Recently, it has been noticed that surface plasmon resonance of metal nanoparticles can alter the intrinsic properties of nearby fluorophores. Field enhancement and radiative decay engineering are major principles for understanding a number of experimental observations such as enhanced and quenched emission of fluorophores in the vicinity of metal nanoparticles. At the same time, there are apparent similarities between surface-plasmon-coupled fluorescence and fluorescence resonance energy transfer (FRET), as both are near-field through-space interactions. From this perspective, we hypothesize that donor-acceptor interaction in the FRET can be altered by metal nanoparticles. Our approach is based on diblock copolymer micelles, which have been widely applied for nanoscale arrangement of functionalities. By applying self-assembling techniques of copolymer micelles to organize the spatial location of semiconductor quantum dots, fluorescent dyes, and metal nanoparticles, the FRET in hybrid assemblies can be switched off by plasmonic effects.
The synthesis of poly(methyl methacrylate) (PMMA) exhibiting one fluorescent dye (Texas Red) and one methyl disulfide end group is described. It is shown that the latter end group enabled the exchange of both oleic amine on gold nanoparticles (AuNP) and of oleic acid on CdSe/ZnS quantum dots (QD), allowing for a phase transfer of both types of nanoparticles (NP) from hexane into dimethylformamide due to the solubility provided by the PMMA chains. For AuNP, a fluorescence quenching of the dye was found due to fluorescence resonance energy transfer (FRET) from the dye to the AuNP, while QDs caused a fluorescence enhancement by FRET from the QD to the attached dyes. Due to the hetero-telechelic geometry of the polymer, the separation between NP and dye is governed by the end-to-end distance of the polymer.
Photonic crystals can be represented by periodic nanostructures with alternating refractive indices, which create artificial stop bands with the appearance of colors. In this regard, nanodomains of block copolymers and the corresponding structural colors have been intensively studied in the past. However, the practical application of photonic crystals of block copolymers has been limited to a large degree because of the presence of large defects and grain boundaries in the nanodomains of block copolymers. The present study focuses on the alternative opportunity of short-range ordered nanodomains of block copolymers for fluorescence enhancement, which also has a direct relevance to the development of fluorescence sensors or detectors. The enhancement mechanism was found to be interconnected with the excitation process rather than the alternation of the decay kinetics. In particular, we demonstrate that randomly oriented, but regular grains of lamellae of polystyrene-block-polyisoprene, PS-b-PI, diblock copolymers and their blend with PS homopolymers can behave as Bragg mirrors to induce multiple reflections of the excitation source inside the photonic structures. This process in turn significantly increases the effective absorption of the given fluorophores inside the polymeric photonic structures to amplify the fluorescence signal.
We demonstrate precise control of multiple FRET within LbL assemblies to produce simultaneous light emission with enhanced intensity from a single excitation with a blue wavelength. Three different fluorescent dyes were attached to neat polyelectrolytes and then incorporated into the LbL assembly. With designed deposition sequence, the layer of blue‐absorbing dyes was placed in the adjacent layer of green‐ and red‐emitting dyes, while the layers of emitting dyes were separated with each other beyond their Förster radius by inserting neat polyelectrolytes between them. The LbL assemblies not only allowed FRET from the absorbing dyes to the emitting dyes but also prohibited FRET between the emitting dyes to produce simultaneously enhanced green and red emission. magnified image
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