title: Distance and wavelength dependent quenching of molecular fluorescence by Au@SiO2 core-shell nanoparticles.
abstract: Gold nanoparticles and nearby fluorophores interact via electromagnetic coupling upon light excitation. We determine the distance and wavelength dependence of this coupling theoretically and experimentally via steady-state and time-resolved fluorescence spectroscopy. For the first time, the fluorescence quenching of four different dye molecules, which absorb light at different wavelengths across the visible spectrum and into the near-infrared, is studied using a rigid silica shell as a spacer. A comprehensive experimental determination of the distance dependence from complete quenching to no coupling is carried out by a systematic variation of the silica shell thickness. Electrodynamic theory predicts the observed quenching quantitatively in terms of energy transfer from the molecular emitter to the gold nanoparticle. The plasmonic field enhancement in the vicinity of the 13 nm gold nanoparticles is calculated as a function of distance and excitation wavelength and is included in all calculations. Relative radiative and energy transfer rates are determined experimentally and are in good agreement with calculated rates. We demonstrate and quantify the severe effect of dye-dye interactions on the fluorescence properties of dyes attached to the surface of a silica nanoparticle in control experiments. This allows us to determine the experimental conditions, under which dye-dye interactions do not affect the experimental results.
authors.affiliation: Department of Materials Engineering, Faculty of Engineering and #School of Chemistry, Faculty of Science, Monash University, Clayton, 3800 VIC, Australia.
authors.forename: Philipp
authors.initials: P
authors.lastname: Reineck
authors.forename: Daniel
authors.initials: D
authors.lastname: Gómez
authors.forename: Soon Hock
authors.initials: SH
authors.lastname: Ng
authors.forename: Matthias
authors.initials: M
authors.lastname: Karg
authors.forename: Toby
authors.initials: T
authors.lastname: Bell
authors.forename: Paul
authors.initials: P
authors.lastname: Mulvaney
authors.forename: Udo
authors.initials: U
authors.lastname: Bach
mesh_terms: D004396:Coloring Agents / Q000737:chemistry; D004247:DNA / Q000737:chemistry; D060733:Electromagnetic Radiation; D004735:Energy Transfer; D005453:Fluorescence; D005456:Fluorescent Dyes / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D053758:Nanoparticles / Q000737:chemistry; D036103:Nanotechnology / Q000379:methods; D055095:Optics and Photonics; D012822:Silicon Dioxide / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013499:Surface Properties
chemical_list: D004396:Coloring Agents; D005456:Fluorescent Dyes; D006046:Gold; D012822:Silicon Dioxide; D004247:DNA