Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects

International audienceFully inorganic, colloidal gold nanoclusters (NCs) constitute a new class of nanomaterials that are clearly distinguishable from their commonly studied metal–organic ligand-capped counterparts. As their synthesis by chemical methods is challenging, details about their optical properties remain widely unknown. In this work, laser fragmentation in liquids is performed to produce fully inorganic and size-controlled colloidal gold NCs with monomodal particle size distributions and an fcc-like structure. Results reveal that these NCs exhibit highly pronounced photoluminescence with quantum yields of 2%. The emission behavior of small (2–2.5 nm) and ultrasmall (<1 nm) NCs is significantly different and dominated by either core- or surface-based emission states. It is further verified that emission intensities are a function of the surface charge density, which is easily controllable by the pH of the surrounding medium. This experimentally observed correlation between surface charge and photoluminescence emission intensity is confirmed by density functional theoretical simulations, demonstrating that fully inorganic NCs provide an appropriate material to bridge the gap between experimental and computational studies of NCs. The presented study deepens the understanding of electronic structures in fully inorganic colloidal gold NCs and how to systematically tune their optical properties via surface charge density and particle size

Catalytic Oxygenation of Hydrocarbons by Mono-mu-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu-I/Cu-II Peroxo Complexes

One of the challenges of catalysis is the transformation of inert C−H bonds to useful products. Copper-containing monooxygenases play an important role in this regard. Here we show that low-temperature oxygenation of dinuclear copper(I) complexes leads to unusual tetranuclear, mixed-valent $μ_4$-peroxo [Cu$^I$/Cu$^{II}$]$_2$ complexes. These Cu$_4$O$_2$ intermediates promote irreversible and thermally activated O−O bond homolysis, generating Cu$_2$O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu$_2$O species can also be produced with N$_2$O, demonstrating their capability for small-molecule activation. The binding and cleavage of O$_2$ leading to the primary Cu$_4$O$_2$ intermediate and the Cu$_2$O complexes, respectively, is elucidated with a range of solution spectroscopic methods and mass spectrometry. The unique reactivities of these species establish an unprecedented, 100 % atom-economic scenario for the catalytic, copper-mediated monooxygenation of organic substrates, employing both O-atoms of O$_2$

SoftQuali - Systematische Software-Qualitaetsverbesserung durch zielorientiertes Messen und Bewerten sowie explizite Wiederverwendung des Software-Entwicklungs-Know-Hows Schlussbericht

Available from TIB Hannover: DtF QN1(76,51) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEBundesministerium fuer Bildung und Forschung (BMBF), Bonn (Germany)DEGerman

Shot noise limited soft X-ray absorption spectroscopy in solution at a SASE-FEL using a transmission grating beam splitter

X-ray absorption near-edge structure (XANES) spectroscopy provides element specificity and is a powerful experimental method to probe local unoccupied electronic structures. In the soft x-ray regime, it is especially well suited for the study of 3d-metals and light elements such as nitrogen. Recent developments in vacuum-compatible liquid flat jets have facilitated soft x-ray transmission spectroscopy on molecules in solution, providing information on valence charge distributions of hetero atoms and metal centers. Here, we demonstrate XANES spectroscopy of molecules in solution at the nitrogen K-edge, performed at FLASH, the Free-Electron Laser (FEL) in Hamburg. A split-beam referencing scheme optimally characterizes the strong shot-to-shot fluctuations intrinsic to the process of self-amplified spontaneous emission on which most FELs are based. Due to this normalization, a sensitivity of 1% relative transmission change is achieved, limited by fundamental photon shot noise. The effective FEL bandwidth is increased by streaking the electron energy over the FEL pulse train to measure a wider spectral window without changing FEL parameters. We propose modifications to the experimental setup with the potential of improving the instrument sensitivity by two orders of magnitude, thereby exploiting the high peak fluence of FELs to enable unprecedented sensitivity for femtosecond XANES spectroscopy on liquids in the soft x-ray spectral region