Adsorption Promoted Aggregation-Induced Emission Showing Strong Dye Lateral Interactions

Aggregation-induced emission (AIE) is a powerful method to produce fluorescence for a diverse range of applications. While most previous work induced aggregation by change of solvent, ionic strength, pH, or self-assembly, we herein explored adsorption-induced aggregation using 4,4'-(hydrazine-1,2-diylidene bis(methanylylidene)) bis(3-hydroxybenzoic acid) (HDBB) as an AIE luminogen. HDBB is known to aggregate with AIE at low pH but not at neutral pH, and its aggregation facilitates excited state intramolecular proton transfer for enhanced emission. Using a nonquenching nanomaterial, Y₂O₃ nanoparticles, HDBB showed sevenfold fluorescence increase at pH 7.0. Fluorescence lifetime showed that HDBB was in the aggregated state in the presence of Y₂O₃. For comparison, a fluorescent porphyrin compound showed that adsorption caused quenching after mixing with Y₂O₃, whereas other dyes such as fluorescein, calcein, and rhodamine B failed to be adsorbed by Y₂O₃. Adsorption did not follow a Langmuir isotherm, but it showed strong lateral HDBB interactions because adsorption was only achieved with a high concentration of HDBB. Adsorption was inhibited by salt and by phosphate, indicating the importance of electrostatic and metal-binding interactions. Comparisons were made with other nanomaterials, where graphene oxide and CeO₂ quenched HDBB and a cationic liposome also enhanced its emission, although with a less red-shifted peak wavelength. This study provides a simple method to induce aggregation of an AIE dye and its aggregation in turn-enhanced adsorption.