Fluorescence sensor array based on pore-size sieving effect of Zr-MOFs for monitoring ATP hydrolysis and ATP-related physiological phosphates

Abstract

Monitoring the hydrolysis of adenosine triphosphate (ATP) and differentiating its associated phosphates are critical but challenging. Herein, we presented a high-throughput fluorescence sensor array based on three zirconium metal–organic frameworks (Zr-MOFs), namely PCN-221, PCN-222, and PCN-224, with different topological structures and pore sizes for the accurate recognition of ATP-related phosphates. Initially, these Zr-MOFs exhibit weak fluorescence due to ligand-to-metal charge transfer (LMCT) phenomenon. Interestingly, interaction between Zr clusters and phosphates enhance the fluorescence of Zr-MOFs, because the formation of robust Zr-O-P bonds effectively disrupt the LMCT process. Notably, benefiting from the pore-size screening effects of three Zr-MOFs, meanwhile, ATP-related phosphates with different phosphate group numbers, molecular sizes, and steric effects could alter the LMCT of each Zr-MOF to varying degrees, leading to the diverse fluorescence responses. Consequently, this multi-dimensional sensor array generates unique fluorescence “fingerprints” for precise identification of ATP-related phosphates rely on the modulating MOF-phosphate interactions, along with real-time ATP hydrolysis monitoring. Moreover, the proposed array achieved superior sensitivity and anti-interference capabilities, even for multi-component phosphate detection in complex biological environments. This study not only provides a versatile tool for investigating ATP hydrolysis, but also opens new avenues for MOF-based multimolecular detection in biological sensing applications.