Potential-Resolved Electrochemiluminescence via Interfacial Electronic Engineering in Au25@FeMOP Heterostructures for...

Area of Science:

• Nanomaterials Science
• Analytical Chemistry
• Biomedical Engineering

Background:

• Precise control of reactive oxygen species (ROS) is crucial for advanced electrochemiluminescence (ECL) sensing.
• Detecting ROS in complex biofluids like urine presents significant challenges for current sensing technologies.

Purpose of the Study:

• To develop a hierarchical hollow nanocomposite (Au25@FeMOP) for precise ROS modulation in ECL sensing.
• To investigate the interfacial mechanisms governing electron transfer and catalytic activity.
• To establish an intelligent sensing platform for discriminating urinary metabolites.

Main Methods:

• Synthesis of a hierarchical hollow nanocomposite (Au25@FeMOP) encapsulating Au25(Cys)18 nanoclusters within an Fe-porphyrin-based microporous organic polymer.
• Spectroscopic analysis and density functional theory (DFT) calculations to elucidate interfacial electronic coupling.
• Electrochemical and ECL measurements to demonstrate potential-resolved catalytic behavior and metabolite discrimination.

Main Results:

• A robust Au-Cys-Fe interfacial bridge was identified, facilitating directional electron transfer and optimizing Fe center properties.
• The Au25@FeMOP architecture exhibited potential-resolved ECL, selectively catalyzing superoxide radical (O2•−) at cathodic potentials and hydroxyl radical (•OH) at anodic potentials.
• An intelligent sensing platform was constructed, generating distinct ECL "fingerprints" for precise discrimination of urinary metabolites in simulated urine.

Conclusions:

• The study elucidates the atomic-level synergistic mechanism of bimetallic ECL catalysts.
• The developed nanocomposite offers a new pathway for precise ROS modulation in ECL sensing.
• This work establishes a foundation for noninvasive health monitoring through advanced biosensing.