A molecularly imprinted chitosan doped with carbon quantum dots for fluorometric determination of perfluorooctane sulfonate.

Abstract

A molecularly imprinted polymer (MIP) was fabricated for selective recognition of the highly persistent pollutant perfluorooctane sulfonate (PFOS). The MIP was prepared from chitosan and doped with fluorescent carbon quantum dots (CQDs). It was characterized by fluorescence spectrophotometry, scanning electron microscopy, and Fourier transform infrared spectroscopy. The fluorescence of the CQDs, best measured at excitation/emission wavelengths of 350/460nm, is enhanced by PFOS, and the effect is much stronger for the MIP than for the nonimprinted polymer (NIP). The imprinting factor is 2.75. The method has good specificity over sodium dodecyl sulfate (SDS), perfluorooctanoic acid (PFOA), sodium dodecyl sulfonate (SDS'), sodium dodecyl benzene sulfonate (SDBS), perfluorooctanesulfonyl fluoride (POSF), perfluorobutane sulfonate (PFBS) and 1-octanesulfonic acid sodium (OSA). Fluorescence increases linearly in the 20-200pg·L-1 POSF concentration range in aqueous solution. The method was applied to the determination of PFOS in spiked serum and urine samples. The limits of detection are 66 and 85pg·L-1 for serum and urine samples respectively. The recoveries ranged from to 81-98%, with relative standard deviations in the range of 1.8-8.2%. Compared with LC-MS/MS, this assay is more convenient since the material can be prepared flexibly and the method can be applied on-site. Graphical abstract Schematic of the fabrication of a molecularly imprinted chitosan hydrogel doped with CQDs for selective fluorometric determination of PFOS. a. The photo of chitosan hydrogel. b, c, d, e represents the hydrogel observed under UV lamp. b', c', d', e' represents the inner structure of hydrogel bead.