Porphyrin based hydrogen bond organic frameworks as enhanced ECL luminophore for the ultrasensitive detection of breast cancer 1 gene.

The demand for high-performance electrochemiluminescence (ECL) emitters in aqueous media continues to grow due to requirements for ultrasensitive biomedical detection. In this work, we report the synthesis of Zn (II) meso-tetra(4-carboxyphenyl) porphine (ZnTCPP) integrated with 4,4',4″-tricarboxytriphenylamine (TBA) for forming porphyrin-based hydrogen bond organic frameworks (ZnP-HOFs). The ZnP-HOFs showed strong ECL emission using K2S2O8 as coreactant, achieving a 5.85-fold amplification in ECL efficiency alternative to the ZnTCPP monomer. The enhanced mechanism was carefully discussed through electron paramagnetic resonance (EPR) and ultraviolet photoelectron spectroscopy (UPS) studies. With this advanced ECL luminophore, a "signal off-on" ECL biosensor was constructed for determining breast cancer 1 gene (BRCA1) by signal recovery after removing a black hole quencher (BHQ) linked DNA, showing a wide linear range from 1.0 pM to 0.1 μM, an ultralow limit of detection (LOD) down to 0.44 pM, and even the excellent recovery in serum sample. Thus, this work highlights the potential of HOFs-based materials in bioanalysis and establishes a universal, robust strategy for ECL biosensing applications.