Dual recognition strategy for selective fluorescent detection of dopamine and antioxidants based on graphite carbon nitride in human blood serum.

In this work, a strong blue-emitting fluorescent biosensor based on graphite carbon nitride nanoparticles (GCNNs) (Ex = 340 nm and Em = 435 nm) was synthesized by a facile one-step hydrothermal method. With the aid of hydrogen peroxide and horseradish peroxidase, pyrocatechol structure of dopamine (DA) was oxidized to o-quinone structure of polydopamine (PDA) by hydroxyl radical. PDA was able to rapidly and significantly quench fluorescence of GCNNs. In the meanwhile, oxidative self-polymerization from DA to PDA would be blocked by antioxidants, such as glutathione (GSH) and ascorbic acid (AA). Thus, the fluorescence of GCNNs@DA sensor would be recovered owing to the decrease of o-quinone. Based on above-mentioned dual recognition strategy of "turn-off" and "turn off-on", a fast, simple and ultrasensitive method was developed to measure DA and antioxidants. Under the optimal experimental conditions, the detection limits of DA, GSH and AA were 0.064 μmol L-1, 0.11 μmol L-1 and 0.16 μmol L-1 with relative standard deviations of 1.7%, 9.3% and 8.0%, respectively. As one of metal-free quantum dots, our GCNNs-based sensors were also successfully applied to the determination of DA as well as GSH and AA in human serum. The recoveries for the spiked samples were in the range of 93.8%-109% and 95.0%-110% of DA and antioxidants, which shows great promise to clinicalapplication.