Dual-Mode Sensing Platform for Cancer Antigen 15-3 Determination Based on a Silica Nanochannel Array Using Electrochemiluminescence and Electrochemistry

An electrochemiluminescence-electrochemistry (ECL-EC) dual-mode sensing platform based on a vertically-ordered mesoporous silica films (VMSF) modified electrode was designed here for the sensitive and selective determination of cancer antigen 15-3 (CA 15-3), a specific biomarker of breast cancer. VMSF was assembled through a rapid electrochemically assisted self-assembly (EASA) method and plays a crucial role in signal amplification via a strong electrostatic interaction with the positively charged bifunctional probe Ru(bpy)32+. To construct the biorecognition interface, epoxy functional silane was linked to the surface of VMSF for further covalent immobilization of the antibody. As a benefit from the specific combination of antigen and antibody, a non-conductive immunocomplex layer was formed in the presence of CA 15-3, leading to the hinderance of the mass and electron transfer of the probes. Based on this strategy, the dual-mode determination of CA 15-3 ranging from 0.1 mU/mL to 100 mU/mL with a LOD of 9 μU/mL for ECL mode, and 10 mU/mL to 200 U/mL with a LOD of 5.4 mU/mL for EC mode, was achieved. The proposed immunosensor was successfully employed for the detection of CA 15-3 in human serum without tedious pretreatment.