Investigation of copper oxidation states in plasmonic nanomaterials by XAS and Raman spectroscopy.

Plasmonic core-shell-isolated nanoparticles are promising nanoplatforms for photocatalysis and for low detection analysis. This paper describes the characterization of a 2,2'-bipyridine phosphonate functionalized Ag@TiO2 nanocomposite which complexes copper ions by enhanced Raman spectroscopy and X-ray absorption (XANES and EXAFS). We distinguished Cu(i) from Cu(ii) complexes using shell-isolated nanoparticle enhanced Raman (SHINERS) combined with XAS spectroscopy.

Functionalized core-shell Ag@TiO2 nanoparticles for enhanced Raman spectroscopy: a sensitive detection method for Cu(ii) ions.

This paper demonstrates the use of surface plasmon resonance of core-shell Ag@TiO2 particles in SHINERS experiments. A copper(ii) complex grafted onto Ag@TiO2 surface was probed by Raman spectroscopy using resonance excitation profiles vs. excitation wavelengths (514, 633 and 785 nm) to tune the Raman signals. Enhancement factors of the SHINERS assembly have been estimated and compared to the SERS effect of unmodified silver NPs colloidal dispersions. Finally, the grafting of the copper(ii) complex onto Ag@TiO2 was advantageously compared to the grafting onto Ag@SiO2 shell.

Phosphonate-Mediated Immobilization of Rhodium/Bipyridine Hydrogenation Catalysts.

RhL2 complexes of phosphonate-derivatized 2,2'-bipyridine (bpy) ligands L were immobilized on titanium oxide particles generated in situ. Depending on the structure of the bipy ligand-number of tethers (1 or 2) to which the phosphonate end groups are attached and their location on the 2,2'-bipyridine backbone (4,4'-, 5,5'-, or 6,6'-positions)-the resulting supported catalysts showed comparable chemoselectivity but different kinetics for the hydrogenation of 6-methyl-5-hepten-2-one under hydrogen pressure. Characterization of the six supported catalysts suggested that the intrinsic geometry of each of the phosphonate-derivatized 2,2'-bipyridines leads to supported catalysts with different microstructures and different arrangements of the RhL2 species at the surface of the solid, which thereby affect their reactivity.

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

Non-photochemical catalytic hydrolysis of methyl parathion using core-shell Ag@TiO2 nanoparticles.

Highly water-dispersible core-shell Ag@TiO2 nanoparticles were prepared and shown to be catalytically active for the rapid degradation of the organothiophosphate pesticide methyl parathion (MeP). Formation of the hydrolysis product, p-nitrophenolate was monitored at pH 7.5 and 8.0, using UV-Vis spectroscopy. 31P NMR spectroscopy confirmed that hydrolysis is the predominant pathway for substrate breakdown under non-photocatalytic conditions. We have demonstrated that the unique combination of TiO2 with silver nanoparticles is required for catalytic hydrolysis with good recyclability. This work represents the first example of MeP degradation using TiO2 doped with AgNPs under mild and ambient conditions. Analysis of catalytic data and a proposed dark mechanism for MeP hydrolysis using core-shell Ag@TiO2 nanoparticles are described.