Dumbbell hybridization chain reaction coupled with positively charged Au@luminol nanoparticles for enhanced electrochemiluminescent sensing of exosomal miRNA-21

MicroRNAs (miRNAs) are important cancer biomarkers in cancer cell-derived exosomes. Herein, positively charged Au@luminol nanoparticles ((+)Au@luminol NPs) with enhanced electrochemiluminescence (ECL) and extreme stability were firstly established for the sensitive detection of miRNA-21 in exosome. In the presence of miRNA-21, dumbbell hybridization chain reaction (DHCR) happened at gold nanoparticles and ZIF-67 metal-organic framework modified glass carbon electrode (AuNP/ZIF-MOF/GCE) with the help of dumbbell DNA fuel strands (DHP1 and DHP2). The formed DHCR polymers were negatively charged and could electrostatically adsorb numbers of (+)Au@luminol NPs to produce strong ECL signal. Combing DHCR signal amplification with (+)Au@luminol NPs enhancer, sensitive detection of miRNA-21 realized with a detection limit of 0.43 fM. Moreover, the proposed method was successfully applied for the analysis of miRNA-21 in serum samples of healthy individuals and breast cancer patients, indicating a potential application value in early clinical diagnosis.