Sensitive detection and intracellular imaging of free copper ions based on DNA-templated silver nanoclusters...

Free copper ions (Cu⁺ and Cu²⁺) have critical toxicity to cells, although copper is an essential element for human body. Hence, sensitive monitoring is crucial to avoid over intake of Cu⁺/Cu²⁺. We herein designed a ssDNA sequence (A₃₁) for synthetizing A₃₁-templated silver nanoclusters (AgNCs), and demonstrated that Cu⁺/Cu²⁺ can induce the aggregation of A₃₁-templated AgNCs and thus greatly enhanced the fluorescence emission of A₃₁-templated AgNCs. Based on Cu⁺/Cu²⁺-induced fluorescence enhancement effect of A₃₁-templated AgNCs, a label-free and signal-on fluorescent sensing platform was developed for the specific and sensitive detection of Cu⁺/Cu²⁺ in biological samples and intracellular imaging of Cu⁺/Cu²⁺ in cells. The signal-on fluorescent sensing platform could be used to rapidly detect Cu⁺ and Cu²⁺ with a detection limit of 0.1 µM within 30 min., and to perform the intracellular imaging of Cu⁺ and Cu²⁺ in cells with good cell permeability and biocompatibility. By using the signal-on fluorescent sensing platform, we have successfully detected Cu⁺ and Cu²⁺ in cells fluids and human serum with a recovery of 90-104% and a RSD (n = 5) < 5%, and performed the imaging of Cu⁺/Cu²⁺ in Hela cells. The developed fluorescent sensing platform has obvious analytical and imaging advantages such as signal-on, simple operation, short analysis time, both Cu⁺ and Cu²⁺ detection, similar or higher sensitivity, good cell permeability and biocompatibility, which promising a reliable approach for the rapid and on-site detection or imaging of free copper ions in biological samples in clinical diagnosis.