Hemin-Bridged MOF Interface with Double Amplification of G‑Quadruplex Payload and DNAzyme Catalysis: Ultrasensitive Lasting Chemiluminescence MicroRNA Imaging

Here, we report a double-amplified sensing platform for ultrasensitive chemiluminescence (CL) miRNA detection in real patients’ blood in which a hemin-bridged metal–organic framework (MOF) is employed as a functional interface to boost the payload and catalysis of G-quadruplex (G4) DNAzymes. Hemin is here used as the organic ligand for the MOF synthesis, which endows the MOF with an intrinsic peroxidase-like catalytic activity. Most importantly, the MOF surface provides a large amount of binding sites for polymeric G4 DNAzymes that are produced by miRNA-triggered rolling circle amplification reactions, and meanwhile, the interfaced G4 DNAzymes on MOFs (G4/MOFzymes) display an about 100-fold higher catalytic activity than those in solution. By using the G4/MOFzyme catalysts in the luminol/H₂O₂ CL system, the amplification detection of two acute myocardial infarction (AMI)-related miRNAs (low to 1 fM seen with naked eyes) is achieved in human serum with a smartphone as a portable imaging detector, which provides a facile methodology for point-of-care (POC) diagnosis of AMI. Compared with previous smartphone-based counterparts not requiring sophisticated equipment, this new facile methodology shows both 6 orders of magnitude higher sensitivity and an ∼50-fold longer duration for CL miRNA imaging. These unique features allow our developed G4/MOFzymes to be further employed as a novel luminescent ink for printing commonly used patterns.