The purpose of this study was to explore the feasibility and mechanism of synthesizing silver nanoclusters (AgNCs) using a double-stranded DNA (dsDNA) template and to use the AgNCs as probes for captopril detection. The results showed that the binding of silver ions towards DNA bases deduced the destruction of the initial dsDNA structure, and AgNCs with decent quantum yield (43.54%) were obtained. The detection using these AgNCs probes showed good performance for captopril, with a linear range of 0.1–0.8 μg·mL−1 and a detection limit of 0.045 μg·mL−1. Recovery results in real samples of Apocynum venetum leaf tea and Ginkgo biloba leaf tablet demonstrated its good applicability. This work not only extended the understanding of DNA-AgNCs but also provided a fast and cost-effective tool for captopril detection.
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