Enhancing the Electrochemiluminescence of Porphyrin via Crystalline Networks of Metal–Organic Frameworks for Sensitive Detection of Cardiac Troponin I

Abstract

Porphyrins easily aggregate due to unfavorable π-π accumulation, causing luminescent quenching in the aqueous phase and subsequently reducing luminescent efficiency. It is a feasible way to immobilize porphyrin molecules through metal–organic framework materials (MOFs). In this study, 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) was introduced into the metal–organic skeleton (PCN-224) as a ligand. The result showed that the electrochemiluminescence (ECL) and photoluminescence (PL) efficiency of the MOF skeleton was 8.2 and 6.5 times higher than TCPP, respectively. Impressively, the periodic distribution of porphyrin molecules in the MOF framework can overcome the bottleneck of porphyrin aggregation, resulting in the organic ligand TCPP participating in the electron transfer reaction. Herein, based on the PCN-224, a sandwich-type ECL immunosensor was constructed for the determination of cardiac troponin I (cTnI). It provided sensitive detection of cTnI in the range of 1 fg/mL to 10 ng/mL with a detection limit of 0.34 fg/mL. This work not only innovatively exploited a disaggregation ECL (DIECL) strategy via the crystalline framework of MOF to enhance the PL and ECL efficiency of porphyrin but also provided a promising ECL platform for the ultrasensitive monitoring of cTnI.

Silver Nanoparticles In Situ Enhanced Electrochemiluminescence of the Porphyrin Organic Matrix for Highly Sensitive and Rapid Monitoring of Tetracycline Residues

“…14 Lu et al reported a sandwich-type ECL immunosensor based on Zr 6 -5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin framework (PCN-224) for the determination of cardiac troponin I. 15 Li's team proposed a new zirconium metal−organic framework (Zr-DPA@TCPP) as a single luminophore, which showed synchronous anodic and cathodic ECL signals. 16 Chen et al exploited a cage-like porous complex as the microreactor to attenuate the aggregation-caused quenching effect of mesotetra(4-carboxyphenyl) porphine.…”

“…Since Bard’s group first reported the ECL properties of porphyrins, the development and investigation of porphyrins as ECL emitters are now in the ascendant . Lu et al reported a sandwich-type ECL immunosensor based on Zr 6 -5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin framework (PCN-224) for the determination of cardiac troponin I . Li’s team proposed a new zirconium metal–organic framework (Zr-DPA@TCPP) as a single luminophore, which showed synchronous anodic and cathodic ECL signals .…”

Coreactant-Free Zirconium Metal–Organic Framework with Dual Emission for Ratiometric Electrochemiluminescence Detection of HIV DNA

“…Metal–organic framework (MOF) is a kind of crystalline material with a periodic framework structure consisting of organic ligands as bridges and central metal ions or clusters as nodes. , With a designable structure and function of the MOF material, the prepared MOF can be obtained with desired and excellent performance. , Thus, MOF as a ECL luminophore has broad application space − and has enormous potential for fabricating the coreactant-free ratiometric biosensor. It is gratifying that some MOF luminophores have been developed, which achieved coreactant-free or dual-emission ECL.…”