Investigating metal‐enhanced fluorescence effect on fluorescein by gold nanotriangles and nanocubes using time‐resolved fluorescence spectroscopy

• Published in: Journal of the Chinese Chemical Society (Taipei) Vol. 69; no. 1; pp. 82 - 93
• Main Authors: Luo, Xue‐Feng, Lai, Chien‐Chang, Lee, Yin‐Yu, Kuo, Chun‐Hong, Chen, I‐Chia
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley‐VCH Verlag GmbH & Co. KGaA 01.01.2022; Wiley Subscription Services, Inc
• Subjects: core–shell nanoparticle; Energy transfer; Fluorescein; Fluorescence; Gold; Metal surfaces; metal‐enhanced fluorescence; Nanoparticles; Nanostructure; Rate constants; Silicon dioxide; Spectroscopy; Spectrum analysis; Thickness
• ISSN: 0009-4536; 2192-6549
• DOI: 10.1002/jccs.202100294

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 core–shell nanoparticles such as AuNTs and AuNC@SiO2@FITC enhanced the fluorescence of fluorescein isothiocyanate by a factor of 2–3 times for smallest silica shell particles. The values of rate constants for the interaction pathways between fluorescein and gold nanoparticles were obtained based on the time‐resolved fluorescence emission data.