Embedded Au Nanoparticles-Based Ratiometric Electrochemical Sensing Strategy for Sensitive and Reliable Detection of Copper Ions.

The ratiometric method allows the measurement of ratio changes between two signals, which can reduce the detection signal fluctuations caused by distinct background conditions and greatly improve the reproducibility and reliability of detection. However, in contrast with the emerging dual excitation or dual emission dyes applied in ratiometric luminescence measurement, only a few internal reference probes have been exploited for ratiometric electrochemical detection. In this paper, a gold nanoparticles@carbonized resin nanospheres composite with thermally reduced graphene oxide as scaffold (AuNPs@CRS-TrGNO) has been fabricated, and the AuNPs embedded in the CRS were first used as an internal reference probe for ratiometric electrochemical detection. The detachment and aggregation of AuNPs is suppressed by embedding in the CRS, so its redox signal is very stable, which provides feasibility for ratiometric detection. Moreover, the embedment of AuNPs, carbonization of resin spheres, and hybridization with TrGNO all have played positive roles in improving the charge transfer rate, which leads to excellent electrochemical performance of the composite. Based on these characteristics of the AuNPs@CRS-TrGNO, a new ratiometric electrochemical detection platform was constructed, and copper ions (Cu2+) in simulated seawater were successfully detected. This ratiometric method has the advantages of simple design and convenient operation, and obviously it improves the reproducibility and reliability of the electrochemical sensor.