A Binary Functional Substrate for Enrichment and Ultrasensitive SERS Spectroscopic Detection of Folic Acid Using Graphene Oxide/Ag Nanoparticle Hybrids

Herein graphene oxide/Ag nanoparticle hybrids (GO/PDDA/AgNPs) were fabricated according to a self-assembly procedure. Using the obtained GO/PDDA/AgNPs as SERS substrates, an ultrasensitive and label-free detection of folic acid in water and serum was demonstrated based on the inherent SERS spectra of folic acid. The modified graphene oxide exhibited strong enrichment of folic acid due to the electrostatic interaction, and the self-assembled Ag nanoparticles greatly enhanced the SERS spectra of folic acid, both of which led to an ultrahigh sensitivity. Therefore, although the SERS enhancement of p-ATP on GO/PDDA/AgNPs was weaker than that on Ag nanoparticles, the SERS signals of folic acid on GO/PDDA/AgNPs were much stronger than that on Ag nanoparticles. To improve the detection, the concentration of GO/PDDA/AgNPs was optimized to reduce background of the graphene oxide. The SERS spectra of the folic acid showed that the minimum detected concentration of folic acid in water was as low as 9 nM with a linear response range from 9 to 180 nM. To estimate the feasibility of the detection method based on GO/PDDA/AgNPs for the practical applications, diluted serum containing different concentrations of folic acid was taken as real samples. It was established that the sensitivity and the linear range for the folic acid in serum were comparable to that in water. This ultrasensitive and label-free SERS detection of folic acid based on GO/PDDA/AgNPs offers great potential for practical applications of medicine and biotechnology.