Fast Fluorescence Switching within Hydrophilic Supramolecular Assemblies

We designed a supramolecular strategy to modulate fluorescence in water under optical control. It is based on the entrapment of fluorophore–photochrome dyads within the hydrophobic interior of an amphiphilic polymer. The polymeric envelope around the dyads protects them from the aqueous environment, while imposing hydrophilic character on the overall supramolecular construct. In the resulting assemblies, the photochromic component can be operated reversibly on a microsecond timescale under the influence of ultraviolet stimulations. In turn, the reversible transformations control the emission intensity of the adjacent fluorophore. As a result, the fluorescence of such nanostructured constructs can be photomodulated for hundreds of cycles in water with microsecond switching speeds. Thus, our protocol for fast fluorescence switching in aqueous solutions can eventually lead to the realization of functional probes for the investigation of biological samples. Photoswitchable fluorophores can be entrapped within the hydrophobic interior of an amphiphilic polymer. The fluorescence of the resulting supramolecular assemblies can be switched for hundreds of cycles on a microsecond timescale in aqueous environments (see scheme).