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PEGylation Improved Electrochemiluminescence Supramolecular Assembly of Iridium(III) Complexes in Apoferritin for Immunoassays Using 2D/2D MXene/TiO2 Hybrids as Signal Amplifiers

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journal contribution
posted on 07.12.2021, 07:05 by Lei Yang, Tingting Wu, Yu Du, Nuo Zhang, Ruiqing Feng, Hongmin Ma, Qin Wei
Dynamic self-assembly of iridium complexes in water-soluble nanocontainers is an important bottom-up process for fabricating electrochemiluminescence (ECL) bioprobes. PEGylated apoferritin (PEG-apoHSF) as the host offers a confined space to alter and modify the self-assembly of trans-bis­(2-phenylpyridine)­(acetylacetonate)­iridium­(III) [Ir­(ppy)2(acac)] based on a pH-dependent depolymerization/reassembly pathway, allowing the formation of ECL-active iridium cores in PEG-apoHSF cavities (Ir@PEG-apoHSF). With an improved encapsulation ratio in PEG-apoHSF, the coreactant ECL behavior of the fabricated Ir@PEG-apoHSF nanodots with tri-n-propylamine (TPrA) was further demonstrated, exhibiting maximum ECL emission at 530 nm that was theoretically dominated by the band gap transition. The application of Ir@PEG-apoHSF as a bioprobe in a “signal-on” ECL immunosensing system was developed based on electroactive Ti3C2Tx MXenes/TiO2 nanosheet (Ti3C2Tx/TiO2) hybrids. Combining with the efficiently catalyzed electro-oxidation of TPrA and Ir­(ppy)2(acac) by Ti3C2Tx/TiO2 hybrids, the developed immunosensor showed dramatically amplified ECL responses toward the target analyte of neuron-specific enolase (NSE). Under experimental conditions, linear quantification of NSE from 100 fg/mL to 50 ng/mL was well established by this assay, achieving a limit of detection (LOD) of 35 fg/mL. The results showcased the capability of PEGylated apoHSF to host and stabilize water-insoluble iridium complexes as ECL emitters for aqueous biosensing and immunoassays.