Photoswitchable NIR-Emitting Gold Nanoparticles.

Photo-switching of the NIR emission of gold nanoparticles (GNP) upon photo-isomerization of azobenzene ligands, bound to the surface, is demonstrated. Photophysical results confirm the occurrence of an excitation energy transfer process from the ligands to the GNP that produces sensitized NIR emission. Because of this process, the excitation efficiency of the gold core, upon excitation of the ligands, is much higher for the trans form than for the cis one, and t→c photo-isomerization causes a relevant decrease of the GNP NIR emission. As a consequence, photo-isomerization can be monitored by ratiometric detection of the NIR emission upon dual excitation. The photo-isomerization process was followed in real-time through the simultaneous detection of absorbance and luminescence changes using a dedicated setup. Surprisingly, the photo-isomerization rate of the ligands, bound to the GNP surface, was the same as measured for the chromophores in solution. This outcome demonstrated that excitation energy transfer to gold assists photo-isomerization, rather than competing with it. These results pave the road to the development of new, NIR-emitting, stimuli-responsive nanomaterials for theranostics.

Ultra-bright and stimuli-responsive fluorescent nanoparticles for bioimaging.

Fluorescent nanoparticles (NPs) are unique contrast agents for bioimaging. Examples of molecular-based fluorescent NPs with brightness similar or superior to semiconductor quantum dots have been reported. These ultra-bright NPs consist of a silica or polymeric matrix that incorporate the emitting dyes as individual moieties or aggregates and promise to be more biocompatible than semiconductor quantum dots. Ultra-bright materials result from heavy doping of the structural matrix, a condition that entails a close mutual proximity of the doping dyes. Ground state and excited state interactions between the molecular emitters yield aggregation-caused quenching (ACQ) and proximity-caused quenching (PCQ). In combination with Föster resonance energy transfer (FRET) ACQ and PCQ originate collective phenomena that produce amplified quenching of the nanoprobes. In this focus article, we discuss strategies to achieve ultra-bright nanoprobes avoiding ACQ and PCQ also exploiting aggregation-induced emission (AIE). Amplified quenching, on the other hand, is also proposed as a strategy to design stimuli-responsive fluorogenic probes through disaggregation-induced emission (DIE) in alternative to AIE. As an advantage, DIE consents to design stimuli-responsive materials starting from a large variety of precursors. On the contrary, AIE is characteristic of a limited number of species. Examples of stimuli-responsive fluorogenic probes based on DIE are discussed.