A hybrid computational and experimental approach was employed toward the rational design of a silver nanoparticle (AgNP)/polydiacetylene (PDA) metal-enhanced fluorophore (MEF) ensemble system contained within a poly(ethylene oxide) (PEO) electrospun nanofiber matrix for creation of high-performance sensors. Simulations based on Mie theory and finite-difference time domain (FDTD) algorithms were performed to understand and optimize spectral overlap between the AgNP localized surface plasmon resonance and the absorbance and emission spectra of PDA, a supramolecular polymer fluorophore. A series of AgNPs of varied sizes were investigated for fluorescence enhancement capability, and an optimal size of 134 nm in diameter was chosen for synthesis and incorporation into the electrospun nanofibers of a PDA/PEO composite for experimental characterization and confirmation. Results on individual nanofibers indicated a clear metal-enhanced fluorescence effect, and a 4.6-fold enhancement over neat PDA/PEO fluorescent nanofibers was observed. The nanofiber/nanoparticle/MEF ensemble system offers new avenues for generating effective sensing devices with polymeric fluorophores using a straightforward incorporation approach.
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