The assembly of monomeric building blocks can manifest the display of new properties, including optical, mechanical, and electrochemical functionalities. In this study, we sought to develop a functional fluorophore self-assembly that can generate reactive oxygen species only when aggregated. With an anthrylphenylene (AP) group, negatively charged and neutral fluorescein units form non-fluorescent H-aggregates in aqueous solution because of the weak intermolecular interaction between the anthracene and fluorescein moieties. In stark contrast, a boron dipyrromethene (BODIPY) and AP dyad produces two-color-emissive aggregates through the formation of an intermolecular charge-transfer (CT) complex between the electron-rich anthracene and electron-deficient BODIPY moieties. Furthermore, to our surprise, the BODIPY and AP dyad aggregates generate singlet oxygen ( O ) and photocytotoxicity upon excitation, indicating that the BODIPY-anthracene CT state favors an intersystem crossing process. Based on X-ray crystallographic analysis, the lattice-like molecular packing between the BODIPY and AP moieties was determined to bring about the unprecedented aggregation-induced O generation (AISG).

We propose a new sensor design that maximizes fluorescence contrast, inspired by whispering-gallery mode lasing (WGM). Aptamer-modified glass microspheres (cf. 1-38 mm) and thrombin are used as a model sensory cavity and target protein, respectively. Two types of microsphere are prepared to compare fluorescence contrast: turn-on and turn-off types by using fluorophore-labeled target protein and fluorophore-labeled DNA duplex with thrombin-binding aptamer (TBA), respectively. For the turn-on type, a fluorescence increase was detected in the presence of 100 nM thrombin, but signal amplification upon excitation power did not occur. As for the turn-off type, in the absence of thrombin, fluorophores are densely populated around the microsphere, leading to fluorescence confinement and intensity amplification upon increasing the pump intensity. By adding thrombin, a complementary strand of TBA is dissociated from the microsphere, and the G-quadruplex structure of the thrombin aptamer recognizes and binds to thrombin. As the fluorophore density around the microsphere decreases, fluorescence amplification based on WGM resonance is halted, resulting in 29-fold enhanced contrast under increased excitation power.