Gold nanotriangles (AuNTs) and nanocubes (NCs) coated with silica shell and fluorescein were synthesized to study the effects of metal‐enhanced fluorescence. The interaction between gold nanoparticles (GNPs) and fluorescein with silica shells of different thicknesses as spacers was investigated by using time‐resolved fluorescence spectroscopy. From the biexponential decay of fluorescence of fluorophore and the kinetic mechanism for the interaction, we obtained the rate constants of energy transfer processes. Both energy transfer rates from fluorophore to the bright and dark modes of gold nanoparticles decreased with distance d (= silica thickness) with a dependence ∝ d−n and n ≈ 2. The rate constant of nanosurface energy transfer kNEST, considering dipolar interaction between fluorophore and metal surface, has an estimated value 1.7 times slower at d = 9 nm and about four times slower at 25 nm than the obtained rate constant for energy transfer from fluorophore to GNP dipolar mode in the AuNT system. For the AuNC system, the rate constants are greater than the AuNT system because of better spectral overlap between emission of fluorescein and surface plasmon resonance.
The effects of metal‐enhanced fluorescence (MEF) of rhodamine dye by gold sub‐micro hexagonal plates were studied. A multilayered avidin–biotin complex was designed and used as a spacer to connect the fluorophore and the sub‐microplate. Fluorescence lifetime image microscopy (FLIM) combined with time‐correlated single‐photon counting was used to obtain lifetime images and intensities of dye on single particles. Gold hexagon plates ~900 nm were synthesized, and the avidin–biotin complexes were placed layer‐by‐layer for up to 4 layers onto the sub‐microplates. All emission curves of fluorophore displayed biexponential decay with short lifetimes of 18–23 ps and long lifetimes of 249, 271, 304, and 348 ps for 1–4 layers on gold sub‐microplates, respectively. Using the kinetic model of energy transfer between fluorophore and nanoparticles to explain the coupling mechanism, we found that the excited fluorophore transferred energy mostly to the high‐order modes for the 1‐layered avidin–biotin complexes enclosing gold nanospheres, consequently resulting in a non‐emissive pathway. The 4‐layered samples had the highest emission intensity because, at those distances, the enhancement by the gold sub‐microplates during plasmonic excitation remained high and became comparable to the energy quenching rate. Using the composed complexes, the MEF effect achieved the maximal enhancement in this system.
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