Tunable Competitive Absorption-Induced Signal-On Photoelectrochemical Immunoassay for Cardiac Troponin I Based on Z-Scheme Metal–Organic Framework Heterojunctions

Recently emerged Z-scheme heterostructure-based immunoassays have presented new opportunities for photoelectrochemical (PEC) biosensing development. Here, we described a tunable signal-on PEC biosensor for the detection of cardiac troponin I (cTnI), which exploited a competitive absorption effect between Cu(II) ions and a Zr metal-organic framework (Zr-MOF) constructed on TiO₂ nanorods (Cu²⁺@Zr-MOF@TiO₂ NRs). Water-stable Zr-MOF was coated onto TiO₂ NRs on fluorine-doped tin oxide to form a Z-scheme heterostructure substrate (Zr-MOF@TiO₂ NRs), which exhibited a high photoelectric response. Cu²⁺@Zr-MOF@TiO₂ NRs, constructed by loading Cu(II) ions onto the architecture of Zr-MOF by electrostatic interaction, demonstrated a low background signal. After sandwich immunorecognition within a 96-well plate, H₂S, generated by confined alkaline phosphatase on zeolitic imidazolate framework-8, was directed to react with Cu(II) ions to form CuS. This resulted in an in situ change in the photoelectrode and an enhanced photoelectric signal. The developed PEC biosensing platform exhibited high sensitivity and selectivity for the cTnI immunoassay with a detection limit of 8.6 pg/mL. The Z-scheme-based competition absorption modulation of photoelectrochemistry provides a new strategy for general PEC biosensing development.