Metal-Organic framework incorporated luminescent PTCA combined with novel co-reactant accelerator for ultra-sensitive electrochemiluminescence detection of CA19-9

Polycyclic aromatic hydrocarbons (PAHs) are commonly used as electrochemiluminescence (ECL) luminophores. However, PAHs are limited by the aggregation-caused quenching (ACQ) effect, which reduces ECL emission. Therefore, developing an ECL system from PAHs with efficient luminescence is a significant challenge. In this work, a two-ligand strategy was proposed to assemble 3, 4, 9, 10-perylenetetracarboxylic acid (PTCA) into zeolitic imidazole framework-8 (ZIF-8). The ACQ effect of PTCA was inhibited by participating in the formation of metal–organic frameworks (MOFs) and a luminescent ZIF-8-PTC (Z8P) composite was obtained. Satisfactorily, conceptual experiments demonstrated that the significantly higher ECL efficiency of Z8P was achieved compared with PTCA monomers and aggregates. On the sensing substrate, a novel co-reactant accelerator (Au@MFNC) was used to achieve continuous catalysis of the persulfate (K2S2O8) with the Prussian blue analogues (PBAs) as a template under the efficient synergistic effect of MoS2. Through the reversible transformation of the transition metal valence states, a sufficient amount of sulfate radicals (SO4•−), again amplifying the ECL signal of Pd@Z8P. Under ideal conditions, the constructed dual-MOFs ECL immunosensor had a wide response range (1 × 10−4–1 × 102 U/mL) and a low limit of detection (LOD) (6 × 10−5 U/mL), which provided an alternative method for CA19-9 ultrasensitive detection, and broadened a new idea for the development of high-performance luminescent MOFs.