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| - Detection of Adsorption of Ru(II) and Os(II) Polypyridyl Complexes on Gold and SilverNanoparticles by Single-Photon Counting Emission Measurements
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| - The present study describes a new application of ruthenium(II) tris(bipyridine) (Ru(bpy)32+) and osmium(II)tris(bipyridine) (Os(bpy)32+) as phosphorescent labels for the quantification of surface binding of moleculesto gold and silver nanoparticles. The fraction of Ru(bpy)32+ and Os(bpy)32+ that is in solution can bedistinguished from the surface-bound fraction by the relative lifetimes and integrated emission yields asdetermined by time-correlated single-photon counting (TCSPC) spectroscopy. Complementary steady-statemeasurements were carried out to confirm surface attachment of the phosphorescent label molecules. Althoughthe emission of solutions of Ru(bpy)32+ and Os(bpy)32+ is quenched proportional to the concentration of10 nm Au or 20 nm Ag nanoparticles, the quenching is static and not diffusional quenching observed inStern−Volmer plots. The results demonstrate that time-resolved spectroscopy provides a rapid method forthe measurement of surface binding of labeled molecules on metallic nanoparticles. While steady-statemeasurements require the preparation of a series of samples with varying quencher concentrations and areference, the method described herein requires a single sample plus reference. The mechanism forphosphorescence quenching on Au and Ag nanoparticles is discussed in terms of energy and electron transfertheories.
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