Metal-enhanced fluorescence model

We are now looking at extending the simple model for free-space fluorescence to the case of Metal Enhanced Fluorescence (MEF). We therefore consider a fluorophore with known free-space properties in the presence of optically-active objects (in particular metallic objects). 

The EM theory of Metal Enhanced Fluorescence (MEF) was studied and developed extensively in the 70-80 s [2,3,4,5,6], All the EM mechanims involved in MEF can be understood within classical EM theory [3,4,5,6] as confirmed in the simplest cases by quantum studies [2,12,17,18], In most of these models, the emitter is depicted as a simple two- (or three-) level system, i.e. only one emission wavelength is considered. This is appropriate in general to understand modifications of absorption or emission rates, but it entirely ignores the spectral profile of the fluorescence emission. We will first review... 

Most models for SEF focus on the plasmonics, and treat the molecule as a classical dipole. While the plasmonics models increasingly give more realistic results for the plasmon observed in the system, the treatment of the molecule, and thus the molecule-metal system, is not always as well developed. In their 2005 paper, Johansson, Xu, and Kail [44] present a unified model of enhanced Raman scattering and enhanced fluorescence within the context of quantum optics. This model is easily modified to include the field enhancement (M) and decay enhancement (Md), which may be calculated through plasmonics methodology. 

Recently, Schalkhammer et al. have discussed the relevance of surface enhanced fluorescence in immunosensing apphcations (surface-enhanced fluoroimmunoas-say, SE-FIA) [322]. The enhancement mechanism was explained by an electrodynamic model and the interaction between metal particle and fluorophore for the excitation and emission process was discussed. It was shown that the discrimination power increased with decreasing quantum efficiency of the fluorophore. This suggested that in SE-FIA a low-quantum efficiency fluorophore needs to be used, as was shown by experiments with model compounds. 

As demonstrated in this chapter, the binding of metal ions to maclocyclic ligands (e.g., porphyrins) results in the change in both the thermodynamic and dynamic properties of ET reactions of metalloporphyrins. Excellent models of the photosynthetic reaction center were developed by the appropriate choice of combination of metal ions and macrocyclic ligands. The lifetimes of the CS states in models of photosynthetic reaction center composed of electron donors and acceptors also were controlled by binding of metal ions to radical anions of electron acceptor moieties in the electron donor-acceptor hnked molecules. The control of ET processes by coordination of metal ions to the dyads led us to develop a unique fluorescence sensor for the ion. The binding of metal ions to radical anions of electron acceptors results in acceleration of thermal ET reactions, which would otherwise be impossible to occur. Such effects of metal ions to enhance the ET... 

Mahdavi, F., Liu, Y., Blair, S., (2007). Modeling Fluorescence Enhancement from Metallic Nanocavities. Plasmonics 2 129-141. 

There are essentially two models that describe the interaction between an excited fluorophore and the SPR of the metal to account for quenching and enhancement of the fluorescence. They both depend on coupling of the fluorophore excited state to the SPR and this is dependent of the spectral overlap of the emission of the fluorophore and the SPR, and the distance between the fluorophore and the metal nanoparticle surface. 

Understanding the field enhancement of radiative rates is insufficient to predict how molecular photophysical properties such as enhancement of fluorescence quantum yield will be affected by interactions of the molecule with plasmons. A more detailed model of the photophysics that accounts for non-radiative rates is necessary to deduce effects on photoluminescence (PL) yields. Such a model must include decay pathways present in the absence of metal nanoparticles as well as additional pathtvays such as charge transfer quenching that are associated with the introduction of the metal particles. Schematically, we depict the simplest conceivable model in Figure 19. IB. Note that both the contributions of radiative rate enhancement and the excited state quenching by proximity to the metal surface will depend on distance of the chromophore from the metal assembly. In most circumstances, one expects the optimal distance of the chromophores from the surface to be dictated by the competition between quenching when it is too close and reduction of enhancement when it is too far. The amount of PL will be increased both due to absorption enhancement and emissive rate enhancement. Hence, it is possible to increase PL substantially even for molecules with 100 % fluorescence yield in the absence of metal nanoparticles. 

The presence of at least two fluorophores, and possibly a third, associated with metal ion binding in fulvic acid strongly suggests the need for multiple binding site models. Existing linear and nonlinear models will be reviewed for both fluorescence quenching and enhancement. A new modified 1 1 Stem - Volmer model will be introduced as well as two site and multiple site models. Application of the models to Cu binding by fulvic acid and certain well defined model systems are discussed. 

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