Surfen-Assembled Graphene Oxide for Fluorescence Turn-On Detection of Sulfated Glycosaminoglycans in Biological Matrix.

Abstract

Sulfated glycosaminoglycans (GAGs) not only serve as a biomarker for mucopolysaccharidoses disease but also participate in various biological processes, such as blood clot medication (heparin) and signal transduction (heparan sulfate). However, few fluorescent sensors, such as 1,9-dimethylmethylene blue, have been developed for the detection of sulfated GAGs in the real world. Herein, we fabricated a surfen/few-layer graphene oxide (FLGO) nanocomplex for sensing sulfated GAGs in biological fluids. Surfen molecules are self-assembled onto the surface of FLGO through electrostatic attraction, and their fluorescence was then quenched by the creation of the FLGO-surfen complex (static quenching) and partially combined with the energy transfer from surfen to FLGO (dynamic quenching). The presence of sulfated GAGs resulted in the fluorescence recovery through the formation of the surfen-GAGs complex, which exhibits weak binding to FLGO and keeps surfen molecules away from the FLGO surface. Because FLGO efficiently reduced the fluorescence background from surfen and competed with sulfated GAGs for binding to surfen, surfen-assembled FLGO exhibited higher sensitivity and better selectivity for sulfated GAGs than surfen. The strategy mentioned above was exemplified by the analysis of heparin in human plasma and sulfated GAGs in an artificial cerebrospinal fluid; the limits of detection at a signal-to-noise ratio of 3 for heparin, dermatan sulfate, and heparin sulfate were determined to be 30, 30, and 60 ng/mL, respectively.