Silver nanoparticles in electrochemical immunosensing and the emergence of silver-gold galvanic exchange detection

Nanoparticle-based electrochemical immunosensors demonstrate high sensitivity toward biomarker detection due to the large surface area of the nanoparticles and their ability to amplify the signal of the target molecule. Additionally, they have a fast response time, relatively lower cost, and can be easily miniaturized for point-of-care applications. Among noble metals, silver nanoparticles (AgNPs) have been extensively used in electrochemical sensors due to their unique properties, such as catalytic activity and excellent electrical conductivity. This Feature Article describes six approaches for incorporating AgNPs in electrochemical platforms, featuring the most recent developments in the silver-gold galvanic exchange-based detection strategy. With a few exceptions, many of these detection methods use AgNP oxidation into Ag⁺ ions, followed by electrodeposition of Ag⁺ ions onto the working electrode as zero-valent Ag metal and a final stripping step using a voltammetric technique. Combining these steps provides desirable low detection limits and good sensitivity for various biomarkers. A few other methods involved the reduction of Ag⁺ ions and depositing them as Ag metal onto the electrode using a reagent mixture so that the striping analysis could be performed. Typically, this reagent mixture includes Ag⁺ ions, a reducing agent, or an enzyme substrate. Besides, AgNPs have also been directly used to modify the surface of electrodes to facilitate kinetically favored redox-mediated electrochemical reactions. In addition to Ag detection methods, this report will also provide recent examples to illustrate how the size and shape of AgNPs impact the detection limits and sensitivity of an electrochemical assay. Finally, we discuss recent developments in lab-on-a-chip type immunosensors designed explicitly for Ag-based metalloimmunoassay detection, and we envision that this article will provide a comprehensive summary of the operational principles and new insights into such immunoassay systems.