Cellular and subcellular distribution of metals in molluscs

The cellular processes involved in metal metabolism in molluscs are reviewed, with emphasis on the contribution of microscopy (AMG, ARG, EPMA, and SIMS) to both basic research of metal cell biology and applied environmental research. In molluscs, metal uptake may occur by facilitated diffusion, active transport, or endocytosis, and can be enhanced by MT synthesis or formation of mineralized granules. In aquatic molluscs, gills constitute a key interface for dissolved metal uptake, where metals are bound to MT, incorporated into lysosomes, and released basally towards the blood plasma and circulating hemocytes. However, particulate metal uptake is mainly achieved via the digestive tract by endocytosis; further metals are transferred first to lysosomes and then to residual bodies, especially in the digestive cells of the digestive gland. Additionally, metals can be accumulated selectively in specific cell types. As ligands pools differ from cell to cell, different metals may be retained in different cell types. Class "a" metals are localized in cells with granules composed of carbonate, oxalate, phosphate, and sulfate (oxygen donors), whereas "b" metals are associated with those cell types rich in sulfur and nitrogen ligands (sulfur donors). In molluscs, oxygen donors occur in connective tissue calcium cells and basophilic cells, whereas sulfur donors are present in digestive cells, podocytes, nephrocytes, and rhogocytes. Hemocytes, which constitute the most relevant system for metal transport between tissues, move around the body and may penetrate tissues and remove metals from the inner medium to be accumulated in lysosomes as nondigested products. Rhogocytes also participate in metal mobilization, accumulation, and release. The assessment of metal levels in target cells of sentinel molluscs by microscopic techniques provides an early-warning measure, with promising applications as an exposure biomarker for environmental monitoring programs.     

Optical properties of microfabricated fully-metal-coated near-field probes in collection mode

A study of the optical properties of microfabricated, fully-metal-coated quartz probes collecting longitudinal and transverse optical fields is presented. The measurements are performed by raster scanning the focal plane of an objective, focusing azimuthally and radially polarized beams by use of two metal-coated quartz probes with different metal coatings. A quantitative estimation of the collection efficiencies and spatial resolutions in imaging both longitudinal and transverse fields is made. Longitudinally polarized fields are collected with a resolution approximately 1.5 times higher as compared with transversely polarized fields, and this behavior is almost independent of the roughness of the probe's metal coating. Moreover, the coating roughness is a critical parameter in the relative collection efficiency of the two field orientations.     

Categorization of individuals on the basis of multiple social features.

Five experiments used a name-matching paradigm developed by S. E. Taylor et al (1978) to investigate how people use the immediately apparent features of others as a basis of social categorization. Ss were more likely to categorize targets according to their sex than their race but also tended to categorize using a single subordinate category that represented sex and race simultaneously. Racially prejudiced Ss categorized to greater degree by race than did nonprejudiced Ss, but manipulations of construct accessibility and processing goals did not influence categorization by race or sex. Processing goals did influence the use of clothing style as a categorization feature. Results are discussed in terms of the functional utility of person features as a basis of categorization and the effects of categorization on social stereotyping and prejudice. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Calixarene‐Derived Mono‐Iminophosphoranes: Highly Efficient Ligands for Palladium‐ and Nickel‐Catalysed Cross‐Coupling

The first mono‐iminophosphoranes based on a calix[4]arene skeleton have been synthesised and tested in the arylation of aryl bromides and aryl chlorides. Combining these ligands with [Pd(OAc)₂] or [Ni(cod)₂] resulted in highly active Suzuki–Miyaura and Kumada–Tamao–Corriu cross‐coupling catalysts, respectively. TOFs up to ca. 4×10⁵ mol(ArBr)⋅mol(M)⁻¹⋅h⁻¹ were obtained in each case. The remarkable activities observed probably arise from the ligands’ ability to form complexes with cavity‐entrapped “MArX” moieties (endo‐complexes), their highly crowded metal environment favouring formation of mono‐ligated intermediates over that of less reactive bis‐ligated ones. Possible supramolecular interactions within the cavity involving the receptor wall and the aromatic substrate may also significantly influence the reaction rates, notably by increasing the proportion of endo‐complexes.     

Unexpected effect of copper ions on electrochemical impedance behaviour of self-assembled alkylaminethiol monolayer

Effect of copper ions on the electrochemical behaviour of an alkylaminethiol monolayer has been studied by electrochemical impedance spectrosocpy. RAMAN experiment shows the effective adsorption of receptor onto the gold surfaces. The study of Nyquist plot shows that the gold/monolayer/electrolyte interface can be described by a serial combination of two R, CPE electrical circuits. In the presence of increasing amounts of copper, the Nyquist plots at low frequencies were modified showing an increase of the resistance of the second R, CPE electrical circuit. Moreover, this increase of resistance varies linearly with the amounts of copper ions added in solution from 10^? 8 mol·L^? 1 to 10^? 5 mol·L^? 1.     

Effect of the structure of Pt-Ru/C particles on COad monolayer vibrational properties and electrooxidation kinetics

In this paper, we combined FTIR spectroscopy and CO_ad stripping voltammetry to investigate CO_ad adsorption and electrooxidation on Pt-Ru/C nanoparticles. The Pt:Ru elemental composition and the metal loading were determined by ICP-AES. The X-ray diffraction patterns of the Pt-Ru/C indicated formation of a Pt-Ru (fcc) alloy. HREM images revealed an increase in the fraction of agglomerated Pt-Ru/C particles with increasing the metal loading and showed that agglomerated Pt-Ru/C nanoparticles present structural defects such as twins or grain boundaries. In addition, isolated Pt-Ru/C nanoparticles have similar mean particle size (ca. 2.5 nm) and particle size distributions whatever the metal loading. Therefore, we could determine precisely the effect of particle agglomeration on the CO_ad vibrational properties and electrooxidation kinetics. FTIR measurements revealed a main CO_ad stretching band at ca. , which we ascribed to a-top CO_ad on Pt domains electronically modified by the presence of Ru. As the metal loading increased, the position of this band was blue shifted by ca. 5 cm⁻¹ and a shoulder around 2005 cm⁻¹ developed, which was ascribed to a-top CO_ad on Ru domains. The reason for this was suggested to be the increasing size of Ru domains on agglomerated Pt-Ru/C particles, which lifts dipole-dipole coupling and allows two vibrational features to be observed (CO_ad/Ru, CO_ad/Pt). This is evidence that FTIR spectroscopy can be used to probe small chemical fluctuations of the Pt-Ru/C surface. Finally, we comment on the CO_ad electrooxidation kinetics. We observed that CO_ad was converted more easily into CO₂ as the metal loading, i.e. the fraction of agglomerated Pt-Ru/C nanoparticles, increased.     

Fluidized bed chemical vapor deposition of silicon on carbon nanotubes for Li-ion batteries

Silicon was deposited on balls of entangled multi-walled carbon nanotubes (CNT) with a mean diameter of several hundreds of microns, by Fluidized Bed Chemical Vapor Deposition from silane (SiH4). The weight total percentage of deposited silicon was between 30 and 70%, to test their efficacy in Li-ion battery anodes. TEM and SEM imaging revealed that silicon deposits were of the form of nanoparticles uniformly dispersed on the whole CNT surface. The diameter of these nanoparticles increases with the deposited silicon percentage from 18 to 36 nm whereas their density remains constant at 5 10(22) nanoparticles/g of CNT. This indicates a low affinity of chemical species born from silane pyrolysis with the CNT surface for nucleation. The increase of the silicon nanoparticles diameter leads to the decrease of the specific surface area and the porous volume of the balls, probably due to the filling of the pores of the CNT network by silicon. A slight increase of the mean diameter of the balls was observed for the two highest silicon percentages, certainly due to the ability of the CNT network to be deformed under the mechanical stress induced by the silicon nanoparticles growth.     

Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru_xSe_y) and non-precious transition metals (M_xX_y: M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru_xSe_y), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.     

Fluorescence spectroscopy as a non invasive tool to follow in situ the polymerization in miniemulsion

Miniemulsion polymerization is a powerful technique to produce a whole variety of latexes with controlled colloidal and chemical properties, which has gained an increasing importance in the past years. For many applications, the following of the kinetics of polymerization is of crucial importance. In this study, we developed a technique based on the use of fluorescent probes that could be a very promising noninvasive method to follow the reaction in situ. It was possible to follow qualitatively the kinetics of methyl methacrylate (MMA) polymerization by measuring the photophysical properties of fluorescent probes sensitive to the modification of the viscosity of the microenvironment along the reaction course. Two fluorescent sensors have been considered: 1,1‐dicyano‐4‐(4′‐dimethylaminophenyl)‐1,3‐butadiene) and pyrene. In this article, we will show that using these two different fluorescent probes allow the detection of MMA polymerization in miniemulsion. The results will be compared with a classical NMR method. This method could be easily adapted to different monomers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011