Ultrasensitive photoelectrochemical microcystin-LR immunosensor using carboxyl-functionalized graphene oxide enhanced gold nanoclusters for signal amplification

An ultrasensitive photoelectrochemical (PEC) immunosensor based on gold nanoclusters (AuNCs) with 11-mercaptoundecanoic acid (MUA) ligands was fabricated for determination of microcystin-LR (MC-LR). The PEC immunosensor was developed by loading the monoclonal MC-LR antibody (Ab) to the MUA-AuNCs modified gold electrodes. After different measurement conditions being optimized, silver nanoparticles (AgNPs), gold nanorods (AuNRs), graphene oxide (GO) and carboxyl-functionalized graphene oxide (cGO) were introduced into MUA-AuNCs to enhance the sensing properties. The experimental result revealed that the sensitivity of PEC immunosensors was enhanced by both their photoelectrochemical properties and antibody loading properties with dependent relationship, which was different from the enhancement strategy of PEC sensors based on redox reactions. Among different hybrid nanocomposites, MUA-AuNCs/cGO not only improved the photoelectrochemical properties, but also loaded more antibodies for sensing, which resulted in best sensing performance. Thus, a universal method was proposed to enhance the sensing performance of PEC immunosensors based on impedance changes. Finally, MUA-AuNCs/cGO based PEC immunosensors exhibited a wide linear range of 0.001 nM-1000 nM with low detection limit of 0.011 pM (S/N = 3) for MC-LR determination. Meanwhile, the designed PEC immunosensors showed high selectivity, reproducibility and specificity, which provided the promising applications in aquatic environment.