of cyclosiloxanes initiated by trimethylsilylmethyllithium

Summary A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes, in toluene or in the bulk, in the presence of the cryptand [211] or DMSO. Suitable conditions have been found in which monomodal distributions of molecular weights are observed for homopolymers of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (V₄) as well as for copolymers of V₄ with D₃ or D₄. Laboratoire de Chimie Macromoléculaire associé au CNRS, URA 24     

Dissociations entre musique et langage après atteinte cérébrale: Un nouveau cas d'amusie sans aphasie.

Presents the case of a 40-yr-old female, I.R., who sustained bilateral damage to the temporal lobes and to the right frontal lobe as a result of successive brain surgeries. Her performance is compared to that of 4 neurologically intact Ss who were matched in terms of education, sex and age. I.R.'s performance on various tests aiming at assessing her general cognitive functioning is reported with a particular focus on auditory aspects. Results show that I.R.'s speech abilities are essentially intact. The only language impairments are related to a short-term memory deficit, to some abnormal sensitivity to retroactive interference in long-term memory and to articulation. These difficulties do not, however, affect linguistic communication, which is obviously undisturbed. I.R. does not experience and difficulty in the recognition and memorization of familiar sounds such as animal cries, traffic noises and the like. I.R. is severely impaired in most musical abilities: She can no longer discriminate nor identify melodies that were once highly familiar to her; she can no longer discriminate nor memorize novel melodies. Her pattern of musical losses is compatible with a basic and severe perceptual deficit that compromises access to and registration in memory systems. (PsycINFO Database Record (c) 2010 APA, all rights reserved)