Glycosaminoglycan-Induced Emissive J-Aggregate Formation in a meso-Ester BODIPY Dye

Abstract

The analyte-directed formation of emissive J-aggregates of a meso-ester BODIPY dye is explored in the design of fluorescence "light-up" probes. The heparin-specific pyridinium-functionalized meso-ester BODIPY dye C10-Py+ self-assembles in aqueous buffer into spherical aggregated nanostructures with spectroscopic features indistinguishable from the monomeric dye (signal off). In the presence of heparin, the aggregated assemblies rearrange and associate with heparin through charge-pairing interactions, triggering the spontaneous formation of emissive J-type aggregates (signal on). The heparin-induced J-aggregate formation of C10-Py+ provides an excellent "turn-on" signal with large spectral shifts. The response is highly selective for heparin over other closely related glycosaminoglycan (GAG) analogues, sensitive, fast, and operationally simple. Assays for heparin in human serum, and for the adulterant OSCS in heparin are demonstrated, confirming the reliability and robustness of the J-aggregation approach using meso-ester BODIPY dyes in the design of aggregation-induced emission (AIE)-based fluorogenic probes.