Plasmonic Enhancement of Molecular Fluorescence near Silver Nanoparticles: Theory, Modeling, and Experiment

Metal-enhanced fluorescence of molecular probes in plasmonic nanostructures offers highly sensitive chemical and biomedical analyses, but a comprehensive theory of the phenomenon is far from being complete. In this study, a systematic theoretical analysis is provided for overall luminescence enhancement/quenching for fluorophores near silver spherical nanoparticles. The approach accounts for local intensity enhancement, radiative and nonradiative rates modification, light polarization, molecule position, and its dipole moment orientation. Numerical modeling has been performed for fluorescein-based labels (e.g., Alexa Fluor 488) widely used in biomedical studies and development. The maximal enhancement exceeding 50 times is predicted for nanoparticle diameter 50 nm, the optimal excitation wavelength being 370 nm. For long-wave excitation, bigger particles are more efficient. The experiments with a fluorescein isothiocyanate conjugate of bovine serum albumin confirmed theoretical predictions. The results provide an extensive and promising estimate for simple and affordable silver-based nanostructures to be used in fluorescent plasmonic sensors.