A "clickable" titanium surface platform.

A straightforward functionalization of a titanium surface using "click" chemistry is reported. A "clickable" titanium surface platform was prepared by the immobilization of an azide-functionalized electroactive catechol anchor and was subsequently derivatized with an electroactive or fluorinated probe via the CuAAC (copper-catalyzed azide-alkyne cycloaddition) reaction. The course of the reaction was investigated by contact angle, XPS, and electrochemical measurements.

Clicking ferrocene groups to boron-doped diamond electrodes.

Covalent linking of ethynyl ferrocene to azide-terminated boron-doped diamond surfaces using click chemistry is demonstrated; the course of the reaction was followed using X-ray photoelectron spectroscopy, water contact angle and electrochemical measurements.

Polypropylene film chemical and physical modifications by dielectric barrier discharge plasma treatment at atmospheric pressure.

Dielectric barrier discharge (DBD) technologies have been used to treat a polypropylene film. Various parameters such as treatment speed or electrical power were changed in order to determine the treatment power impact at the polypropylene surface. Indeed, all the treatments were performed using ambient air as gas to oxidize the polypropylene surface. This oxidation level and the surface modifications during the ageing were studied by a wetting method and by X-ray photoelectron spectroscopy (XPS). Moreover polypropylene film surface topography was analyzed by atomic force microscopy (AFM) in order to observe the surface roughness modifications. These topographic modifications were correlated to the surface oxidation by measuring with a lateral force microscope (LFM) the surface heterogeneity. The low ageing effects and the surface reorganization are discussed.

A surfactant-assisted preparation of well dispersed rhodium nanoparticles within the mesopores of AlSBA-15: characterization and use in catalysis.

Well dispersed and efficient Rh(0) hydrogenation catalysts were obtained by the reduction of Rh(III)-exchanged mesoporous aluminosilicates by sodium borohydride in the presence of N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium chloride.

Peptide immobilization on amine-terminated boron-doped diamond surfaces.

This paper reports on the formation and characterization of semicarbazide termination on aminated boron-doped diamond (BDD) surfaces, and further preparation of peptide microarray through site-specific alpha-oxo semicarbazone ligation. Hydrogen-terminated BDD electrodes were first aminated using NH3 plasma treatment and then reacted with triphosgene and Fmoc-protected hydrazine to yield a protected semicarbazide termination. Subsequent deprotection and chemical reaction with glyoxylyl peptides led to the covalent immobilization of the peptides on the surface through site-specific ligation. The resulting surfaces were characterized using X-ray photoelectron spectroscopy (XPS) and fluorescence measurements.

Preparation of superhydrophobic silicon oxide nanowire surfaces.

The paper reports on the preparation of superhydrophobic amorphous silicon oxide nanowires (a-SiONWs) on silicon substrates with a contact angle greater than 150 degrees by means of surface roughness and self-assembly. Nanowires with an average mean diameter in the range 20-150 nm and 15-20 microm in length were obtained by the so-called solid-liquid-solid (SLS) technique. The porous nature and the high roughness of the resulting surfaces were confirmed by AFM imaging. The superhydrophobicity resulted from the combined effects of surface roughness and chemical modification with fluorodecyl trichlorosilane.

A systematic study of the interactions between chemical partners (metal, ligands, counterions, and support) involved in the design of Al2O3-supported nickel catalysts from diamine-Ni(II) chelates.

1.5 Ni wt %/Al2O3 catalysts have been prepared by incipient wetness impregnation using [Ni(diamine)x(H2O)(6-2x)]Y2 precursors (diamine = 1,2-ethanediamine (en) and trans-1,2-cyclohexanediamine (tc); x = 0, 1, and 2; Y = NO3- and Cl-), to avoid the formation, during calcination, of difficult-to-reduce nickel aluminate. N2 was chosen for thermal treatment to help reveal and take advantage of the reactions occurring between Ni2+, ligands, counterions, and support. In the case of [Ni(en)2(H2O)2]Y2 salts used as precursors, in situ UV-vis and DRIFT spectroscopies show that after treatment at 230 degrees C Ni(II) ions are grafted to alumina via two OAl bonds and that the diamine ligands still remain coordinated to grafted nickel ions but in a monodentate way, bridging the cation with the alumina surface. With Y = Cl-, the chloride counterions desorb as hydrogen chloride, and hydrogen released upon decomposition of the en ligands is able to reduce a fraction of nickel ions into metal as evidenced by XPS. In contrast, with Y = NO3-, compounds such as CO or NO are formed during thermal treatment, indicating that nitrate ions burn the en ligands. After thermal treatment at 500 degrees C, a surface phase containing Ni(II) ions forms, characterized by XPS and UV-vis spectroscopy. Temperature-programmed reduction shows that these ions can be quantitatively reduced to the metallic state at 500 degrees C, in contrast with the aluminate obtained when the preparation is carried out from [Ni(H2O)6]2+, which is reduced only partly at 950 degrees C. On the other hand, a total self-reduction of nickel complexes leading to 2-5-nm metal particles is obtained upon thermal treatment via the hydrogen released by a hydrogen-rich ligand such as tc, whatever the Y counterion. An appropriate choice of the ligand and the counterion allows then to obtain selectively Ni(II) ions or a dispersed reduced nickel phase after treatment in N2, as a result of the reactions occurring between the chemical partners present on alumina.

Speciation of PM10 sources of airborne nonferrous metals within the 3-km zone of lead/zinc smelters.

The purpose of this study was to estimate the speciation of PM10 sources of airborne Pb, Zn, and Cd metals (PM10 is an aerosol standard of aerodynamic diameter less than 10 microm.) in the atmosphere of a 3 km zone surrounding lead/zinc facilities in operation for a century. Many powdered samples were collected in stacks of working units (grilling, furnace, and refinery), outdoor storages (ores, recycled materials), surrounding waste slag (4 Mt), and polluted topsoils (3 km). PM10 samples were generated from the raw powders by using artificial resuspension and collection devices. The bulk PM10 multielemental analyses were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The proportions in mass of Pb (50%), Zn (40%), and Cd (1%) contents and associated metals (traces) reach the proportions of corresponding raw powdered samples of ores, recycled materials, and fumesize emissions of plants without specific enrichment. In contrast, Pb (8%) and Zn (15%) contents of PM10 of slag deposit were found to be markedly higher than those of raw dust, Pb (4%), and Zn (9%), respectively. In the same way, Pb (0.18%), Zn (0.20%), and Cd (0.004%) were enriched by 1.7, 2.1, and 2.3 times, respectively, in PM10 as compared with raw top-soil corresponding values. X-ray wavelength dispersive electron-microprobe (EM-WDS) microanalysis did not indicate well-defined phases or simple stoichiometries of all the PM10 samples atthe level of the spatial resolution (1 microm3). X-ray photoelectron spectroscopy (XPS) indicated that minor elements such as Cd, Hg, and C are more concentrated on the particle surface than in the bulk of PM10 generated by the smelting processes. (XPS) provided also the average speciation of the surface of PM10; Pb is mainly represented as PbSO4, Zn as ZnS, and Cd as CdS or CdSO4, and small amounts of coke were also detected. The speciation of bulk PM10 crystallized compounds was deduced from XRD diffractograms with a raw estimation of the relative quantities. PbS and ZnS were found to be the major phases in PM10 generated by the smelting facilities with PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, Pb metal, and ZnO as minor phases. The slag waste PM10 was found to contain some amounts of PbCO3, PbSO4 x PbO, and ZnFe2O4 phases. The large heterogeneity at the level of the individual particle generates severe overlap of chemical information even at the microm scale using electron microprobe (WDS) and Raman microprobe techniques. Fortunately, scanning Raman microspectrometry combined with SIMPle-to-use Interactive Self-modeling Mixture Analysis (SIMPLISMA) performed the PM10 speciation at the level of individual particles. The speciation of major Pb, Zn, and Cd compounds of PM10 stack emissions and wind blown dust of ores and recycled materials were found to be PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, PbO, metallic Pb, ZnS, ZnO, and CdS. The PM10 dust of slag waste was found to contain PbCO3, Pb(OH)2 x 2PbCO3, PbSO4 x PbO, and ZnS, while PM10-bound Pb, Zn of the top-soils contain Pb5(PO4)3Cl, ZnFe2O4 as well as Pb(II) and Zn(II) compounds adsorbed on Fe(III) oxides and in association with clays.