An ultrasensitive electrochemical biosensor for bisphenol A based on aptamer-modified MrGO@AuNPs and ssDNA-functionalized AuNP@MBs synergistic amplification.

Bisphenol A (BPA) is a harmful endocrine disruptor, sensitive and rapid quantification of BPA is highly desirable. In this work, a novel synergistic signal-amplifying electrochemical biosensor was developed for BPA detection by using a recognition probe (RP) constructed by BPA aptamer modified gold nanoparticles-loaded magnetic reduced graphene oxide (Aptamer-MrGO@AuNPs), and a signal probe (SP) constructed by BPA aptamer-complementary single-stranded DNA (ssDNA) functionalized methylene blue (MB)-loaded gold nanoparticle (ssDNA-AuNP@MBs). The RP and SP can self-assemble to form a stable RP-SP complex through complementary base pairing. The current intensity of the biosensor correlates with the number of RP-SP complexes. In the presence of BPA, the BPA aptamer can capture BPA with high selectivity and affinity, form an RP-BPA complex and dissociate the RP-SP complex to release SP, resulting in a decrease in the current signal intensity of the biosensor. A single AuNP could be loaded with multiple BPA aptamers and MBs, which improves the recognition efficiency and enhances the signal intensity. Due to the magnetic properties of MrGO@AuNPs, the magnetic separation and adsorption of RP or RP-SP complex is very convenient, enabling all reaction processes to be carried out in solution, which not only improves the mass transfer efficiency, but also simplifies the operation. Under optimal conditions, the developed biosensor had a detection limit as low as 0.141 pg/mL and had been successfully applied to the detection of real environmental water samples. Therefore, the synergistic signal amplification strategy of RP and SP has potential value in the detection of trace pollutants in the water environment.