A novel ratiometric fluorescence probe based on calix[4]arene functionalized polymer dots for bisphenol A detection in real water samples.

Bisphenol A (BPA) is one of key raw materials used in the production of epoxy resins and plastics, which has toxicological effects on humans by disrupting cell functions through a variety of cell signaling pathways. Therefore, it is of great significance to develop a simple, rapid, and accurate BPA detection method in real water samples. In this study, a ratiometric fluorescence method based on yellow-emitting surface-functionalized polymer dots (PFBT@L Pdots) and blue-emitting carbon dots (Cdots) was described for the detection of BPA. Pdots as the detecting part were synthesized by using highly fluorescent hydrophobic Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-(2,1',3)-thiadiazole)] (PFBT) polymer and (R)-5,11,17,23-Tetra-tert-butyl-25,27-bis[(diphenylphosphinoyl)methoxy]-26-(3-oxabutyloxy)-28-[(1-phenylethyl)- carbamoylmethoxy]calix [4]arene (L) functionalizing ligand, and Cdots as internal reference were prepared by hydrothermal treatment of citric acid and urea. In the presence of BPA, chemical binding of the phosphorus atoms of nearby PFBT@L Pdots with BPA hydroxyl functional groups led to the aggregation of the PFBT@L Pdots aggregation and quenching their yellow emission, but the blue emission of Cdots, on the other hand, remained stable. The proposed PFBT@L Pdots probe was successfully applied for the detection of BPA in real water samples, and the results were in good agreement with those obtained by HPLC-FLD. To the best of our knowledge, this is the first report that the calixarene has been utilized to modify Pdots.