Extending N-heterocyclic carbene ligands into the third dimension: a new type of hybrid phosphazane/NHC system

A simple, “click” synthetic approach to a new type of hybrid phosph(III)azane/NHC system is described. The presence of the phosphazane P₂N₂ ring unit, with P atoms flanking the NCN fragment and with this ring perpendicular to the binding site of the NHC, provides unique opportunities for modifying the electronic and steric character of these carbenes.     

Effect of pH on the synthesis and properties of luminescent SiO2/calcium phosphate:Eu3+ core-shell nanoparticles

A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.     

Electroless silver plating of the surface of organic semiconductors

The integration of nanoscale processes and devices demands fabrication routes involving rapid, cost-effective steps, preferably carried out under ambient conditions. The realization of the metal/organic semiconductor interface is one of the most demanding steps of device fabrication, since it requires mechanical and/or thermal treatments which increment costs and are often harmful in respect to the active layer. Here, we provide a microscopic analysis of a room temperature, electroless process aimed at the deposition of a nanostructured metallic silver layer with controlled coverage atop the surface of single crystals and thin films of organic semiconductors. This process relies on the reaction of aqueous AgF solutions with the nonwettable crystalline surface of donor-type organic semiconductors. It is observed that the formation of a uniform layer of silver nanoparticles can be accomplished within 20 min contact time. The electrical characterization of two-terminal devices performed before and after the aforementioned treatment shows that the metal deposition process is associated with a redox reaction causing the p-doping of the semiconductor.     

A Strong Szegö-Widom Limit Theorem for operators with almost periodic diagonal

The classical Strong Szegö-Widom Limit Theorem describes the asymptotic behavior of the determinants of the finite sections PnT(a)Pn of Toeplitz operators, i.e., of operators which have constant entries along each diagonal. We generalize these results to operators which have almost periodic sequences as their diagonals.