Abstract
Fluorescence experiments are typically performed in sample geometries that are large relative to the size of the fluorophores and relative to the absorption and emission wavelengths. In this arrangement the fluorophores radiate into free space. Most of our knowledge and intuition about fluorescence is derived from the spectral properties observed in these free-space conditions. However, the presence of nearby metallic surfaces or particles can alter the free-space condition, which can result in dramatic spectral changes which are distinct from those observable in the absence of metal surfaces. Remarkably, metal surfaces can increase or decrease the radiative decay rates of fluorophores and increase the extent of resonance energy transfer (RET) (Figure 1).These effects are due to interactions of the excited-state fluorophores with free electrons in the metal, the so-called surface plasmon electrons, which polarize the metal and produce favorable effects on the fluorophore. The effects of metallic surfaces are complex and include quenching at short distances, spatial variation of the incident light field, and changes in the radiative decay rates (Figure 2). We refer to the use of fluorophore-metal interactions as radiative decay engineering (RDE) or metal enhanced fluorescence (MEF).
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Geddes, C.D., Asian, K., Gryczynski, I., Malicka, J., Lakowicz, J.R. (2005). Radiative Decay Engineering (RDE). In: Geddes, C.D., Lakowicz, J.R. (eds) Radiative Decay Engineering. Topics in Fluorescence Spectroscopy, vol 8. Springer, Boston, MA. https://doi.org/10.1007/0-387-27617-3_14
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