Jiahui Lin, Zhongping Mao, Fei Yan
Developing an ultrasensitive electrochemiluminescence (ECL) detection platform remains challenging due to the limited enrichment efficiency of ECL emitters and co-reactants at the electrode interface, as well as the insufficient catalytic enhancement of co-reactant conversion. Moreover, simultaneous in situ analyte enrichment and efficient anti-interference capability are often difficult to achieve in a single sensing interface. Herein, a new ECL platform was developed based on nanocatalyst-supported nanochannel-confined surfactant micelle (SM) system, which integrates an enhanced luminol-dissolved oxygen (DO) ECL response for the ultrasensitive detection of antibiotic rifampicin (RIF). A nanocomposite comprising nitrogen-doped graphene quantum dots and a molybdenum disulfide nanosheet (NGQDs@MoS2) was modified on an indium tin oxide (ITO) electrode. This nanocomposite layer catalyzed the oxygen reduction reaction (ORR), boosting the co-reactant efficiency of DO. Vertically ordered mesoporous silica film filled with surfactant micelles (SM@VMSF) was subsequently grown in situ on the NGQDs@MoS2 surface. The hydrophobic micelles enable the simultaneous enrichment of luminol, DO, and RIF. Integrating the triple-enrichment effect of surfactant micelles with the high electrocatalytic effect of NGQDs@MoS2 nanocomposite results in significant ECL enhancement of the luminol–DO. SM@VMSF also provides an excellent molecular sieving effect, endowing the sensor with high anti-interference capability and stability. RIF quenches the ECL signal by consuming superoxide anion radicals, enabling sensitive detection. Detection of RIF was established with a high sensitivity (2927 a.u. per nM) wide linear range (10 pM to 10 μM) and a low limit of detection (LOD, 2.5 pM). The fabricated sensor exhibits good selectivity and high fabrication reproducibility (relative standard deviation, RSD, of 1.9%). Additionally, the determination of RIF in eye drops and seawater samples was realized. This work offers new insights for the design of high-performance ECL sensing interfaces and sensitive detection of RIF.