Combining quasi-ZIF-67 hybrid nanozyme and G-quadruplex/hemin DNAzyme for highly sensitive electrochemical sensing

Zeolitic imidazolate frameworks (ZIFs), a famous subfamily of metal-organic frameworks (MOFs), are considered promising electrocatalysts. Herein, ZIF-67 was selected as an electrocatalyst for designing electrochemical sensors due to having the best electrocatalytic activity in ZIFs. To overcome the insufficient electrocatalytic activity of ZIFs, ZIF-67 derivatives (QZIF-67-X, where X represents calcination time) were obtained by calcining at 250 °C for a certain time. The porous structure of the precursor in QZIF-67-X is maintained, exposing more active centers. QZIF-67-X could accelerate electron transfer and lead to improve the electrocatalytic performance. Moreover, QZIF-67-2 was chosen as an Au nanoparticle-supported nanocarrier to further bind G-quadruplex/hemin DNAzymes with strong catalytic activity due to the best supporting activity of QZIF-67-2 among QZIF-67-X. The synergistic catalysis of QZIF-67-2 and G-quadruplex/hemin DNAzymes effectively amplified the reduction current signal of H2O2. The linear range of the prepared electrochemical sensor was 2 μM-65 mM, and the detection limit was 1.2 μM. Moreover, the real-time detection of H2O2 from HepG2 cells was achieved by the sensor, providing a novel technique for efficient anticancer drug evaluation. These results suggested that QZIF-67 can be utilized as an efficient electrocatalyst for improving the sensitivity of sensors.