Metal-Organic framework incorporated luminescent PTCA combined with novel co-reactant accelerator for ultra-sensitive electrochemiluminescence detection of CA19-9
Haiyang Li, Mingyue Shao, Jinglong Fang, Yuyang Li, Xiaojun Sun, Xiang Ren, Qin Wei, Huangxian Ju, Hongmin Ma
Abstract
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 (K 2 S 2 O 8 ) with the Prussian blue analogues (PBAs) as a template under the efficient synergistic effect of MoS 2 . Through the reversible transformation of the transition metal valence states, a sufficient amount of sulfate radicals (SO 4 •− ), 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 × 10 2 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.