Enzymatic deposition of gold nanoparticles at vertically aligned carbon nanotubes for electrochemical stripping analysis and ultrasensitive immunosensing of carcinoembryonic antigen

Herein we combine the sandwich immunoreaction at a vertically aligned single-walled carbon nanotube (SWCNT)-based immunosensor and the enzymatically catalytic deposition of gold nanoparticles (Au NPs) by a gold nanoprobe to develop a novel electrochemical immunosensing method. The vertically arranged nanostructure was prepared through the covalent linking of terminally carboxylated SWCNTs at an aryldiazonium-modified electrode. It not only provides an excellent platform for the high density immobilization of antibodies to obtain the immunosensor but also serves as useful molecular wires to accelerate electron transfer during the electrochemical immunosensing process. Meanwhile, the enzymatic reaction of the nanoprobe prepared by surface functionalization of the nanocarrier of Au NPs by high-content glucoamylases can catalyze the deposition of a large number of Au NPs at the immunosensor. The electrochemical stripping analysis of these nanoparticles enabled the convenient signal transduction of the method. Due to the sensitive gold stripping analysis at the vertically aligned SWCNTs and the multi-enzyme signal amplification of the nanoprobe, the electrochemical signal response was greatly enhanced. Thus, the method can be used for the ultrasensitive detection of the tumor biomarker of carcinoembryonic antigen in a wide linear range of 5 orders of magnitude with a low detection limit of 0.48 pg mL. Considering its obvious performance superiorities, this immunosensing method exhibits an extensive prospect for practical applications.